共查询到20条相似文献,搜索用时 20 毫秒
1.
Ulrike Schreiber Benjamin Hosemann Sabine Beuermann 《Macromolecular chemistry and physics.》2011,212(2):168-179
Block copolymers of 1H,1H,2H,2H‐perfluorodecyl acrylate (AC8) were obtained from ARGET ATRP. To obtain block copolymers of low dispersity the PAC8 block was synthesized in anisole with a CuBr2/PMDETA catalyst in the presence of tin(II) 2‐ethylhexanoate as a reducing agent. The PAC8 block was subsequently used as macroinitiator for copolymerization with butyl and tert‐butyl acrylate carried out in scCO2. To achieve catalyst solubility in CO2 two fluorinated ligands were employed. The formation of block copolymers was confirmed by size exclusion chromatography and DSC.
2.
Dražen Pavlović Jeffrey G. Linhardt Jay F. Künzler Devon A. Shipp 《Macromolecular chemistry and physics.》2010,211(13):1482-1487
Amphiphilic ABCBA pentablock copolymers based on PVP, PS, and PDMS were synthesized using a combination of ATRP and RAFT polymerizations. The PVP‐block‐PS‐block‐PDMS‐block‐PS‐block‐PVP pentablock copolymer was characterized using a variety of chromatography and spectroscopic methods which showed that a high degree of end group and molecular weight control can be achieved. Preliminary analysis of the aqueous solution behavior of the pentablock copolymer showed that it self‐assembles in water in order to shield the PDMS and PS segments from the water.
3.
Luis Martín‐Gomis Marta Fernndez‐García Jos Luis de la Fuente Enrique Lpez Madruga María L. Cerrada 《Macromolecular chemistry and physics.》2003,204(16):2007-2016
The physical properties of well‐defined poly(butyl methacrylate)‐block‐poly(butyl acrylate)‐block‐poly(butyl methacrylate) (PBMA‐b‐PBA‐b‐PBMA) triblock copolymers synthesized by atom transfer radical polymerization (ATRP) are reported. The glass transition and the degradation temperature of copolymers were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC measurements showed phase separation for all of the copolymers with the exception of the one with the shortest length of either inner or outer blocks. TGA demonstrated that the thermal stability of triblock copolymers increased with decreasing BMA content. Dynamic mechanical analysis was used for a preceding evaluation of adhesive properties. In these block copolymers, the deformation process under tension can take place either homogeneously or by a neck formation depending on the molecular weight of the outer BMA blocks and on the length of the inner soft BA segments. Microindentation measurements were also performed for determining the superficial mechanical response and its correlation with the bulk behavior.
4.
Massimo Lazzari Oscar Chiantore Raniero Mendichi M. Arturo Lpez‐Quintela 《Macromolecular chemistry and physics.》2005,206(14):1382-1388
Summary: The synthesis of polyacrylonitrile‐block‐polystyrene (PAN‐b‐PS) copolymers by atom transfer radical polymerization (ATRP) is reported. Chain extension of bromine terminated PAN macroinitiators with styrene was performed using a CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine catalyst system and 2‐cyanopyridine as a solvent. The first‐order kinetic plots of styrene consumption showed a significant curvature, indicating a progressive decrease in the concentration of active species during copolymerization. The loss of the bromide end group was mainly ascribed to the elimination of HBr, as shown by 1H NMR spectroscopy. By varying the molar ratio of either the catalyst or the monomer to the initiator, a series of PAN‐b‐PS copolymers were prepared, with polydispersities as low as 1.3, and molar compositions ranging from 8.6/91.4 to 35.5/64.5.
5.
Xiaohua He Liyuan Liang Meiran Xie Yiqun Zhang Shaoliang Lin Deyue Yan 《Macromolecular chemistry and physics.》2007,208(16):1797-1802
A new strategy to synthesize a series of well‐defined amphiphilic PEO‐b‐PS‐b‐PCL block copolymers is presented. First, bromine‐terminated diblock copolymers PEO‐b‐PS‐Br are prepared by ATRP of styrene, and converted into azido‐terminated PEO‐b‐PS‐N3 diblock copolymers. Then propargyl‐terminated PCL is prepared by ROP of ε‐caprolactone. The PEO‐b‐PS‐b‐PCL triblock copolymers with from 1.62 × 104 to 1.96 × 104 and a narrow PDI from 1.09 to 1.19 are finally synthesized from these precursors. The structures of these triblock copolymers and their precursors have been characterized by NMR, IR, and GPC analysis.
6.
Radical Trap‐Assisted Atom Transfer Radical Coupling of Diblock Copolymers as a Method of Forming Triblock Copolymers 下载免费PDF全文
Benjamin D. McFadden Maya M. Arce Elizabeth M. Carnicom Julie Herman Jessica Abrusezze Eric S. Tillman 《Macromolecular chemistry and physics.》2016,217(22):2473-2482
The formation of ABA‐type triblock copolymers is studied as a function of chain end structure of the second block (benzylic alkyl bromides compared to α‐bromo esters) and the inclusion of the radical trap 2‐methyl‐2‐nitrosopropane (MNP) in the coupling reaction. In the case of coupling poly(methyl methacrylate)‐block‐polystyrene (PMMA‐b‐PSBr), both traditional atom transfer radical coupling (ATRC) reactions and analogous radical trap‐assisted ATRC (RTA‐ATRC) reactions lead to ABA‐type triblock copolymers. Contrastively, coupling of polystyrene‐block‐poly(methyl acrylate) precursors is unsuccessful in ATRC reactions lacking the nitroso radical trap, yet forming high amounts of triblock in analogous RTA‐ATRC reactions, consistent with lower KATRP values of the chain end α‐bromo ester. Synthesis of the triblocks is also attempted using coupling reactions of dibrominated PS and monobrominated poly(methyl acrylate), relying on selective coupling to be successful. In the presence of the radical trap MNP, substantial coupling is observed with gel permeation chromatography data indicating the formation of the triblock. Traditional ATRC reactions performed in an analogous manner do not produce the triblock to an appreciable extent, with lowered extents of coupling overall.
7.
Christine Strissel Krzysztof Matyjaszewski Oskar Nuyken 《Macromolecular chemistry and physics.》2003,204(9):1169-1177
Alternating copolymers of 1,3‐diisopropenylbenzene and 1,1,3,3‐tetramethyldisiloxane were synthesized by hydrosilylation–polyaddition. These linear copolymers were functionalized at both ends with 2‐bromoisobutyryl or benzyl chloride moieties. Subsequently, the obtained organomodified siloxane‐containing macroinitiators were successfully used for the preparation of ABA‐type block copolymers by atom transfer radical polymerization (ATRP) of styrene and tert‐butyl acrylate. The high chain‐end functionality of the macroinitiators was confirmed by 1H NMR analysis of the macroinitiators and GPC measurements of the obtained ABA‐type block copolymers. The macroinitiator peaks disappeared in GPC traces after ATRP, and the obtained block copolymers showed a significantly narrower molecular‐weight distribution than the macroinitiators.
8.
Ying Zhang Im Sik Chung Jinyu Huang Krzysztof Matyjaszewski Tadeusz Pakula 《Macromolecular chemistry and physics.》2005,206(1):33-42
Summary: A series of telechelic OH polysulfones (PSU) were converted to atom transfer radical polymerization (ATRP) macroinitiators by reaction with 2‐bromoisobutyryl bromide. Three macroinitiators with different chain lengths were extended with poly(butyl acrylate) (PBA) to form ABA triblock copolymers. The structure and dynamics of the ABA triblock copolymers with PSU central segments and various molecular weight PBA side chains were investigated by small‐angle X‐ray scattering and rheology. The block copolymers form micelles with a PSU core and PBA corona. The length of each block has an important effect on the structure and resulting dynamics of the copolymers. Dynamic mechanical measurements indicate three relaxation modes: (i) PBA segmental relaxation at high frequency; (ii) PBA relaxation of the corona block at intermediate frequency; (iii) an additional relaxation process related to structural rearrangement of the micelles at low frequency. The shear modulus plateau corresponding to a soft rubbery state extends over a very broad time or temperature range because of this slow additional relaxation.
9.
Wojciech Jakubowski Betul Kirci‐Denizli Roberto R. Gil Krzysztof Matyjaszewski 《Macromolecular chemistry and physics.》2008,209(1):32-39
The bromine chain‐end functionality of polystyrene (PSt) prepared by activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) was analyzed using 500 MHz 1H nuclear magnetic resonance (NMR). Bulk polymerization of styrene (St) was carried out with 50 ppm of copper in the presence of tris[2‐(dimethylamino)ethyl]amine (Me6TREN) ligand and tin(II) 2‐ethylhexanoate [Sn(EH)2] reducing agent at 90 °C. Due to the use of a low concentration of an active Cu/ligand catalyst complex, it was possible to significantly decrease the occurrence of catalyst‐based side reactions (β‐H elimination). As a result, compared to PSt prepared via normal ATRP, PSt with improved chain‐end functionality was obtained. For example, at 92% monomer conversion in normal ATRP only 48% of chains retained chain‐end functionality, whereas 87% of the chains in an ARGET ATRP still contained halogen functionality. PSt with controlled molecular weight ( = 11 600 g · mol?1, = 9 600 g · mol?1) and narrow molecular weight distribution ( = 1.14) was prepared under these conditions. In addition, as a result of decreased frequency of side reactions in ARGET ATRP, PSt with relatively high molecular weight was successfully prepared ( = 185 000 g · mol?1, = 1.35).
10.
Robert B. Grubbs 《Macromolecular chemistry and physics.》2005,206(6):625-627
Summary: Anionic polymerization has proven especially useful for the precise construction of multiblock copolymers with controlled compositions and narrow molecular weight distributions. The block copolymer sequences which can be easily prepared are however largely restricted by the relative nucleophilicities of the anionic species involved. This highlight discusses a recent article by Wiesner and co‐workers (Macromol. Rapid Commun. 2004 , 25, 1889) in which the effective preparation of ABC triblock copolymers, with poly(ethylene oxide) as the central block, through the combination of living anionic polymerization, atom transfer radical polymerization, and polymer modification techniques is described. This method will prove to have a great deal of versatility in allowing the incorporation of PEO blocks in interior positions of block copolymers.
11.
Wolf Hiller Pritish Sinha Harald Pasch 《Macromolecular chemistry and physics.》2007,208(18):1965-1978
Blends and copolymers of PS and PMMA were analysed by LC coupled to 1H NMR at the critical point of adsorption. The separation of the polymers was achieved at chromatographic conditions that correspond to the critical point of PS and the size‐exclusion mode of PMMA. Copolymers and blends were analysed by on‐line coupled 1H NMR. For the homopolymer blends, separation into the components was achieved, while the copolymers were separated with regard to the block lengths of the PMMA blocks. The tacticity of the PMMA blocks could be determined as a function of molar mass by HPLC‐NMR. This technique can deliver the true molar mass and the true chemical composition of the copolymers.
12.
Mustafa Degirmenci Selma Alter Nasrettin Genli 《Macromolecular chemistry and physics.》2011,212(15):1575-1581
A combination of ATRP and “click” chemistry is employed for efficient preparation of a novel well‐defined mid‐chain functional macrophotoinitiator of polystyrene. Bromo‐terminated polystyrene (PSt‐Br) is prepared by ATRP of styrene using a methyl‐2‐bromopropanoate initiator with CuBr/PMDETA. Subsequently, PSt‐Br is converted to PSt‐N3 by a simple nucleophilic substitution reaction. A dialkyne‐functionalized photoinitiator (alkyne‐PI‐alkyne) is synthesized using a dihydroxy‐functional photoinitiator and propargyl bromide. Then the “click” reaction between PSt‐N3 and alkyne‐PI‐alkyne is performed by Cu(I) catalysis. Spectroscopic studies reveal that low‐polydispersity polystyrene with the desired photoinitiator functionality in the middle of the chain (PSt‐PI‐PSt) is obtained.
13.
Zhiqiang Cao Wenguang Liu Guixiang Ye Xiaoli Zhao Xiaoze Lin Peng Gao Kangde Yao 《Macromolecular chemistry and physics.》2006,207(24):2329-2335
Summary: Tri‐arm star diblock copolymers, poly(2‐hydroxyethyl methacrylate)‐block‐poly(N‐isopropylacrylamide) [P(HEMA‐b‐NIPAAm)] with PHEMA and PNIPAAm as separate inner and outer blocks were synthesized via a two‐step ATRP at room temperature. The formation, molecular weight and distribution of polymers were examined, and the kinetics of the reaction was monitored. The PDI of PHEMA was shown to be lower, indicating well‐controlled polymerization of trifunctional macro‐initiator and resultant star copolymers. The thermoresponsive behavior of diblock copolymer aqueous solution were studied by DSC, phase diagrams, temperature‐variable 1H NMR, TEM and DLS. The results revealed that introducing a higher ratio of HEMA into copolymers could facilitate the formation of micelles and the occurrence of phase transition at lower temperatures. TEM images showed that I‐(HEMA40‐NIPAAm320)3 solutions developed into core‐shell micelles with diameters of approximately 100 nm. I‐(HEMA40‐NIPAAm320)3 was used as a representative example to elucidate the mechanism underlying temperature‐induced phase transition of copolymer solution. In this study we proposed a three‐stage transition process: (1) separately dispersed micelles state at ≈17–22 °C; (2) aggregation and fusion of micelles at ≈22–29 °C; (3) sol‐gel transition of PNIPAAm segments at ≈29–35 °C, and serious syneresis of shell layers.
14.
Jeffrey Pyun Shijun Jia Tomasz Kowalewski Krzysztof Matyjaszewski 《Macromolecular chemistry and physics.》2004,205(4):411-417
Summary: The synthesis of an ABC triblock copolymer containing glassy and rubbery segments was conducted using a combination of living anionic and atom transfer radical polymerizations (ATRP). A poly(dimethylsiloxane) (pDMS) macroinitiator ( = 6 200; = 1.19) was prepared by living anionic ring‐opening polymerization, followed by hydrosilation reactions to incorporate 2‐bromoisobutyrate end groups for initiation of ATRP. The ATRP of styrene (S) using the pDMS macroinitiator yielded a diblock copolymer ( = 66 730; = 1.38). Chain extension of the pDMS‐b‐pS macroinitiator with 3‐(dimethoxymethylsilyl)propyl acrylate (DMSA) by ATRP yielded an ABC triblock copolymer. The latter reactive segment was covalently attached to silanol groups on a silicon wafer. The presentation of either glassy pS or flexible pDMS segments of the brushes attached to the surface was reversibly controlled by treatment with selective solvents for each segment.
15.
Mathias Hehn Wolf Hiller Thomas Wagner Jürgen Thiel Harald Pasch 《Macromolecular chemistry and physics.》2012,213(4):401-410
The online coupling of size‐exclusion chromatography and NMR is used to characterize block copolymers consisting of polyisoprene (PI) and poly(methyl methacrylate) (PMMA) regarding their distributions of molar mass (MMD) and chemical composition (CCD). Using the CCD, $\overline{M}_{\rm n}$ and $\overline{M}_{\rm w}$ are calculated on the basis of PI and PMMA homopolymer calibrations. The microstructure distribution of PMMA and the distribution of isomeric units of PI in dependence of molar mass is also demonstrated. Furthermore, a simulation analysis is presented for a bimodal eluting sample. It allows for full separation, quantification and molar mass determination of the coeluting co‐ and homopolymer fractions. The quantification of the fractions is verified by liquid chromatography at critical conditions. 相似文献
16.
Yanika Schneider Brian T. McVerry Guillermo C. Bazan 《Macromolecular chemistry and physics.》2011,212(5):507-514
Hydrophilic polyolefin materials were prepared by grafting tBA from PE macroinitiators bearing functionalized norbornene units capable of initiating an ATRP. This method produced semicrystalline graft copolymers (PE‐graft‐PtBA) with narrow molecular weight distributions (1.2–1.4) and tunable tBA content (2–21 mol‐%). Incorporation of tBA resulted in a decrease in crystallinity, but little change in the melting point of the products. Subsequently, the tBA moieties were converted into acrylic acid units through chemical and thermal means to generate PE‐graft‐PAA copolymers. The increased hydrophilicity of the resulting materials was verified by ATR‐IR, solid‐state 13C NMR spectroscopy, contact angle measurements, and TGA.
17.
Xinde Tang Longcheng Gao Xinghe Fan Xiaochao Liang Qifeng Zhou 《Macromolecular chemistry and physics.》2009,210(18):1556-1562
The self‐assembly and photoresponsivity of amphiphilic azobenzene‐containing ABA triblock copolymers PA6Cm‐b‐PEGn‐b‐PA6Cm synthesized by atom transfer radical polymerization (ATRP) were reported. Different self‐assembly morphologies formed by the gradual addition of water to the copolymer solutions in THF. The formation process and aggregate morphology were characterized by UV–Visible spectroscopy and transmission electron microscope (TEM). The triblock copolymers start to form aggregates at the critical water content (CWC). With the addition of water, the aggregates show different morphologies, such as spherical micelles, vesicles, network‐like aggregates, and colloidal spheres, which involves the transformation between primary and secondary aggregates and the association/disassociation of aggregates. Photoresponsive property and aggregation behavior of these copolymers in solution under UV–Visible light irradiation were also investigated.
18.
Summary: Diblock copolymers, poly(trimethylene oxide)‐block‐poly(styrene)s abbreviated as poly(TMO)‐block‐poly(St), and triblock copolymers, poly(TMO)‐block‐poly(St)‐block‐poly(MMA)s (MMA = methyl methacrylate), with controlled molecular weight and narrow polydispersity have been successively synthesized by a combination of atom transfer radical polymerization (ATRP) and cationic ring‐opening polymerization using the bifunctional initiator, 2‐hydroxylethyl α‐bromoisobutyrate, without intermediate function transformation. The gel permeation chromatography (GPC) and NMR analyses confirmed the structures of di‐ and triblock copolymers obtained.
19.
Eva Díez‐Pea Isabel Quijada‐Garrido Jos Manuel Barrales‐Rienda Ingo Schnell Hans Wolfgang Spiess 《Macromolecular chemistry and physics.》2004,205(4):430-437
Summary: The nature of the pH dependent collapse of poly(methacrylic acid) (PMAA) hydrogels is investigated using recent 1H solid‐state NMR methods. In aqueous solution, PMAA changes from an expanded conformation at high pHs to a compact contracted form at low pHs, where hydrogen bonds play a central role. In solid‐state 1H NMR spectra, recorded under fast magic angle spinning (MAS), dried PMAA samples previously collapsed at low pHs show characteristic signals in the spectral region of the carboxylic acid protons. With the aid of 2D 1H‐1H double‐quantum (DQ) MAS NMR spectra, three signals can be distinguished at 8, 10.5 and 12.5 ppm, which are attributed to free carboxylic groups and two different types of hydrogen bonded forms, respectively. The 12.5 ppm signal arises from the hydrogen bond with the shortest H? H distance, corresponding to the form that is most stable with respect to increasing temperature and pH. The weaker hydrogen‐bonded form (with a signal at 10.5 ppm) requires a slightly lower pH, while the free acid signal (at 8 ppm) emerges under the most acidic medium. Moreover, the stabilities of the hydrogen‐bonded carboxylic acid dimers can be inferred from the proton‐proton distances within the dimers, i.e. (275 ± 5) pm and (295 ± 15) pm for the protons at 12.5 and 10.5 ppm, respectively, which are determined by means of DQ MAS sideband patterns. Both the stability of the hydrogen bonds and the acidity of the protons may be related to the stereochemistry and the conformation of the PMAA chains.
20.
Kyung‐Youl Baek Hyun‐Ji Kim Sang‐Ho Lee Kie‐Yong Cho Hyeong Tae Kim Seung Sang Hwang 《Macromolecular chemistry and physics.》2010,211(6):613-617
Well‐defined sulfonated block copolymers were prepared by direct thermolysis with block copolymers of n‐butyl acrylate (nBA) and neopentyl styrene sulfonated (NSS), which were synthesized by Cu‐based living radical polymerization ( <1.20). A simple thermal process for 10 min at 150 °C completely deprotected the neopentyl groups in the poly(NSS) block segment to give fully sulfonated polystyrene backbone. SAXS profile of the block copolymer with 47 wt.‐% of poly(NSS) showed lamella structure, which appeared more clearly with long ranged order after sulfonation of the block copolymer.