Copolymerization of 2‐isothiocyanatoethyl methacrylate and 2‐hydroxyethyl methacrylate or methacrylic acid based on a nucleophile‐tolerant property of the isothiocyanato group

Radical copolymerizations of 2‐isothiocyanatoethyl methacrylate (ITEMA) and 2‐hydroxyethyl methacrylate (HEMA) or methacrylic acid (MAA) were examined, and fundamental properties of the obtained copolymers were investigated. The copolymerizations of various ITEMA/HEMA or ITEMA/MAA compositions proceeded effectively in THF or DMF by using 2,2′‐azobisbutyronitrile (AIBN) as an initiator, keeping the isothiocyanato groups and hydroxyl or carboxyl groups unchanged. Glass transition temperatures (T_g)s of poly(ITEMA‐co‐HEMA)s ranged from 68 to 100 °C, and they were thermally stable up to 200 °C. Meanwhile, T_gs of poly(ITEMA‐co‐MAA)s (ITEMA/MAA = 91/9, 76/24) were determined to be 91 and 109 °C, respectively. However, poly(ITEMA‐co‐MAA)s were thermally unstable, and significant weight loss was observed around 180 °C, which may be due to an addition of carboxyl groups to isothiocyanato groups followed by an elimination of COS to form amide structure in the copolymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5221–5229     

Preparation of P(MBA‐co‐MAA)/Zr(OH)4/P(EGDMA‐co‐MAA)/TiO2 Tetra‐layer Hybrid Microspheres and the Corresponding ZrO2/TiO2 Double‐shelled Hollow Microspheres

Double‐shelled zirconia/titania (ZrO₂/TiO₂) hollow microspheres were prepared by the selective removal of the polymer components via the calcination of the corresponding tetra‐layer poly(N,N′‐methylenebisacryl amide‐co‐methacrylic acid) (P(MBA‐co‐MAA))/Zr(OH)₄/poly(ethyleneglycol dimethacrylate‐co‐methacrylic acid) (P(EGDMA‐co‐MAA))/TiO₂ hybrid microspheres. These tetra‐layer microspheres were synthesized by the combination of the distillation copolymerization of N,N(‐methylenebisacryl amide‐co‐methacrylic acid (MBA) or ethyleneglycol dimethacrylate (EGDMA) crosslinker and methacrylic acid (MAA) for the preparation of polymer core and third‐layer as well as the controlled sol‐gel hydrolysis of inorganic precursors for the construction of zirconium hydroxide (Zr(OH)₄) and titania (TiO₂) layers. The thicknesses of zirconia and titania shell‐layers were conveniently controlled via varying the feed of zirconium n‐butoxide (Zr(OBu)₄) and titanium tetrabutoxide (TBOT) during the sol‐gel hydrolysis, while the sizes of polymer layers were tuned through a multi‐stage distillation precipitation copolymerization. The structure and morphology of the resultant microspheres were characterized by transmission electron microscopy (TEM), X‐ray diffractometer (XRD), X‐ray photoelectronic spectroscopy (XPS), and thermogrametric analysis (TGA).     

Glycopolymeric inhibitors of β‐glucuronidase. III. Configurational effects of hydroxy groups in pendant glyco‐units in polymers upon inhibition of β‐glucuronidase

Two kinds of new glycopolymers, (P(VB‐1‐GlcaH‐co‐AAm), 9 ) and (P(VB‐1‐Glco‐co‐AAm), 10 ), were synthesized through the radical copolymerization of styrene derivatives bearing pendant D ‐glucaric and D ‐gluconic moieties, N‐(p‐vinylbenzyl)‐1‐D ‐glucaramide (VB‐1‐GlcaH, 7 ), and N‐(p‐vinylbenzyl)‐D ‐gluconamide (VB‐1‐Glco, 8 ), with acrylamide (AAm). Glycopolymer 9 bearing the pendant glucaric moiety at the first position inhibited the hydrolysis of a model compound for xenobiotics‐β‐glucuronide conjugates, p‐nitrophenyl β‐D ‐glucuronide, uncompetitively, in contrast to the competitive inhibition in the presence of the corresponding isomeric glycopolymer bearing the pendant D ‐glucaric unit at the sixth position (P(VB‐6‐GlcaH‐co‐AAm), 3 ) reported in our previous article. On the other hand, another copolymer 10 bearing the gluconic moiety was found not to inhibit the hydrolysis as well as the corresponding copolymer bearing pendant gulonic unit (P(VB‐6‐Glco‐co‐AAm), 4 ). These results indicate that the hydrolysis is influenced not only by existence of pendant carboxyl units but also by the direction on the linkage of the glyco‐units to the polymer frame. Therefore the configurational position of hydroxy groups in pendant glyco‐units in macromolecular inhibitors may be essential for the interaction with β‐glucuronidase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4895–4903, 2006     

A new type of eco‐friendly resist based on nonchemically amplified system

Novel water‐processable photopolymers were designed to be useful as environment‐friendly photolithographic materials. By copolymerization of 2‐(2‐diazo‐3‐oxo‐butyryloxy)ethyl methacrylate (DOBEMA), hydroxyethyl methacrylate (HEMA), methacryllic acid (MAA), and sodium 4‐vinylbenzenesulfonate (SVBS), two kinds of polymers, poly(DOBEMA‐co‐HEMA‐co‐SVBS) for negative‐tone resist and poly(DOBEMA‐co‐MAA) for positive‐tone resist, were synthesized and their photolithographic properties were investigated. The single component negative‐tone resist produced 0.8 μm line and space patterns using a mercury‐xenon lamp in a contact printing mode using pure water as casting and developing solvent at a exposure dose of 25 mJ cm^?2. On the other hand, the single component positive‐tone resist produced 0.8 μm line and space patterns at a much higher dose of 150 mJ cm^?2. Thus, the negative resist showed much improved sensitivity when compared with the positive resist and the reported nonchemically amplified resists. This sensitivity is comparable with those of typical chemically amplified resists. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7534–7542, 2008     

Preparation of high oxygen permeable transparent hybrid copolymers with silicone macro-monomers

In this study, high oxygen permeable transparent hybrid copolymers were prepared with hydrophilic monomer such as 2-hydroxyethylmethacrylate (HEMA) or N,N-dimethylacrylamide (DMAA) and mono- or difunctional silicone macro-monomer introduced methacryl groups. In HEMA-based hybrid copolymers, difunctional silicone macro-monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker were required in order to prepare transparent hybrid materials, while high transparent DMAA-based hybrid copolymers could be prepared without EGDMA cross-linker. The polymerization kinetics investigation revealed that this difference between HEMA and DMAA in preparation condition to transparent hybrid material originated to monomer reactivity in copolymerization and DMAA showed high reactivity compared with HEMA. Moreover, DMAA-based hybrid copolymers indicated high water content and high oxygen permeability as against HEMA-based hybrid copolymers because of its low cross-linking density.     

Synthesis and Characterization of Poly(methyl methacrylate‐co‐hydroxyethyl methacrylate)‐b‐polyisobutylene‐b‐poly(methyl methacrylate‐co‐hydroxyethyl Methacrylate) Triblock Copolymers

The synthesis of poly[(methyl methacrylate‐co‐hydroxyethyl methacrylate)‐b‐isobutylene‐b‐(methyl methacrylate‐co‐hydroxyethyl methacrylate)] P(MMA‐co‐HEMA)‐b‐PIB‐b‐P(MMA‐co‐HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished by the combination of living cationic and anionic polymerizations. P(MMA‐co‐HEMA)‐b‐PIB‐b‐P(MMA‐co‐HEMA) triblock copolymers with different compositions were prepared by a synthetic methodology involving the transformation from living cationic to anionic polymerization. First, 1,1‐diphenylethylene end‐functionalized PIB (DPE‐PIB‐DPE) was prepared by the reaction of living difunctional PIB and 1,4‐bis(1‐phenylethenyl)benzene (PDDPE), followed by the methylation of the resulting diphenyl carbenium ion with dimethylzinc (Zn(CH₃)₂). The DPE ends were quantitatively metalated with n‐butyllithium in tetrahydrofuran, and the resulting macroanion initiated the polymerization of methacrylates yielding triblock copolymers with high blocking efficiency. Microphase separation of the thus prepared triblock copolymers was evidenced by the two glass transitions at ?64 and +120°C observed by differential scanning calorimetry. These new block copolymers exhibit typical stress‐strain behavior of thermoplastic elastomers. Surface characterization of the samples was accomplished by angle‐resolved X‐ray photoelectron spectroscopy (XPS), which revealed that the surface is richer in PIB compared to the bulk. However, a substantial amount of P(MMA‐co‐HEMA) remains at the surface. The presence of hydroxyl functionality at the surface provides an opportunity for further modification.     

Synthesis and characterization of well‐defined poly(2‐hydroxyethyl methacrylate‐co‐styrene)‐graft‐poly(ε‐caprolactone) by sequential controlled polymerization

A new graft copolymer, poly(2‐hydroxyethyl methacrylate‐co‐styrene) ‐graft‐poly(?‐caprolactone), was prepared by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with coordination‐insertion ring‐opening polymerization (ROP). The copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) was carried out at 60 °C in the presence of 2‐phenylprop‐2‐yl dithiobenzoate (PPDTB) using AIBN as initiator. The molecular weight of poly (2‐hydroxyethyl methacrylate‐co‐styrene) [poly(HEMA‐co‐St)] increased with the monomer conversion, and the molecular weight distribution was in the range of 1.09 ～ 1.39. The ring‐opening polymerization (ROP) of ?‐caprolactone was then initiated by the hydroxyl groups of the poly(HEMA‐co‐St) precursors in the presence of stannous octoate (Sn(Oct)₂). GPC and ¹H‐NMR data demonstrated the polymerization courses are under control, and nearly all hydroxyl groups took part in the initiation. The efficiency of grafting was very high. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5523–5529, 2004     

Radical copolymerization of vinylidene fluoride with 1‐bromo‐2,2‐difluoroethylene

The radical copolymerization of vinylidene fluoride (VDF) and 1‐bromo‐2,2‐difluoroethylene (BDFE) in 1,1,1,3,3‐pentafluorobutane solution at different monomer molar ratios (ranging from 96/4 to 25/75 mol %) and initiated by tert‐butylperoxypivalate (TBPPI, mainly) is presented. Poly(VDF‐co‐BDFE) copolymers of various aspects (from white powders to yellow viscous liquids) were produced depending on the copolymer compositions. The microstructures of the obtained copolymers were characterized by ¹⁹F and ¹H NMR spectroscopy and by elementary analysis and these techniques enabled one to assess the contents of both comonomers in the produced copolymers. VDF was shown to be more incorporated in the copolymer than BDFE. From the extended Kelen and Tudos method, the kinetics of the radical copolymerization led to the determination of the reactivity ratios, r_i, of both comonomers (r_VDF = 1.20 ± 0.50 and r_{BDFE =} 0.40 ± 0.15 at 75 °C) showing that VDF is more reactive than BDFE. Alfrey‐Price's Q and e values of BDFE monomer were calculated to be 0.009 (from Q_VDF = 0.008) or 0.019 (from Q_VDF = 0.015) and +1.22 (vs. e_VDF = 0.40) or +1.37 (vs. e_VDF = 0.50), respectively, indicating that BDFE is an electron‐accepting monomer. Statistic cooligomers were produced with molar masses ranging from 1,800 to 5,500 g/mol (assessed by GPC with polystyrene standards). A further evidence of the successful copolymerization was shown by the selective reduction of bromine atoms in poly(VDF‐co‐BDFE) cooligomers that led to analog PVDF. The thermal properties of the poly(VDF‐co‐BDFE) cooligomers were also determined and those containing a high VDF amount exhibited a high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3964–3976, 2010.     

Synthesis and properties of amphiphilic and biodegradable poly(ε‐caprolactone‐co‐glycidol) copolymers

We have synthesized poly(ε‐caprolactone‐co‐tert‐butyl glycidyl ether) (CL‐co‐BGE) statistical copolymers using 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis [tris(dimethylamino)phophoranylidenamino]‐2Λ5,4Λ5‐catenadi(phosphazene) (t‐BuP₄) as the catalyst. The hydrolysis of the resulting polymers yields amphiphilic poly(ε‐caprolactone‐co‐glycidol) (CL‐co‐GD) copolymers. By use of the quartz crystal microbalance with dissipation (QCM‐D), we have investigated the enzymatic degradation of the copolymers. It is shown that the degradation rate increases with the content of hydrophilic (GD) units. (3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide) (MTT) assay experiments demonstrate that the CL‐co‐GD copolymers have low cytotoxicity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 846–853     

Synthesis and Characterization of pH‐sensitive Poly(IA‐co‐AAc‐co‐AAm) Hydrogels via Frontal Polymerization

In this work, we report a series of poly(itaconic acid‐co‐acrylic acid‐co‐acrylamide) (poly(IA‐co‐AAc‐co‐AAm)) hydrogels via frontal polymerization (FP). FP starts on the top of the reaction mixture with aid of heating provided from soldering iron gun. Once polymerization initiated, no further energy is required to complete the process. The influences of IA/AAc weight ratios on frontal velocities, temperatures, and conversions on the reaction time are thoroughly investigated and discussed where the amount of AAm monomer remains constant. Fourier transform‐infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscope (SEM), dynamic mechanical analysis, and the swelling measurement are applied to characterize the as‐synthesized poly(IA‐co‐AAc‐co‐AAm) hydrogels. Interestingly, the swelling ratios of the hydrogels are changed with different IA/AAc contents, and the maximum swelling ratios are ~4439% in water. SEM images describe highly porous morphologies and explain good swelling capabilities. Moreover, the poly(IA‐co‐AAc‐co‐AAm) hydrogels exhibit superior pH‐responsive ability. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2214–2221     

Synthesis and characterization of amphiphilic heterograft copolymers with PAA and PS side chains via “Grafting from” approach

The amphiphilic heterograft copolymers poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate)‐graft‐(poly(acrylic acid)/polystyrene) (P(MMA‐co‐BIEM)‐g‐(PAA/PS)) were synthesized successfully by the combination of single electron transfer‐living radical polymerization (SET‐LRP), single electron transfer‐nitroxide radical coupling (SET‐NRC), atom transfer radical polymerization (ATRP), and nitroxide‐mediated polymerization (NMP) via the “grafting from” approach. First, the linear polymer backbones poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate) (P(MMA‐co‐BIEM)) were prepared by ATRP of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA) and subsequent esterification of the hydroxyl groups of the HEMA units with 2‐bromoisobutyryl bromide. Then the graft copolymers poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate)‐graft‐poly(t‐butyl acrylate) (P(MMA‐co‐BIEM)‐g‐PtBA) were prepared by SET‐LRP of t‐butyl acrylate (tBA) at room temperature in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxyl (TEMPO), where the capping efficiency of TEMPO was so high that nearly every TEMPO trapped one polymer radicals formed by SET. Finally, the formed alkoxyamines via SET‐NRC in the main chain were used to initiate NMP of styrene and following selectively cleavage of t‐butyl esters of the PtBA side chains afforded the amphiphilic heterograft copolymers poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)ethyl methacrylate)‐graft‐(poly(t‐butyl acrylate)/polystyrene) (P(MMA‐co–BIEM)‐g‐(PtBA/PS)). The self‐assembly behaviors of the amphiphilic heterograft copolymers P(MMA‐co–BIEM)‐g‐(PAA/PS) in aqueous solution were investigated by AFM and DLS, and the results demonstrated that the morphologies of the formed micelles were dependent on the grafting density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Copolymerization of 2,3,4,5,6‐Pentafluorostyrene and Methacrylic Acid by Nitroxide‐Mediated Polymerization: The Importance of Reactivity Ratios

Amphiphilic block copolymers of 2,3,4,5,6‐pentafluorostyrene (PFS) and methacrylic acid (MAA) are synthesized via nitroxide‐mediated polymerization (NMP). It is established that to obtain a controlled copolymerization a minimum of 40 mol% of PFS is required, which is significantly greater than other copolymerization systems such as using 4.5–8 mol% styrene or 1 mol% of 9‐(4‐vinylbenzyl)‐9H‐carbazole to control the copolymerization of methacrylates. It is surmised that this lack of control is due to the reactivity ratios that favor the addition of MAA rather than PFS (r_PFS = 0.14, r_MAA = 6.97). However this reactivity ratio pair suggests that a one‐shot delayed injection approach can be utilized to synthesize almost pure block copolymers in one pot. Therefore, poly(PFS)‐b‐(PFS‐ran‐MAA) block copolymers are synthesized by a one‐shot delayed addition of MAA. While the concentration of irreversibly terminated chains is evident these results suggest a promising route to the synthesis of fluorinated amphiphilic block copolymers by NMP.

     

Half‐lanthanocene/dialkylmagnesium‐mediated coordinative chain transfer copolymerization of styrene and hexene

The Cp*La(BH₄)₂(THF)₂/n‐butylethylmagnesium (BEM) catalytic system has been assessed for the coordinative chain transfer copolymerization of styrene and 1‐hexene. Poly(styrene‐co‐hexene) statistical copolymers were obtained with number‐average molecular weight up to 7600 g/mol, PDI around 1.4 and 1.5 and up to 23% hexene content. The occurence of chain transfer reactions in the presence of excess BEM is established in the course of the statistical copolymerization. Thanks to this transfer process, the quantity of 1‐hexene in the copolymer is increased by a factor of about 3 for high ratio of hexene in the feed, extending the range of our concept of a chain transfer induced control of the composition of statistical copolymers to poly(styrene‐co‐hexene) copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Novel copolymer networks via the combination of polyaddition and anionic polymerization

A two‐step synthetic route to novel copolymer networks, consisting of polymethacrylate and polyacetal components, was developed by combining the polyaddition and anionic polymerization techniques. The functional polymethacrylates containing hydroxyl or vinyloxyl side groups were used as crosslinkers. They were anionically synthesized as follows: the copolymer of 2‐hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) was prepared by the anionic copolymerization of 2‐(trimethylsiloxy)ethyl methacrylate and MMA, followed by hydrolysis. The copolymer poly(HEMA‐co‐MMA) thus obtained possessed a hydroxyl group in each of its HEMA units. Another kind of vinyloxyl‐containing (co)polymer was prepared by the anionic homopolymerization of 2‐(vinyloxy)ethyl methacrylate (VEMA) or its copolymerization with MMA. The resulting (co)polymer possessed reactive vinyloxyl side groups. The copolymer networks were obtained by reacting each of the above‐mentioned (co)polymers with a polyacetal prepared via the polyaddition between a divinyl ether and a diol. Three divinyl ethers (ethylene glycol divinyl ether, 1,4‐butanediol divinyl ether, and 1,6‐hexanediol divinyl ether) and three diols (ethylene glycol, 1,4‐butanediol, and 1,6‐hexanediol) were employed as monomers in the polyaddition step, and their combinations generated nine kinds of polyacetals. When a polyaddition reaction was terminated with a divinyl ether monomer, a polyacetal with two vinyloxyl end groups was obtained, which could further react with the hydroxyl groups of poly(HEMA‐co‐MMA) to generate a copolymer network. On the other hand, when a diol was used as terminator in the polyaddition, the resulting polyacetal possessed two hydroxyl end groups, which could react with the vinyloxyl groups of poly(VEMA) or poly(VEMA‐co‐MMA), to generate a copolymer network. All the copolymer networks exhibited degradation in the presence of acids. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 117–126, 2001     

Simultaneous reversible addition fragmentation chain transfer and ring‐opening polymerization

The simultaneous ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) and 2‐hydroxyethyl methacrylate (HEMA) polymerization via reversible addition fragmentation chain transfer (RAFT) chemistry and the possible access to graft copolymers with degradable and nondegradable segments is investigated. HEMA and ε‐CL are reacted in the presence of cyanoisopropyl dithiobenzoate (CPDB) and tin(II) 2‐ethylhexanoate (Sn(Oct)₂) under typical ROP conditions (T > 100 °C) using toluene as the solvent in order to lead to the graft copolymer PHEMA‐g‐PCL. Graft copolymer formation is evidenced by a combination of size‐exclusion chromatography (SEC) and NMR analyses as well as confirmed by the hydrolysis of the PCL segments of the copolymer. With targeted copolymers containing at least 10% weight of PHEMA and relatively small PHEMA backbones (ca. 5,000–10,000 g mol^?1) the copolymer grafting density is higher than 90%. The ratio of free HEMA‐PCL homopolymer produced during the “one‐step” process was found to depend on the HEMA concentration, as well as the half‐life time of the radical initiator used. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3058–3067, 2008     

Ru(II)‐mediated living radical polymerization: block and random copolymerizations of N,N‐dimethylacrylamide and methyl methacrylate

RuCl₂(PPh₃)₃ led to living radical copolymerization of N,N‐dimethylacrylamide (DMAA) and methyl methacrylate (MMA) in conjunction with a halide‐initiator (R‐X; CHCl₂COPh, CCl₃Br) and Al(Oi‐Pr)₃ in toluene at 80°C. Both the monomers were polymerized at almost the same rate into random copolymers, where the number‐average molecular weights (M_n) increased in direct proportion to weight of the obtained polymers, and the molecular weight distributions (MWDs) were narrow throughout the reactions (M_w/M_n = 1.2‐1.6). MMA was consumed faster in the copolymerization than in the homopolymerization, which was due to the interaction of DMAA with the ruthenium complex. The Ru(II)‐based initiating system was also effective in block copolymerization of DMAA and MMA.     

Synthesis and characterization of polytulipalin‐g‐polylactide copolymers

Graft copolymers of poly(tulipalin A) (PT) and poly(DL‐lactide) (PDLLA) (PT‐g‐PDLLA) having various graft lengths and ratios were synthesized by free‐radical copolymerization of α‐methylene‐γ‐butyrolactone (MBL) and PDLLA macromonomers (HEMA‐PDLLA) terminated by 2‐hydroxyethyl methacrylate (HEMA)‐terminated. HEMA‐PDLLA were synthesized by ring opening polymerization (ROP) of DL‐lactide in the presence of HEMA. Both HEMA‐PDLLA and the copolymers were characterized by NMR spectroscopy and gel permeation chromatography (GPC). The thermal properties of the graft copolymers were found to depend on the graft length and the ratio. The copolymers consisting of PDLLA side chains of M_n = 500 Da showed a single T_g between T_gs of the two component polymers, suggesting a miscible state of PT and PDLLA. In contrast, the copolymers consisting of PDLLA side chains of M_n = 1100, 2000, and 7000 Da showed two isolated T_g, suggesting two segregated domains. The AFM phase images of the copolymers supported the single and phase‐separated morphologies for the former and latter systems, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Swelling behavior of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide‐co‐acrylamide} hydrogels in aqueous solutions of surfactants

Temperature sensitive poly{N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐acrylamide} [P(DMAPMA‐co‐AAm)] hydrogels were prepared by the free‐radical crosslinking copolymerization of corresponding monomers in water with N,N‐methylenebisacrylamide as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the P(DMAPMA‐co‐AAm) hydrogels was investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate and the cationic surfactant dodecyltrimethylammonium bromide. In pure water, regardless of the amount of N,N‐methylenebisacrylamide, the P(DMAPMA‐co‐AAm) hydrogels showed a discontinuous phase transition between 30 and 36 °C. However, the transition temperature changed from discontinuous to continuous with the addition of surfactants; this was ascribed to the conversion of nonionic P(DMAPMA‐co‐AAm) hydrogels into polyelectrolyte hydrogels due to the binding of surfactants through hydrophobic interactions. Additionally, the concentrations of free sodium dodecyl sulfate and dodecyltrimethylammonium bromide ions were measured at different temperatures by conductometry, and it was found that the electric conductivity of the P(DMAPMA‐co‐AAm)–surfactant systems depended strongly on the swelling ratio; most notably, it changed drastically near the phase‐transition temperature of the P(DMAPMA‐co‐AAm) hydrogel. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1645–1652, 2006     

Synthesis and characterization of poly(3,3 bis(azidomethyl)oxetane‐co‐ε‐caprolactone)s

The quasi‐living cationic copolymerization of 3,3‐bis(chloromethyl)oxetane (BCMO) and ε‐caprolactone (ε‐CL), using boron trifluoride etherate as catalyst and 1,4‐butanediol as coinitiator, was investigated in methylene chloride at 0°C. The resulting hydroxyl‐ended copolymers exhibit a narrow molecular weight polydispersity and a functionality of about 2. The reactivity ratios of BCMO (0.26) and ε‐CL (0.47), and the T_g of the copolymers, indicate their statistical character. The synthesis of poly(3,3‐bis(azidomethyl)oxetane‐co‐ε‐caprolactone) from poly(BCMO‐co‐ε‐CL) via the substitution of the chlorine atoms by azide groups, using sodium azide in DMSO at 110°C, occurs without any degradation, but the copolymers decompose at about 240°C. All polymers were characterized by vapor pressure osmometry or steric exclusion chromatography, ¹H‐NMR and FTIR spectroscopies, and DSC. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1027–1039, 1999