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1.
Peter J. Roth Daniel Kessler Rudolf Zentel Patrick Theato 《Journal of polymer science. Part A, Polymer chemistry》2009,47(12):3118-3130
Five different polymers, poly[methyl methacrylate] (PMMA), poly[lauryl methacrylate] (PLMA), poly[diethylene glycol methacrylate] (PDEGMA), poly[N‐isopropylacrylamide] (PNIPA), and poly[styrene] (PS) prepared by the RAFT process and thus terminated with dithioesters were aminolyzed in the presence of S‐3‐butynyl methane thiosulfonate (MTS), which was synthesized in two steps. Analysis of the polymers by 2D NMR, UV–vis absorbance, and gel permeation chromatography revealed them to quantitatively carry acetylene end groups connected with disulfide bridges, indicating that functional MTS reagents can be employed for end group functionalization of RAFT polymers. This versatile method is of advantage compared with conjugations with functional maleimides, where isolation of terminal thiols is often required but inexpedient for poly[(meth)acrylates] because their terminal thiols may undergo backbiting and thus avoid conjugation. The acetylene‐terminated polymers were bound to an azide functionalized glass surface in a Cu(I) catalyzed cycloaddition. The modified surfaces exhibited water contact angles corresponding to the polarity of the attached polymers. In the case of the stimulus responsive polymers PNIPA and PDEGMA, the surfaces showed temperature‐dependent contact angles. The disulfide bond connecting the polymers to the surface could be selectively cleaved and resulted in all surfaces having the same contact angle, independent of the nature of the polymer prior attached to the surface. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3118–3130, 2009 相似文献
2.
M.‐H. Kim J. D. Londono A. Habenschuss 《Journal of Polymer Science.Polymer Physics》2000,38(18):2480-2485
The melt structures of linear polyethylene and the isotactic vinyl polymers polypropylene, poly(1‐butene), and poly(4‐methyl‐1‐pentene), along with the corresponding methyl, ethyl, and isobutyl side chains, were studied with wide‐angle X‐ray diffraction. As the size of the side branch increases from zero (polyethylene) to methyl, ethyl, and isobutyl, a prepeak appears below the main diffraction peak in the total structure factor. The prepeaks become stronger and shift to lower scattering vectors with increasing bulkiness of the side chain. There is a strong correlation between the position of the prepeaks in the melt and the average nearest‐neighbor helix–helix packing distance in the crystals, implying similar helical conformations in the melts. © 2000 John Wiley & Sons, Inc.* J Polym Sci B: Polym Phys 38: 2480–2485, 2000 相似文献
3.
A novel vinyl‐hydantoin monomer, 3‐(4′‐vinylbenzyl)‐5,5‐dimethylhydantoin, was synthesized in a good yield and was fully characterized with Fourier transform infrared (FTIR) and 1H NMR spectra. Its homopolymer and copolymers with several common acrylic and vinyl monomers, such as vinyl acetate, acrylonitrile, and methyl methacrylate, were readily prepared under mild conditions. The polymers were characterized with FTIR and 1H NMR, and their thermal properties were analyzed with differential scanning calorimetry studies. The halogenated products of the corresponding copolymers exhibited potent antibacterial properties against Escherichia coli, and the antibacterial properties were durable and regenerable. The structure–property relationships of the polymers were further discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3348–3355, 2001 相似文献
4.
Prakash S. Sane Bhausaheb V. Tawade Indravadan Parmar Savita Kumari Samadhan Nagane Prakash P. Wadgaonkar 《Journal of polymer science. Part A, Polymer chemistry》2013,51(9):2091-2103
Two new initiators, namely, 4‐(4‐(2‐(4‐(allyloxy) phenyl)‐5‐hydroxypentane 2‐yl) phenoxy)benzaldehyde and 4‐(4‐(allyloxy) phenyl)‐4‐(4‐(4‐formylphenoxy) phenyl) pentyl 2‐bromo‐2‐methyl propanoate containing “clickable” hetero‐functionalities namely aldehyde and allyloxy were synthesized starting from commercially available 4,4′‐bis(4‐hydroxyphenyl) pentanoic acid. These initiators were utilized, respectively, for ring opening polymerization of ε‐caprolactone and atom transfer radical polymerization of methyl methacrylate. Well‐defined α‐aldehyde, α′‐allyloxy heterobifunctionalized poly(ε‐caprolactones) (Mn,GPC: 5900–29,000, PDI: 1.26–1.43) and poly(methyl methacrylate)s (Mn,GPC: 5300–28800, PDI: 1.19–1.25) were synthesized. The kinetic study of methyl methacrylate polymerization demonstrated controlled polymerization behavior. The presence of aldehyde and allyloxy functionality on polymers was confirmed by 1H NMR spectroscopy. Aldehyde‐aminooxy and thiol‐ene metal‐free double click strategy was used to demonstrate reactivity of functional groups on polymers. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
5.
Aydan Dag Hakan Durmaz Gurkan Hizal Umit Tunca 《Journal of polymer science. Part A, Polymer chemistry》2008,46(1):302-313
Diels–Alder click reaction was successfully applied for the preparation of 3‐arm star polymers (A3) using furan protected maleimide end‐functionalized polymers and trianthracene functional linking agent (2) at reflux temperature of toluene for 48 h. Well‐defined furan protected maleimide end‐functionalized polymers, poly (ethylene glycol), poly(methyl methacrylate), and poly(tert‐butyl acrylate) were obtained by esterification or atom transfer radical polymerization. Obtained star polymers were characterized via NMR and GPC (refractive index and triple detector detection). Splitting of GPC traces of the resulting polymer mixture notably displayed that Diels–Alder click reaction was a versatile and a reliable route for the preparation of A3 star polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 302–313, 2008 相似文献
6.
Costas N. Costa Costas S. Patrickios 《Journal of polymer science. Part A, Polymer chemistry》1999,37(11):1597-1607
α‐Hydroxy and α,ω‐dihydroxy polymers of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) of various molecular weights were synthesized by group transfer polymerization (GTP) in tetrahydrofuran (THF), using 1‐methoxy‐1‐(trimethylsiloxy)‐2‐methyl propene (MTS) as the initiator and tetrabutylammonium bibenzoate (TBABB) as the catalyst. The hydroxyl groups were introduced by adding one 2‐(trimethylsiloxy) ethyl methacrylate (TMSEMA) unit at one or at both ends of the polymer chain. The ends were converted to 2‐hydroxyethyl methacrylate (HEMA) units after the polymerization by acid‐catalyzed hydrolysis. Gel permeation chromatography (GPC) in THF and proton nuclear magnetic resonance (1H‐NMR) spectroscopy in CDCl3 were used to determine the molecular weight and composition of the polymers. These mono‐ and difunctional methacrylate polymers can be covalently linked at the hydroxy termini to form star polymers and model networks, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1597–1607, 1999 相似文献
7.
Hong Zhou Jianguo Jiang Keda Zhang 《Journal of polymer science. Part A, Polymer chemistry》2005,43(12):2567-2573
N‐Bromosuccinimide (NBS) was used as a thermal iniferter for the initiation of the bulk polymerizations of methyl methacrylate, methyl acrylate, and styrene. The polymerizations showed the characteristics of a living polymerization: both the yields and the molecular weights of the resultant polymers increased linearly as the reaction time increased. The molecular weight distributions of the polymers were 1.42–1.95 under the studied conditions. The resultant polymers could be used as macroiniferters to reinitiate the polymerization of the second monomer. The copolymers poly(methyl methacrylate)‐b‐polystyrene and polystyrene‐b‐poly(methyl methacrylate) were obtained and characterized. End‐group analysis of the resultant poly(methyl methacrylate), poly(methyl acrylate), and polystyrene confirmed that NBS behaved as a thermal iniferter. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2567–2573, 2005 相似文献
8.
Dimitrios Priftis Marinos Pitsikalis Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5164-5181
A novel heterofunctional initiator, synthesized from pentaerythritol in a three step reaction sequence with two ring opening polymerization (ROP) and two atom transfer radical polymerization (ATRP) initiating sites, was used to prepare A2B2 miktoarm star copolymers of poly(ε‐caprolactone), PεCL, with polystyrene, PS, poly(methyl methacrylate), PMMA, poly(dimethylaminoethyl methacrylate), PDMAEMA, and poly(2‐hydroxyethyl methacrylate), PHEMA. A2B miktoarm stars, A being PεCL or poly(δ‐valerolactone), PδVL and B PS were also prepared from ω,ω‐dihydroxy‐PS, synthesized from ω‐Br‐PS and serinol, by ROP of εCL or δVL. All polymers were characterized by size exclusion chromatography, 1H NMR spectroscopy, and membrane osmometry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5164–5181, 2007 相似文献
9.
Sung‐Young Park Hee‐Young Park Hwa‐Soo Lee Sang‐Wook Park Chang‐Sik Ha Dae‐Won Park 《Journal of polymer science. Part A, Polymer chemistry》2001,39(9):1472-1480
This study was related to the investigation of the chemical fixation of carbon dioxide to a copolymer bearing epoxide and the application of the cyclic carbonate group containing copolymer‐to‐polymer blends. In the synthesis of poly[(2‐oxo‐1,3‐dioxolane‐4‐yl) methyl methacrylate‐co‐ethyl acrylate] [poly(DOMA‐co‐EA)] from poly(glycidyl methacrylate‐co‐ethyl acrylate) [poly(GMA‐co‐EA)] and CO2, quaternary ammonium salts showed good catalytic activity. The films of poly(DOMA‐co‐EA) with poly(methyl methacrylate) (PMMA) or poly(vinyl chloride) (PVC) blends were cast from N,N′‐dimethylformamide solution. The miscibility of the blends of poly(DOMA‐co‐EA) with PMMA or PVC have been investigated both by DSC and visual inspection of the blends. The optical clarity test and DSC analysis showed that poly(DOMA‐co‐EA) containing blends were miscible over the whole composition range. The miscibility behaviors were discussed in terms of Fourier transform infrared spectra and interaction parameters based on the binary interaction model. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1472–1480, 2001 相似文献
10.
Pan Cai‐Yuan Tao Lei Wu De‐Cheng 《Journal of polymer science. Part A, Polymer chemistry》2001,39(18):3062-3072
The polymers poly[(2,2‐dimethyl‐1,3‐dioxolane‐4yl) methyl acrylate] (PDMDMA) and four‐armed PDMDMA with well‐defined structures were prepared by the polymerization of (2,2‐dimethyl‐1,3‐dioxolane‐4yl) methyl acrylate (DMDMA) in the presence of an atom transfer radical polymerization (ATRP) initiator system. The successive hydrolyses of the polymers obtained produced the corresponding water‐soluble polymers poly(2,3‐dihydroxypropyl acrylate) (PDHPA) and four‐armed PDHPA. The controllable features for the ATRP of DMDMA were studied with kinetic measurements, gel permeation chromatography (GPC), and NMR data. With the macroinitiators PDMDMA–Br and four‐armed PDMDMA–Br in combination with CuBr and 2,2′‐bipyridine, the block polymerizations of methyl acrylate (MA) with PDMDMA were carried out to afford the AB diblock copolymer PDMDMA‐b‐MA and the four‐armed block copolymer S{poly[(2,2‐dimethyl‐1,3‐dioxolane‐4yl) methyl acrylate]‐block‐poly(methyl acrylate)}4, respectively. The block copolymers were hydrolyzed in an acidic aqueous solution, and the amphiphilic diblock and four‐armed block copolymers poly(2,3‐dihydroxypropyl acrylate)‐block‐poly(methyl acrylate) were prepared successfully. The structures of these block copolymers were verified with NMR and GPC measurements. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3062–3072, 2001 相似文献
11.
Wei Zhang Xiulin Zhu Di Zhou Xiaoyan Wang Jian Zhu 《Journal of polymer science. Part A, Polymer chemistry》2005,43(12):2632-2642
The reversible addition–fragmentation chain transfer (RAFT) polymerizations of 2‐naphthyl acrylate (2NA) initiated by 2,2′‐azobisisobutyronitrile were investigated with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) as a RAFT agent at various temperatures in a benzene solution. The results of the polymerizations showed that 2NA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first‐order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion. The polydispersities of the polymer were relatively low up to high conversions in all cases. The chain‐extension reactions of poly(2‐naphthyl acrylate) (P2NA) with methyl methacrylate and styrene successfully yielded poly(2‐naphthyl acrylate)‐b‐poly(methyl methacrylate) and poly(2‐naphthyl acrylate)‐b‐polystyrene block polymers, respectively, with narrow polydispersities. The P2NA obtained by RAFT polymerization had a strong ultraviolet absorption at 270 nm, and the molecular weights had no apparent effect on the ultraviolet absorption intensities; however, the fluorescence intensity of P2NA increased as the molecular weight increased and was higher than that of 2NA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2632–2642, 2005 相似文献
12.
Shingo Shimada Toshiyuki Hiroi Tomonori Ida Motohiro Mizuno Kazunaka Endo Ernst Z. Kurmaev Alexander Moewes 《Journal of Polymer Science.Polymer Physics》2007,45(2):162-172
X‐ray fluorescence measurements for O‐containing [polyethylene oxide, polyvinyl alcohol, polyvinyl methyl ether], CO‐containing [polyvinyl methyl ketone, polyethylene terephthalate], N‐containing [poly‐4‐vinylpyridine (P4VP), polyaniline oligomer (PAO)], and S‐containing [polyphenylene sulfide] substances are presented. Carbon Kα X‐ray emission spectra (XES) and X‐ray photoelectron spectra (XPS) are compared with our DFT calculations performed with the Amsterdam density functional (ADF) program. The combined analysis of valence XPS and carbon Kα XES allows us to determine the individual contributions from pσ‐ and pπ‐bonding molecular orbitals of the polymers. The ΔSCF calculations yield the accurate C1s core‐electron binding energies (CEBEs) for all carbon sites of the organic compound. We calculate all CEBEs of the model molecules using the ΔE KS approach. Our simulated C1s photoelectron and C Kα emission spectra are in good agreement with our measurements. We also obtain WD (work function and the other energies) values for the polymers and PAO from the difference between calculated (gas‐phase) and measured (solid) CEBE values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 162–172, 2007 相似文献
13.
Phuong Ghi David J. T. Hill Andrew K. Whittaker 《Journal of Polymer Science.Polymer Physics》2000,38(14):1939-1946
Cylindrical samples (≈5 mm × 20 mm) of poly(2‐hydroxyethyl methacrylate) and copolymers of 2‐hydroxyethyl methacrylate and furfuryl methacrylate were prepared, and the sorption of water into these cylinders was studied by the mass‐uptake method and by the measurement of the volume change at equilibrium. The equilibrium water content and volume change for the cylinders both varied systematically with the copolymer composition. The diffusion of water into the cylinders followed Fickian behavior, with the diffusion coefficients, dependent on the copolymer composition, varying from 2.00 × 10−11 m2s−1 for poly(2‐hydroxyethyl methacrylate) to 5.00 × 10−12 m2s−1 for poly(2‐hydroxyethyl methacrylate‐co‐tetrahydrofurfuryl methacrylate) with a 1 : 4 composition. The polymers that were rich in 2‐hydroxyethyl methacrylate were characterized by a water‐sorption overshoot, which was attributed to a slow reorientation of the polymer chains in the swollen rubbery regions formed after water sorption. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1939–1946, 2000 相似文献
14.
Gisèle Volet Anne‐Cécile Lasne Deschamps Catherine Amiel 《Journal of polymer science. Part A, Polymer chemistry》2010,48(11):2477-2485
The α,ω‐end‐capped poly(2‐methyl‐2‐oxazoline) (Cn‐POXZ‐Cn) have been synthesized by a one‐pot process using cationic ring‐opening polymerization with an appropriate initiator and terminating agent. The polymers bearing different alkyl groups C12 and C18 have molecular weight in the range of 2.4 × 103 to 14 × 103 with a small polydispersity index. The solution behavior of the free chains has been analyzed in a nonselective solvent, dichloromethane, by small‐angle neutron scattering and dynamic light scattering. These amphiphilic polymers associate in water to form flower‐like micellar structures. Critical micelle concentrations, investigated by fluorescence technique, are in the range of 0.03–0.5 g L?1 and are dependent on the hydrophilic/lipophilic balance. The structural properties of the aggregates have also been investigated by viscometry. Intrinsic viscosities of these polymers are in the same range as that of the precursors poly(2‐methyl‐2‐oxazoline) (POXZ) and mono‐functionalized polymers. Large viscosity increase corresponding to intermicellar bridging was observed in the vicinity of the micelle overlap concentration. Addition of hydroxypropyl β‐cyclodextrin (HβCD) has dissociated the aggregates and the intrinsic viscosities of the HβCD‐end‐capped chains have become comparable with the ones of POXZ precursor chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2477–2485, 2010 相似文献
15.
Lihong He Juan Pablo Hinestrosa Joseph M. Pickel Shanju Zhang David G. Bucknall S. Michael Kilbey II Jimmy W. Mays Kunlun Hong 《Journal of polymer science. Part A, Polymer chemistry》2011,49(2):414-422
Linear triblock terpolymers of poly(n‐butyl methacrylate)‐b‐poly(methyl methacrylate)‐b‐poly(2‐fluoroethyl methacrylate) (PnBMA‐PMMA‐P2FEMA) were synthesized by sequential reversible addition fragmentation chain transfer (RAFT) polymerization. Kinetic studies of the homopolymerization of 2FEMA by RAFT polymerization demonstrated controllable characteristics with fairly narrow polydispersities (~1.30). The resultant PnBMA‐PMMA‐P2FEMA triblock terpolymers were characterized via 1H NMR, 19F NMR, and gel permeation chromatography. These polymers formed micellar aggregates in a selective solvent mixture. The as‐formed micelles were analyzed using scanning electron microscopy and dynamic light scattering. It was found that these terpolymers could directly self‐organize into complex micelles in a tetrahydrofuran/methanol mixture with diameters that depended on polymer composition. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
16.
Maria Letizia Focarete Mariastella Scandola Ajay Kumar Richard A. Gross 《Journal of Polymer Science.Polymer Physics》2001,39(15):1721-1729
The Candida antarctica lipase B (Novozyme‐435)‐catalyzed ring‐opening polymerization of ω‐pentadecalactone in toluene was performed. Poly(ω‐pentadecalactone) [poly(PDL)] was obtained in a 93% isolated yield in 4 h with a number‐average molecular weight of 64.5 × 103 g/mol and a polydispersity index of 2.0. The solid‐state properties of poly(PDL) were investigated by thermogravimetric analysis (TGA) coupled with mass spectrometry, differential scanning calorimetry (DSC), stress–strain measurements, wide‐angle X‐ray diffraction, and dynamic mechanical and dielectric spectroscopies. Poly(PDL) is a crystalline polymer that melts around 100 °C. The polyester shows good thermal stability, with a main TGA weight loss centered at 425 °C. Because of the high degree of poly(PDL) crystallinity, the glass transition (?27 °C) is revealed by relaxation techniques such as dynamic mechanical and dielectric spectroscopies, rather than by DSC. In addition to the glass transition, the viscoelastic spectrum of poly(PDL) also shows two low‐temperature secondary relaxations centered at ?130 (γ) and ?90 °C (β). They are attributed to local motions of the long methylene sequence (γ) and complex units involving water associated with the ester groups (β). The mechanical properties of poly(PDL) are typical of a hard, tough material, with an elastic modulus and yield parameters comparable to those of low‐density polyethylene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1721–1729, 2001 相似文献
17.
Kohji Ohno Benjamin Wong David M. Haddleton 《Journal of polymer science. Part A, Polymer chemistry》2001,39(13):2206-2214
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 (Mn) = 55,700, polydispersity index (PDI) = 1.07; Mn = 118,000, PDI = 1.06; polystyrene, Mn = 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 (Mn = 15,000, PDI = 1.03; Mn = 36,500, PDI = 1.14; and Mn = 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 (Mn = 104,000, PDI = 1.05). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2206–2214, 2001 相似文献
18.
Chunzhao Li Brian C. Benicewicz 《Journal of polymer science. Part A, Polymer chemistry》2005,43(7):1535-1543
A series of new reversible addition–fragmentation chain transfer (RAFT) agents with cyanobenzyl R groups were synthesized. In comparison with other dithioester RAFT agents, these new RAFT agents were odorless or low‐odor, and this made them much easier to handle. The kinetics of methyl methacrylate radical polymerizations mediated by these RAFT agents were investigated. The polymerizations proceeded in a controlled way, the first‐order kinetics evolved in a linear fashion with time, the molecular weights increased linearly with the conversions, and the polydispersities were very narrow (~1.1). A poly[(methyl methacrylate)‐block‐polystyrene] block copolymer was prepared (number‐average molecular weight = 42,600, polydispersity index = 1.21) from a poly(methyl methacrylate) macro‐RAFT agent. These new RAFT agents also showed excellent control over the radical polymerization of styrenics and acrylates. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1535–1543, 2005 相似文献
19.
Jieming Li Mario Gauthier 《Journal of polymer science. Part A, Polymer chemistry》2000,38(20):3711-3721
The synthesis of ω‐ and α,ω‐telechelics with sulfonate end groups through the sulfoalkylation of homopolymers and block copolymers of n‐butyl methacrylate and t‐butyl methacrylate with 1,3‐propane sultone is described. The polymerizations are initiated in tetrahydrofuran at −78 °C with either 1,1‐diphenyl‐3‐methylpentyllithium or dilithium 1,1,4,4‐tetraphenylbutane to obtain monofunctional or difunctional polymethacrylate anions, respectively. Narrow molecular weight distributions are obtained for the homopolymers and copolymers in the presence of LiCl in a 10/1 ratio relative to the initiator. The direct reaction of the poly(n‐butyl methacrylate) anions with the sultone results in low functionalization levels: f = 0.24–0.29 for the monofunctional anions and f = 0.32–0.35 for the difunctional anions. The reaction of the poly(t‐butyl methacrylate) anions or end‐capping of the poly(n‐butyl methacrylate) anions with t‐butyl methacrylate units before sulfoalkylation yields telechelics with f = 0.81–1.0 for the monofunctional anions and f = 1.74–1.94 for the difunctional anions. The telechelic polymers, purified by ultrafiltration, have been characterized by size exclusion chromatography, Fourier transform infrared, and 1H NMR spectroscopy. The yield of the sulfoalkylation reactions, determined by colorimetric analysis of a complex formed with methylene blue, is in good agreement with the results obtained by nonaqueous titration of the acidified telechelics. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3711–3721, 2000 相似文献
20.
Moon Suk Kim Fumio Sanda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2001,39(21):3832-3840
Novel phosphates, O‐p‐(hydroxymethyl)benzyl O,O‐diethyl phosphate ( 1 ) and O‐(2‐bromoisobutyryloxymethyl)benzyl O,O‐diethyl phosphate ( 2 ) were synthesized by the reaction of diethyl phosphorochloridate with 1,4‐benzenedimethanol and the successive reaction with 2‐bromoisobutyryl bromide in the presence of triethylamine and submitted to the polymerization of ?‐caprolactone and methyl methacrylate as the initiators. They afforded phosphate end‐functional poly(?‐caprolactone) and poly(methyl methacrylate) with controlled molecular weights and polydispersity ratios by living ring‐opening polymerization and samarium‐induced polymerization. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate end‐functional polymers as the latent polymeric initiators in the presence of ZnCl2. The polymerization of GPE did not proceed below 90 °C, but it rapidly proceeded to afford poly(GPE) above the temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3832–3840, 2001 相似文献