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1.
Using controlled radical polymerization to confirm the lower critical solution temperature of an N‐(alkoxyalkyl) acrylamide polymer in aqueous solution 下载免费PDF全文
Xeniya Savelyeva Lucia Li Milan Marić 《Journal of polymer science. Part A, Polymer chemistry》2015,53(1):59-67
N‐(3‐Methoxypropyl) acrylamide (MPAM) was polymerized by controlled radical polymerization (CRP) methods such as nitroxide‐mediated polymerization (NMP) and reversible addition–fragmentation chain‐transfer polymerization (RAFT). CRP was expected to yield well‐defined polymers with sharp lower critical solution temperature (LCST) transitions. NMP with the BlocBuilder (2‐([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino]oxy)‐2‐methylpropanoic acid) and SG1 ([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino] oxidanyl) initiating system revealed low yields and lack of control (high dispersity, ? ~ 1.5–1.6, and inhibition of chain growth). However, RAFT was far more effective, with linear number average molecular weight, , versus conversion, X, plots, low ? ~ 1.2–1.4 and the ability to form block copolymers using N,N‐diethylacrylamide (DEAAM) as the second monomer. Poly(MPAM) (with = 13.7–25.3 kg mol?1) thermoresponsive behavior in aqueous media revealed cloud point temperatures (CPT)s between 73 and 92 °C depending on solution concentration (ranging from 1 to 3 wt %). The and the molecular weight distribution were the key factors determining the CPT and the sharpness of the response, respectively. Poly(MPAM)‐b‐poly(DEAAM) block copolymer ( = 22.3 kg mol?1, ? = 1.41, molar composition FDEAAM = 0.38) revealed dual LCSTs with both segments revealing distinctive CPTs (at 75 and 37 °C for poly(MPAM) and poly(DEAAM) blocks, respectively) by both UV–Vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 59–67 相似文献
2.
Hua‐Feng Fei Xiaojie Han Bozheng Liu Xiyin Gao Qian Wang Zhijie Zhang Zemin Xie 《Journal of polymer science. Part A, Polymer chemistry》2016,54(6):835-843
Trifluoropropylmethylsiloxane–phenylmethylsiloxane gradient copolysiloxanes were synthesized by anionic and cationic ring‐opening polymerization (ROP) of 1,3,5‐tris(trifluoropropylmethyl)cyclotrisiloxane ( ) and phenylmethylcyclotrisiloxane ( ). The analysis of reactivity ratios revealed that the reactivity of toward anionic ROP was higher than that of ; however, exhibited lower reactivity compared with during the cationic ROP. AB and BAB type gradient copolymers were obtained because of a difference in the reactivity of the monomers. The microstructure of copolymers was characterized by 29Si NMR spectroscopy, gel permeation chromatography, and differential scanning calorimetry. Furthermore, the mechanism for kinetics inverse of copolymerization was proposed based on the results of the optimized molecular configuration. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 835–843 相似文献
3.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(18):2096-2102
An efficient thermally latent initiation system using dual sulfonium salts, consisting S‐benzylsulfonium salt 1 bearing counter anion and S,S‐dimethylsulfonium salt 2 bearing CH3 counter anion, has been developed for the cationic polymerization of epoxides. Compared to the conventional system using 1 as a thermally latent initiator, the newly developed system allowed significant improvement of stability of epoxy formulations during storage at ambient temperature without sacrificing their curability at elevated temperatures. Such a remarkable performance is attributable to the nucleophilic attack of CH3 to cationic species formed unavoidably by the reaction of 1 with epoxide. Such entrapment of cationic species into the corresponding dormant led to the inhibition of undesirable chain growth of polymers during storage of epoxy formulations. In addition, the dormant can undergo dissociation at elevated temperature to give cationic species, which can readily initiate the polymerization of epoxide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2096–2102 相似文献
4.
Heterofunctional RAFT‐derived PNIPAM via cascade trithiocarbonate removal and thiol‐yne coupling click reaction 下载免费PDF全文
Maël Le Bohec Sandie Piogé Sagrario Pascual Laurent Fontaine 《Journal of polymer science. Part A, Polymer chemistry》2017,55(21):3597-3606
An efficient one‐pot process to functionalize the α‐ and ω‐positions of RAFT‐derived poly(N‐isopropylacrylamide) (PNIPAM) by two inherently different mechanistic pathways is reported. The method relies on the RAFT polymerization of NIPAM using a new alkyne‐based RAFT agent, namely 2‐cyano‐5‐oxo‐5‐(prop‐2‐yn‐1‐ylamino)pentan‐2‐yl dodecyltrithiocarbonate (COPYDC) and the combination of thiol‐yne click chemistry and thiocarbonylthio chain‐end removal reactions. COPYDC was prepared in good yield and used as an efficient chain transfer agent during the RAFT polymerization of NIPAM. Well‐defined polymers with controlled molar masses ( = 7500–14,700 g.mol?1) and narrow dispersities (? = 1.18–1.26) are thus obtained. Cascade thiol‐yne click reaction at the alkyne α‐chain end and trithiocarbonate removal at the ω‐chain end are successfully achieved using benzyl mercaptan and excess AIBN. The reported method provides a facile and mild route to heterofunctional telechelic RAFT polymers with predictable molar masses and low dispersities. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3597–3606 相似文献
5.
Stefan Hilf Frederik Wurm Andreas F. M. Kilbinger 《Journal of polymer science. Part A, Polymer chemistry》2009,47(24):6932-6940
This article describes the construction of branched ROMP‐polymer architectures via polycondensation of ABn‐type macromonomers. For this convergent strategy, a polymer was synthesized that carries several hydroxyl‐groups along the polymer chain and one carboxylic acid group at the chain end. An esterification reaction between these functional groups yielded long‐chain branched polymers. The polymers were analyzed by NMR and SEC to monitor the condensation reaction. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009 相似文献
6.
Francisco‐Javier Lpez‐Villanueva Frederik Wurm Andreas F. M. Kilbinger Holger Frey 《Macromolecular rapid communications》2007,28(6):704-709
A facile two‐step synthesis for branched poly(isoprene)s (PI) based on polyaddition of ABn‐type macromonomers is described. The synthesis of the macromonomers was achieved by anionic polymerization of isoprene and subsequent end‐capping of the polymers by addition of chlorodimethylsilane to the living carbanions. This led to PI‐based macromonomers with narrow polydispersity ( / < 1.15) and molecular weights in the range of 1 700 – 22 100 g · mol−1. Synthesis of the branched polymers was carried out by a hydrosilylation‐based polymerization of the macromonomers. Characterization via SEC, SEC‐MALLS, coupled SEC‐viscosimetry and 1H‐NMR‐spectroscopy supported the formation of branched structures. Interestingly, these branched polymers exhibited α‐values that were similar to those reported for hyperbranched polymers based on AB2‐monomers.
7.
Na Yao Wenjing Lin Xiaofang Zhang Huawei Gu Lijuan Zhang 《Journal of polymer science. Part A, Polymer chemistry》2016,54(1):186-196
Multifunctional polymer unimolecular micelles, which are used as templates to fabricate stable gold nanoparticles (GNPs) in one‐step without external reductant, have been designed and prepared. Amphiphilic 21‐arm star‐like block copolymers β‐cyclodextrin‐{poly(lactide)‐poly(2‐(dimethylamino) ethyl methacrylate)‐poly[oligo(2‐ethyl‐2‐oxazoline)methacrylate]}21 [β‐CD‐(PLA‐PDMAEMA‐PEtOxMA)21] and the precursors are synthesized by the combination of ring‐opening polymerization (ROP) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The tertiary amine groups of PDMAEMA block reduce the counterion to zerovalent gold in situ, and these gold atoms combine mutually to form final GNPs. GNPs with relatively small size and narrow size distribution can be obtained in longer DMAEMA block copolymer, larger molar ratio of DMAEMA to HAuCl4 and smaller absolute concentrations of both polymer and HAuCl4. These results showed that the unimolecular micelles can be used as templates for preparing and stabilizing GNPs in situ without any external reducing agents and organic solvents, suggesting that the nanocomposite systems are latent nanocarriers for further biomedical application. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 186–196 相似文献
8.
Manjun Xiao Chunyang Gu Tong Hu Junzhen Ren Mingliang Sun Renqiang Yang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(13):1558-1566
In this article, pendent thiophene (2‐butyl‐5‐octylthiophene) side chain is used to modify the backbone of the polymers containing benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD). Compared with the dodecyloxy side‐chained polymer (P1), pendent thiophene‐based polymers (P2 and P3) show similar number‐average molecular weight (Mn), polydispersity index, thermal stability (Td ~ 334–337 °C), and optical band gaps ( ) (~1.8 eV). Polymer (P2)‐based BDT with pendent thiophene and ethylhexyl‐modified TPD shows relatively low‐lying HOMO energy level (?5.52 eV) and nearly 1 V high open circuit voltage (VOC). The polymer solar cell devices based on three copolymers show power conversion efficiencies from 2.01% to 4.13%. The hole mobility of these polymers tested by space charge limited current method range from 3.4 × 10?4 to 9.2 × 10?4 cm2V?1s?1. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1558–1566 相似文献
9.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(13):1366-1382
Designing and tuning a copolymerization process to obtain specific material properties is still fundamentally empirical and requires the determination of apparent reactivity ratios rs. To this end, PEG–(MMA–DMAEMA)n copolymers obtained via ATRP of MMA and DMAEMA using a PEG‐based initiator in toluene were analyzed to extract monomer relative reactivities; the impact of changing solvent on the latter was also tested. Differing from previous free radical and controlled radical copolymerizations (CRcoP), we found that DMAEMA is preferentially included ( and ) in toluene; increasing the solvent polarity decreased the gap between rs. With these data, kMC simulations based on the copolymerization terminal model were used to investigate copolymer microstructure, which is not amenable to NMR investigation. kMC simulations evidenced both a gradient‐like nature of the copolymers and a somewhat unexpected qualitative change in the probability of finding MMA‐rich triads along the chain depending on initial feed composition. An additional DFT analysis suggested the likely formation of a DMAEMA:CuBr:2‐2′‐bipyridine complex, which being involved in the regeneration of reactive radicals from dormant species, is expected to locally increase DMAEMA concentration favoring its addition to the growing chains. The formation of such complex is also supported by 1H‐NMR experiments. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1366–1382 相似文献
10.
Hanbin Wang Nicolas Desilles Fabrice Burel 《Journal of polymer science. Part A, Polymer chemistry》2014,52(10):1493-1499
The cationic polymerization of dimethylketene is achieved in dichloromethane at ?30 °C, using a stoichiometric mixture of aluminum bromide (AlBr3) and tetra‐n‐butylammonium bromide (n‐Bu4N+Br?) as initiator. Characterizations by 1H and 13C NMR show that the resulting polymers have a perfect polyketonic microstructure. Capillary viscosity, DSC, and SEC analysis show that for a constant monomer/initiator ratio, polymers synthesized in the presence of tetra‐n‐butylammonium bromide are more crystalline and have better properties than those produced only with AlBr3. Melting temperatures, inherent viscosities and average molecular weights are systematically higher. A good linearity is observed between ln (inherent viscosity) versus ln for the system with n‐Bu4N+Br?, showing a good control of the molecular weight by the initial feed ratio. The effect of this compound suggests a reversible equilibrium between active and dormant species, which limits the transfer and/or termination reactions, and enables a better control of the cationic polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1493–1499 相似文献
11.
Nihan Nugay Turgut Nugay Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》2019,57(8):929-935
The synthesis of primary hydroxyl‐telechelic polyisobutylene, HOCH2‐PIB‐CH2OH, often yields product the number average terminal functionality ( ) of which is less than theoretical 2.0, typically = 1.75–1.95. Polyurethane (PU) prepared with such low‐cost imperfect PIB‐diols, unsurprisingly, exhibit poor overall properties. Herein we report that mechanical, rheological, and thermal properties of polyisobutylene‐based polyurethane (PIB‐PU) and PIB‐PU reinforced with organically modified montmorillonite (OmMMT) prepared with PIB‐diol of = 1.85 are significantly enhanced by glycerol. Specifically, we document that calculated minor amounts of glycerol substantially improves tensile strength, ultimate elongation, elastic modulus, toughness, rubbery plateau, flow temperature, creep, permanent set, rate of recovery after loading, and thermal properties of PIB‐PU and OmMMT‐reinforced PIB‐PU prepared with PIB‐diol of = 1.85. The observations are summarized and discussed in terms of chemistry, micromorphology, and viscoelasticity. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 929–935 相似文献
12.
Preparation and orthogonal postmodification of dual‐clickable polymer precursors bearing both aldehyde and alkyne groups 下载免费PDF全文
Lvhuan Lin Jianbing Huang Zhi'an Ma Hui Liang Jiang Lu 《Journal of polymer science. Part A, Polymer chemistry》2017,55(16):2650-2656
A new styrenic monomer 2‐propargyloxy‐5‐vinylbenzaldehyde (PVB) containing both aldehyde and alkyne reactive groups was designed for the synthesis and subsequent orthogonal postfunctionalization of dual‐clickable polymer precursor. Reversible addition‐fragmentation chain transfer polymerization of PVB afforded a structurally well‐defined polymer poly(2‐propargyloxy‐5‐vinylbenzaldehyde) (PPVB) bearing alkyne and aldehyde functionalities that are reactive towards azide ‐ and aminooxy‐containing molecules, respectively. Therefore, the resulting PPVB can be served as a dual‐clickable polymer scaffold for construction of multiple functional polymers via orthogonal alkyne–azide and aldehyde–aminooxy click reactions. Postpolymerization modification of PPVB sequentially with aminooxy‐terminated poly(ethylene oxide)s (H2NO‐PEO) and azide‐functionalized imidazolium‐type ionic liquid (N3‐IL·TFSI, having bis(trifluoromethane)sulfonamide, TFSI, counter‐anion) yielded an interesting multicomponent graft polymer PPVB‐g‐(PEO‐and‐IL·TFSI). After anion exchange of hydrophobic TFSI counter‐anion by bromide (Br) anion, the resulting graft copolymer PPVB‐g‐(PEO‐and‐IL·Br) becomes soluble in water, and its imidazolium units can capture negatively charged tetraphenylethylene disulfonate derivative (TPE‐2 ) guest molecule via electrostatic complexation to form in situ self‐assembled fluorescent nanoaggregates with colloidal stability imparted by hydrophilic PEO chains. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2650–2656 相似文献
13.
Aiqing Zhong Zidong He Hui Zhang Linfeng Xiong Yang Xu Tianqi Wang Minghong Zhou Kun Huang 《Journal of polymer science. Part A, Polymer chemistry》2016,54(19):3079-3085
In this article, we reported a facile method to in‐situ synthesize Au@PNIPAM‐b‐PPy nanocomposites with thermosensitive and photothermal effects using amphiphilic poly(N‐isopropylacrylamide)‐block‐poly(pyrrolylmethylstyrene) (PNIPAM‐b‐PPMS) diblock copolymers as ligands. The hydrophobic PPMS block can in‐situ reduce to zero‐valent gold and simultaneously be oxidatively copolymerized with the free pyrrole monomers to form a crosslinked and conjugated polypyrrole (PPy) layer. The hydrophilic PNIPAM block as a stabilizer can produce highly thermosensitive effect. Moreover, the resultant Au@PNIPAM‐b‐PPy nanomaterials show a strong absorption in the near infrared (NIR) region, which endowed the system excellent photothermal effect. On the basis of the PPy photothermal and PNIPAM thermosensitive effects, the above Au@PNIPAM‐b‐PPy nanomaterials show a reversible, soluble‐precipitate transition upon the NIR irradiation off‐on. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3079–3085 相似文献
14.
Frederik Wurm Francisco Javier López Villanueva Holger Frey 《Journal of polymer science. Part A, Polymer chemistry》2009,47(10):2518-2529
A convenient two‐step approach for the synthesis of ferrocenyl‐functionalized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different ABn type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end‐capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt‐catalyzed hydrosilylation polyaddition, branched, functionalized polydienes were obtained by a concurrent ABn + AR type of copolymerization with mono‐ and difunctional ferrocenyl silanes (fcSiMe2H or fc2SiMeH). Molecular weights of the branched polymers were in the range of 10,000 to 44,000 g/mol (SEC/MALLS). Because of the large number of functional end groups, high loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies showed full conversion of the functional silanes and incorporation into the branched polymer. Further studies using DSC, TGA, and cyclovoltammetry (CV) measurements have been performed. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2‐ and fc2SiMe‐units. The CVs of polymers modified with diferrocenylsilane units exhibit the pattern of communicating ferrocenyl sites with two distinct, separate oxidation waves. The polymers were also deposited on an electrode surface and the electrodes investigated via CV, showing formation of electroactive films with promising results for the use of the materials in biosensors. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2518–2529, 2009 相似文献
15.
Jason L. Freeman Justin R. Martin T. Ross Totsch Farid Marashi Nia Jianwei Wang Yuanli Zhang Benjamin Yancey Jeffrey L. Atkinson Christopher M. Lawson Gary M. Gray 《Journal of polymer science. Part A, Polymer chemistry》2016,54(22):3663-3674
The syntheses of a series of substituted polyphosphonates of the type [OP(X)(Ar)O(CH2)12]n (X = O, S, Se; Ar = phenyl, 2,2′‐bithienyl‐5‐yl) are reported. The s for the polyphosphonates range from 1.1 to 4.6 × 104 Da and are significantly higher than those previously reported for polyphosphonates synthesized via polycondensation reactions. Thermal characterization indicates that all of the polymers are in the rubbery state at room temperature and have thermal stabilities as high as 290 °C. The linear absorption spectra, emission spectra, and emission quantum yields of the 2,2′‐bithenyl‐5‐yl substituted polyphosphonates show distinct trends with respect to the chalcogen attached to the phosphorus. Solutions of these polymers show emission at wavelengths ranging from 380 to 400 nm and, depending on the choice of X, the quantum yields are considerably larger than that of 2,2′‐bithiophene. Nonlinear optical measurements of the polyphosphonates with 2,2′‐bithenyl‐5‐yl substituents show that nonlinear absorbance increases with increasing molecular weight of X. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3663–3674 相似文献
16.
The effects of counter anions on the dynamic mechanical response in polymer networks crosslinked by metal–ligand coordination 下载免费PDF全文
Ying-Li Rao Vivian Feig Xiaodan Gu Ging-Ji Nathan Wang Zhenan Bao 《Journal of polymer science. Part A, Polymer chemistry》2017,55(18):3110-3116
Metal–ligand coordination has been proven to be an attractive strategy to tune a polymer network's dynamic mechanical properties, such as self-healing ability. Nonetheless, the role of counter anions is often overlooked. To address this, a series of polydimethylsiloxane (PDMS) films crosslinked through lanthanide metal cations (Eu3+, Tb3+)–bipyridine interactions have been prepared and studied. Neutral 2,2'-bipyridine ligands were embedded into the linear polydimethylsiloxane (PDMS) chain through polycondensation. With nitrate ( ) as the coordinating anions, metal salts Eu(NO3)3 and Tb(NO3)3 were found to be ineffective crosslinkers. With noncoordinating anions, such as triflate (OTf-: CF3 ), metal salts Eu(OTf)3 and Tb(OTf)3 showed improved interaction strength with bipyridine ligands. Surprisingly, the addition of Eu(OTf)3 and Tb(OTf)3 salts also increased the d-spacing distances of the phase-segregated domains between metal–ligand complexes and the PDMS polymer backbone. For the Eu(OTf)3-, Tb(OTf)3-PDMS films, the much-improved self-healing abilities are attributed to the crosslinker dynamics and the enhanced chain mobility. This work underlines the importance of counter anions on the mechanical properties, and provides further guidance on the future design of self-healing metal−ligand crosslinked polymers.) © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3110–3116 相似文献
17.
Preparation and characterization of layer‐by‐layer self‐assembly membrane based on sulfonated polyetheretherketone and polyurethane for high‐temperature proton exchange membrane 下载免费PDF全文
Jinming Yu Shicheng Cheng Quantong Che 《Journal of polymer science. Part A, Polymer chemistry》2017,55(20):3446-3454
A concept of preparing high‐temperature proton exchange membranes with layer‐by‐layer (LBL) self‐assembly technique was proposed and the sulfonated polyetheretherketone (SPEEK) and polyurethane (PU) with 200 LBL deposition cycles denoting (SPEEK/PU)200 membrane was prepared in this research. Owing to the strong electrostatic interaction between ? group in SPEEK and ? C? N+ group in PU, (SPEEK/PU)200 membrane with LBL self‐assembly structure showed a favorable structural stability. The phosphoric acid (PA)‐doped (SPEEK/PU)200 membrane showed a higher proton conductivity relative to PA doped SPEEK/PU membrane by solution casting method (SPEEK/PU)200/40%PA membrane possessed a proton conductivity value of 2.90 × 10?2 S/cm at 150 °C under anhydrous conditions. The LBL self‐assembly structure provided a possibility to reduce the negative effect from polymer skeleton blocking charge carrier species even immobilizing protons. Moreover, the (SPEEK/PU)200 membrane presented the particularly noteworthy mechanical property even with PA doping. The tensile stress values at break were 72.8 and 24.1 MPa, respectively, for (SPEEK/PU)200 and (SPEEK/PU)200/40%PA membrane at room temperature, which were obviously higher than the reported values of 15.9 and 2.81 MPa for SPEEK/PU and SPEEK/PU/60%PA membrane. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3446–3454 相似文献
18.
Cationic ring‐opening polymerization of trimethylene carbonate to α,ω‐dihydroxy telechelic and star‐shaped polycarbonates catalyzed by reusable o‐benzenedisulfonimide 下载免费PDF全文
Hao Wu Yufeng Ji Zhenjiang Li Xin Wang Qiguo Zhang Saide Cui Wenzhuo Wu Jingjing Liu Kai Guo 《Journal of polymer science. Part A, Polymer chemistry》2015,53(6):729-736
Cationic ring‐opening polymerization of trimethylene carbonate using o‐benzenedisulfonimide as a reusable catalyst under mild conditions was described. The polymerization proceeded homogeneously without decarboxylation and poly(trimethylene carbonates) (PTMCs) were synthesized with well‐controlled molecular weights and narrow polydispersities (Mw/Mn = 1.12–1.18). The spectra of 1H‐NMR, SEC, and MALDI–ToF MS clearly demonstrated the incorporation of the initiator residue into the polymer chains and the controlled/living nature of the polymerizations. Furthermore, the catalyst can be easily recovered, and its efficiency was fully retained. In addition, 1,3‐propanediol, 1,1,1‐trimethylolpropane, and pentaerythritol were successfully used as initiators to produce telechelic and star‐shaped polycarbonates which were determined by intrinsic viscosity experiments. The number of arms estimated by the shrinking factors ( ) were 2.0, 2.6, and 3.5, respectively, indicating the successful syntheses of the two‐, three‐, and four‐armed PTMCs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 729–736 相似文献
19.
Sonashree Saxena Manickam Jayakannan 《Journal of polymer science. Part A, Polymer chemistry》2016,54(20):3279-3293
We report a new pH and enzyme dual responsive biodegradable polymer nanocarrier to deliver multiple anticancer drugs at the intracellular compartment in cancer cells. Natural l ‐aspartic acid was converted into multifunctional monomer and polymerized to yield new classes of biodegradable aliphatic polyester in‐build with pH responsiveness. The transformation of side chain BOC urethanes into cationic in the acidic endosomal environment disassembled the polymers nanoparticles (pH trigger‐1). The biodegradation of aliphatic polyester backbone by esterase enzyme ruptured the nanoassemblies and released the drugs in the cytoplasm (trigger‐2). The polymer scaffolds were capable of delivering multiple drugs such as doxorubicin, topotecan, and curcumin (CUR). The cytotoxicity of the nascent and drug‐loaded nanoparticles were tested in cervical (HeLa) and breast (MCF‐7) cancer cell lines. The nascent polymer nanoscaffolds were found to be nontoxic to cells whereas their drug‐loaded nanoparticles exhibited excellent killing. Confocal microscopic images revealed that the drug‐loaded polymer nanoparticles were taken up by the cells and the dual degradation process delivered the drugs to nucleus and established the proof‐of‐concept. The present investigation opens up new platform for l ‐amino acid based polyester scaffolds, for the first time, in the intracellular drug delivery in cancer treatment. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3279–3293 相似文献
20.
Nga H. Nguyen Xuefei Leng Hao‐Jan Sun Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3110-3122
The efficient Cu(0) wire‐catalyzed single‐electron transfer‐living radical polymerization (SET‐LRP) of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) in DMSO and binary mixtures of DMSO with H2O is reported. Addition of 10–80% H2O to DMSO resulted in an increase in the apparent rate constant of propagation ( ), corresponding to an increase in the polarity and extent of disproportionation. At higher H2O content, decreases, and in H2O is slightly lower than that in DMSO. This unexpected behavior was attributed to the physical inaccessibility of Cu(0) wire catalyst to the hydrophobic reactive centers of OEOMA and initiator which self‐assemble in H2O into micellar aggregates and vesicles. This hypothesis was confirmed by the faster polymerization in H2O than in DMSO during catalysis with Cu(0) nanoparticles generated by disproportionation of CuBr. SET‐LRP of OEOMA can be performed in protic and dipolar aprotic solvents in air by the addition of hydrazine hydrate. The polymerization exhibited no induction period and identical as in the degassed experiment, and led to polymers with narrow molecular weigh distribution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3110–3122 相似文献