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991.
Daniel Leibig Margarita Messerle Tobias Johann Christian Moers Farzaneh Kaveh Hans-Jürgen Butt Doris Vollmer Axel H. E. Müller Holger Frey 《Journal of polymer science. Part A, Polymer chemistry》2020,58(1):181-192
Well-defined polystyrene homopolymers with surface-adhesive triethoxysilyl end group were synthesized via living carbanionic polymerization, epoxide end-functionalization and subsequent hydrosilylation with triethoxysilane. Grafting-to performance of polymers with various molecular weight (Mn = 3000–14,000 g mol−1) to a silicon surface was examined in dependence of reaction time, polymer concentration, solvent and number of alkoxysilyl end groups. Crosslinkable polymers for surface modification were synthesized by statistical carbanionic copolymerization of 4-vinylbenzocyclobutene (4-VBCB) and styrene, followed by epoxide end-functionalization and triethoxysilane modification (Mn = 4000–14,000 g mol−1). The copolymers were characterized by 1H-NMR, THF-SEC, and matrix-assisted laser desorption and ionization time-of-flight mass spectrometry. In situ 1H-NMR kinetic studies in cyclohexane-d12 provided information regarding the monomer gradient in the polymer chains, with styrene being the more reactive monomer (rs = 2.75, r4-VBCB = 0.23). Thin polymer films on silicon wafers were prepared by grafting-to surface modification under conditions derived for the polystyrene homopolymer. The traceless, thermally induced crosslinking reaction of the benzocyclobutene units was studied by DSC in bulk as well as in 3–6 nm thick polymer films. Crosslinked films were analyzed by atomic force microscopy, ellipsometry, and nanoindentation, showing smooth polymer films with an increased modulus. © 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 181–192 相似文献
992.
Dr. Caroline M. Storey Dr. Matthew R. Gyton Dr. Rhiann E. Andrew Dr. Adrian B. Chaplin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14715-14723
Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C2H4)][BArF4] (n=12, 14, 16; ArF=3,5-(CF3)2C6H3)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu2C6H3) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH2)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C2H4)][BArF4] and solvent effects. 相似文献
993.
Although intelligent hydrogels have shown bright potential application in biomedical fields,they were prepared by conventional methods and still face many serious challenges,such as uncontrollable stimulus-response and low response sensitivity.Recently,RAFT polymerization provides a versatile strategy for the fabrication of intelligent hydrogels with improved stimulus-response properties,owing to the ability to efficiently construct hydrogel precursors with well-defined structure,such as block copolymer,graft copolymer,star copolymer.In this review,we summarized the recent progress on intelligent hydrogels based on RAFT polymerization with emphasis on their fabrication strategies and applications for controlled drug delivery. 相似文献
994.
Volume expansion and polysulfide shuttle effect are the main barriers for the commercialization of lithium-sulfur(Li-S) battery.In this work,we in-situ polymerized a cross-linked binder in sulfur cathode to solve the aforementioned problems using a facile method under mild conditions.Polycarbonate diol(PCDL),triethanolamine(TEA) and hexamethylene diisocyanate(HDI) were chosen as precursors to prepare the cross-linked binder.The in-situ polymerized binder(PTH) builds a strong network in sulfur cathode,which could restrain the volume expansion of sulfu r.Moreover,by adopting functional groups of oxygen atoms and nitrogen atoms,the binder could effectively facilitate transportation of Li-ion and adsorb polysulfide chemically.The Li-S battery with bare sulfur and carbon/sulfur composite cathodes and cross-linked PTH binder displays much better electrochemical performance than that of the battery with PVDF.The PTH-bare S cathode with a mass loading of 5.97 mg/cm^2 could deliver a capacity of 733.3 mAh/g at 0.2 C,and remained 585.5 mAh/g after 100 cycles.This in-situ polymerized binder is proved to be quite effective on restraining the volume expansion and suppressing polysulfide shuttle effect,then improving the electrochemical performance of Li-S battery. 相似文献
995.
《中国化学快报》2020,31(6):1660-1664
Poly(N,N-dimethyl acrylamide)-block-poly(styrene)-block-poly(N,N-dimethyl acrylamide)(PDMAc-bPSt-b-PDMAc) amphiphilic triblock copolymer micro/nano-objects were synthesized through reversible addition-fragmentation chain transfer(RAFT) dispersion polymerization of St mediated with poly(N,Ndimethyl acrylamide) trithiocarbonate(PDMAc-TTC-PDMAc) bi-functional macromolecular RAFT agent.It is found that the morphology of the PDMAc-b-PSt-b-PDMAc copolymer micro/nano-objects like spheres,vesicles and vesicle with hexagonally packed hollow hoops(HHHs) wall can be tuned by changing the solvent composition.In addition,vesicles with two sizes(600 nm,264 nm) and vesicles with HHHs features were also synthesized in high solid content systems(30 wt% and 40 wt%,respectively).Besides,as compared with typical AB diblock copolymers(A is the solvophilic,stabilizer block,and B is the solvophobic block),ABA triblock copolymers tend to form higher order morphologies,such as vesicles,under similar conditions.The finding of this study provides a new and robust approach to prepare block copolymer vesicles and other higher order micelles with special structure via PISA. 相似文献
996.
可控/“活性”自由基聚合(CLRP)可以用于制备分子量分布窄、分子链缺陷少的聚合物,如聚乙烯(PE)、聚氯乙烯(PVC)、聚偏氯乙烯(PVDC)和聚偏氟乙烯(PVDF),且易控制上述单体与其他单体共聚得到嵌段聚合物。本文调研了近年来可控/“活性”自由基聚合(如碘转移聚合(ITP)、氮氧稳定自由基聚合(NMP)、可逆加成断裂链转移(RAFT)聚合和金属催化的活性自由基聚合(OMRP)等)制备聚乙烯和聚卤代烯烃等方面的工作,并指出了未来的发展方向。 相似文献
997.
998.
Yu Hoshino Shohei Taniguchi Hinata Takimoto Sotaro Akashi Sho Katakami Yusuke Yonamine Yoshiko Miura 《Angewandte Chemie (International ed. in English)》2020,59(2):679-683
Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences. 相似文献
999.
Zilong Wu Kenward Jung Cyrille Boyer 《Angewandte Chemie (International ed. in English)》2020,59(5):2013-2017
This contribution details an efficient and controlled photopolymerization regulated by far‐red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q‐bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight. 相似文献
1000.
Ross F. Koby Alicia M. Doerr Nicholas R. Rightmire Nathan D. Schley Brian K. Long Timothy P. Hanusa 《Angewandte Chemie (International ed. in English)》2020,59(24):9542-9548
Milling two equivalents of K[1,3‐(SiMe3)2C3H3] (=K[A′]) with MgX2 (X=Cl, Br) produces the allyl complex [K2MgA′4] ( 1 ). Crystals grown from toluene are of the solvated species [((η6‐tol)K)2MgA′4] ([ 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η1) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η3‐allyl configuration on Mg is energetically preferred over the η1‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to K[A′] and greater than the homometallic magnesium complex [{MgA′2}2]. 相似文献