Tertiary amines were found to remarkably enhance the catalytic activity of ATRP catalysts CuBr/tris[(2‐pyridyl)methyl]amine and CuBr/tris[2‐(dimethylamino)ethylamine]. These two catalysts alone failed to polymerize MA, MMA, and styrene at reduced catalyst concentrations. With tertiary amines such as triethylamine both catalysts could mediate fast polymerizations of the three monomers in a controlled manner at as low as 1 mol‐% catalyst relative to initiator. A mechanism study showed that tertiary amines reduced copper(II) complexes to active copper(I) complexes.
The hemoprotein horseradish peroxidase (HRP) catalyzes the polymerization of N‐isopropylacrylamide with an alkyl bromide initiator under conditions of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) in the absence of any peroxide. This is a novel activity of HRP, which we propose to name ATRPase activity. Bromine‐terminated polymers with polydispersity indices (PDIs) as low as 1.44 are obtained. The polymerization follows first order kinetics, but the evolution of molecular weight and the PDI upon increasing conversion deviate from the results expected for an ATRP mechanism. Conversion, and PDI depend on the pH and on the concentration of the reducing agent, sodium ascorbate. HRP is stable during the polymerization and does not unfold or form conjugates.
Summary: Mesoporous silica was used as substrate for the grafting of alkyl halides initiators. The control over the surface‐initiated polymerization of styrene and MMA, in terms of molar mass and molar mass distribution, was successfully achieved using an ATRP mechanism. The occurrence of the polymerization inside the mesopores was confirmed by thermogravimetric analysis.
Transmission electron microscopy and schematic representation of mesoporous silica functionalized by the anchored iniator (left) and the grafted polymer (right). 相似文献
Summary: RAFT is applied to the dendronized macromonomers of the first and second generation, 1 and 2 , respectively. Good results are obtained in the presence of AIBN as radical initiator, with compound 6 as mediator and at mediator to monomer ratios of 2:200 for monomer 1 ( = 320 000, PDI = 1.24) and monomer 2 ( = 178 000, PDI = 1.20). The common characteristics of a controlled polymerization are reasonably met. The more sterically demanding G2 monomer 2 requires higher polymerization temperatures.
A novel helical poly(macromonomer) [poly(M‐PS): absolute = 82 800–252 000, determined by GPC/RALLS] with a polyacetylene main chain and polystyrene (PS) side chains was synthesized by the polymerization of acetylene‐terminated M‐PS [ = 2 000, / = 1.20, = 18] with an Rh catalyst. M‐PS was prepared by ATRP of styrene using the acetylene‐containing initiator 2‐bromo‐2‐methylpropionic acid (S)‐1‐methylpropargyl ester ( l ). In solutions, poly(M‐PS) exhibited an intense CD signal at 345–355 nm, indicating that it possessed a predominantly one‐handed helical conformation. Poly(M‐PS) had a stable helical conformation irrespective of solvents and temperature.
We report a new type of step‐growth radical addition‐coupling polymerization (RACP) involving consecutive addition of carbon‐centered radical derived from α,α′‐dibromo dibasic ester to NO double bond of C‐nitroso compound followed by cross‐coupling of carbon‐centered radical and in situ formed nitroxyl radical, which produces alternating copolymers with high molecular weight and unimodal molecular weight distribution from saturated and unsaturated monomers.
Amphiphilic star shaped polymers with poly(ethylene oxide) (PEO) arms and cross‐linked hydrophobic core were synthesized in water via either conventional free radical polymerization (FRP) or atom transfer radical polymerization (ATRP) techniques using a simple “arm‐first” method. In FRP, PEO based macromonomers (MM) were used as arm precursors, which were then cross‐linked by divinylbenzene (DVB) using 2,2′‐azoisobutyronitrile (AIBN). Uniform star polymers ( < 1.2) were achieved through adjustment of the ratio of PEO MM, DVB, and AIBN. While in case of ATRP, both PEO MM, and PEO based macroinitiator (MI) were used as arm precursors with ethylene glycol diacrylate as cross‐linker. Even more uniform star polymers with less contamination by low MW polymers were obtained, as compared to the products synthesized by FRP.
A novel method is described for transforming an anionic polymerization process into a cationic polymerization process assisted by organosilyl groups. The reaction of the p‐tolyldimethylsilyl end group of polystyrene and trifluoromethanesulfonic acid produced a silyl triflate end group that served as a macroinitiator for the living cationic polymerization of isobutyl vinyl ether. The Si O linkage in the block copolymers underwent specific cleavage by reaction with tetrabutylammonium fluoride.
Well‐defined polymethylene‐block‐polystyrene (PM‐b‐PS) diblock copolymers were synthesized via a combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) of styrene. A series of hydroxyl‐terminated polymethylenes (PM‐OHs) with different molecular weight and narrow molecular weight distribution were prepared using living polymerization of ylides following efficient oxidation in a quantitive functionality. Then, the macroinitiators (PM‐MIs ( = 1 900–15 000; PDI = 1.12–1.23)) transformed from PM‐OHs in ≈ 100% conversion initiated ATRPs of styrene to construct PM‐b‐PS copolymers. The GPC traces indicated the successful extension of PS segment ( of PM‐b‐PS = 5 000–41 800; PDI = 1.08–1.23). Such copolymers were characterized by 1H NMR and DSC.
Summary: A novel hydroxyl‐functionalised initiator for atom transfer radical polymerisation (ATRP) was synthesised by esterification reaction of a non‐reducing sugar, meso‐inositol. Due to steric hindrance, one of the six hydroxyl groups present in the sugar was not derivatised to the corresponding 2‐bromoisobutyrate. The macroinitiator was used in ambient temperature ATRP of a hydrophobic monomer, methyl methacrylate (MMA) and a hydrophilic monomer, oligoethylene glycol methacrylate (OEGMA) using tri(ethylene glycol) monomethyl ether (TEGMME) as the polymerisation solvent and CuCl/CuCl2/PMDETA as the catalytic system. Under these conditions, polymerisation proceeded on to high conversion while maintaining low polydispersity giving well‐defined five‐arm star polymers. Hydrolysis under basic conditions was carried out to deduce the number of linear chains that were attached to the sugar.
The IUPAC recommended factor 2 preceding rate coefficients in the radical termination kinetic equations is claimed to be incorrect and confusing. This recommendation can lead to incorrect analysis of experimental data, especially while applying kinetic Monte Carlo simulations. The statement is based on the derivation of the corresponding relationships.
Summary: A new approach to the preparation of water soluble polymer in inverse miniemulsions is proposed. A redox initiation system consisting of ceric ions and carbohydrate‐based surfactant Span 60 as a reducing agent is successfully used for the polymerization of AAm. This initiation system provides chain nucleation and growth near interfacial boundaries. As a result, stable uniform latex with particle radius of about 50–70 nm is obtained. The prepared PAAm has a rather high of up to about 2 × 106 Da.
Structured hybrid nanoparticles were synthesized via surface‐initiated atom transfer radical polymerization of MMA from ordered mesoporous silica (OMS) nanoparticles with various morphologies. The design of the OMS particles was adjusted to target either spherical core‐shell or cylindrical morphologies with a mean diameter below 400 nm. The polymer growth via ATRP from the silica surface was well‐controlled as demonstrated by the macromolecular characteristics of the grafted chains. Original hybrid multilayered nanoparticles composed of either a dense silica core or hollow core; an inner OMS shell showing radial orientation of the mesopores and an outer PMMA shell with controlled thickness were successfully prepared.
Mussel adhesives function as tools for surface modifications of a wide variety of materials due to their remarkable adhesion properties. Herein, a combination of bioinspired mussel adhesives based on a dopamine derivative, polymer chemistry, and well‐established Diels–Alder (DA) chemistry leads to a bioinspired switchable surface system that possesses the capability of attaching and detaching specific polymers on demand. A dopaminemaleimide compound, which has been attached to a gold surface under maritime conditions undergoes DA‐ and retro‐DA‐click‐conjugations with cyclopentadiene‐carrying PEG chains. The surface attachment and the subsequent DA/rDA cycles are evidenced via XPS analysis.
Summary: The recently developed initiation system, activators generated by electron transfer (AGET), is used in atom transfer radical polymerization (ATRP) in the presence of a limited amount of air. Ascorbic acid and tin(II ) 2‐ethylhexanoate are used as reducing agents in miniemulsion and bulk, respectively. An excess of reducing agent consumes the oxygen present in the system and, therefore, provides a deoxygenated environment for ATRP. ATRP of butyl acrylate is successfully carried out in miniemulsion and in the presence of air. During polymerization the radical concentration remains constant. The polymerization reaches over 60% monomer conversion after 6 h, which results in polymers with a predetermined molecular weight = 14 000 g · mol−1 and a low polydispersity ( = 1.23). AGET ATRP of styrene is also successful in bulk in the presence of air, as evidenced by linear semi‐logarithmic kinetics, which leads to polystyrene with an of 13 400 g · mol−1 and a low polydispersity index ( = 1.14).
Appearance of miniemulsion before and after the reducing agent ascorbic acid was added (left); and GPC traces representing molecular weights during the AGET ATRP of BA in miniemulsion in the presence of air (right). 相似文献
In this article we provide a brief summary of computational techniques applied to investigate polymerization reactions in general, with a focus on systems under confinement and initiated from surfaces. We concentrate on two major classes of techniques, i.e., stochastic methods and molecular modeling. We describe the major principles of the two classes of methodologies and point out their strengths and weaknesses. We review a variety of studies from the literature and conclude with an outlook of these two classes of computer simulation approaches as they are applied to “grafting from” polymerizations.
A PTFE film surface was modified using a combined plasma/ozone‐activated process. The modified PTFE film was further reacted with 2‐bromoisobutyryl bromide to incorporate ATRP initiators in the film surface. Surface‐initiated ATRP on PTFE films was performed using sodium styrene sulfate as a monomer. The poly(sodium styrene sulfate) chain length grafted onto PTFE film surfaces increased with increasing reaction time. Analysis using X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy and a contact angle analyzer gave evidence of the success of the PTFE surface modifications.
The thermal ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate (BTMC) in bulk in the absence of any catalyst resulted in high molecular weight poly(BTMC) ( = 80 300) and subsequent catalytic hydrogenolysis resulted in functional poly(5‐hydroxyl‐trimethylene carbonate) (PHTMC). Similar spontaneous polymerization of BTMC in the presence of PEG ( = 2 000) as a macroinitiator can provide amphiphilic block polymers. The results revealed that the thermal non‐catalyst (co)polymerization of BTMC is a highly attractive preparative method because of the lack of usage of toxic initiators or catalysts. Furthermore, an evaluation of the degradation and cytotoxicity of PHTMC demonstrated enhanced degradability compared to poly(trimethylene carbonate) and similar toxicity compared to PLGA, showing PHTMC to be a promising biomaterial.
Colloidal quantum dots are well‐established probes for quantum optical experiments. However, they possess a limited stability toward their environment. Herein, the generation of hybrid particles composed of a high optical quality quantum dot centered in a polymer particle by means of a miniemulsion polymerization procedure is reported. This embedding strongly enhances emission intensity and photochemical stability of these single‐photon emitters. At the same time, their colloidal mobile nature is not compromised.
A novel tetradentate amine ligand namely N,N,N′,N″,N‴;,N‴;‐hexaoligo(ethylene glycol) triethylenetetramine (HOEGTETA) was employed in the homogenous ATRP of MMA in anisole using CuBr and CuBr2 as the catalyst and ethyl 2‐bromoisobutyrate (EBiB) as an initiator. The effect of the polymerization temperature and the various ratios of Cu(I) to Cu(II) were investigated in detail. Moreover, we demonstrated the ATRP of MMA by using only Cu(II) in the absence of any free radical initiator, reducing agent, or air. The ATRP of MMA with the use of only Cu(II) and HOEGTETA or N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) resulted in well‐defined PMMA.
