All solid-state polymer electrolytes prepared from a graft copolymer consisting of a polyimide main chain and poly(ethylene oxide) based side chains

We prepare an all solid-state, liquid-free, polymer electrolyte (ASPE) from a lithium salt and a graft copolymer consisting of a polyimide main chain and poly(ethylene glycol) methyl ether methacrylate side chains using atom transfer radical polymerization method. The ionic conductivity of ASPEs increases with increasing the side chain length. The ionic conductivity of the ASPE whose POEM content = 60 wt% shows 6.5 × 10⁻⁶ S/cm at 25 °C. The ASPEs having shorter average distance between side chains and/or shorter side chain length show higher mechanical strength. The tensile strength of the ASPEs is more than 10 MPa and about 20 times higher than that of the ASPEs in the previous study [Electrochim. Acta, 50 (1998) 3832]; hence, the ASPEs have sufficiently high mechanical strength for a polymer electrolyte of lithium secondary batteries.     

Synthesis of fluorinated polymer electrolyte membranes by radiation grafting and atom transfer radical polymerization techniques

A novel polymer electrolyte membrane was synthesized by radiation-induced grafting and consequent atom transfer radical polymerization (ATRP). First, bromine-containing perfluorinated grafts were prepared by radiation grafting of 2-bromotetrafluoroethyl trifluorovinyl ether (BrTFF) into a poly(ethylene-co-tetrafluoroethylene) (ETFE) film. Then, the bromine atoms in the ETFE-g-PBrTFF grafted films were acted as initiators, and the films were treated with Cu(I)-based catalytic system of a CuBr and 2,2′-bipyridyl (bpy) for the ATRP. By adjusting the molar ratio of initiator/CuBr/bpy and the reaction temperature, branched poly(styrene) with a grafting yield of above 100% on the poly(BrTFF) main chains was constructed in ETFE-g-PBrTFF films. Thermal analysis revealed that the perfluorinated poly(BrTFF) main chains were miscible to ETFE, whereas the hydrocarbon poly(styrene) branches were phase-separated from the ETFE-g-PBrTFF film. Sulfonic groups could be further introduced into the poly(styrene) grafts of ETFE-g-PBrTFF-g-PS films with homogeneous distribution in a perpendicular direction to the membrane surface. The resulting membrane with a styrene grafting yield of 15% exhibited higher proton conductivity than commercial Nafion 117 membrane. Likewise, it had better chemical stability than ETFE-g-PSSA membrane prepared by conventional radiation-induced grafting.     

Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles

The synthesis of magnetite nanoparticles coated with a well-defined graft polymer is reported. The magnetite nanoparticles with an initiator group for copper-mediated atom transfer radical polymerization (ATRP), 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride. Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer consumption and a proportional relationship between molecular weight of the graft polymer and monomer conversion, thus providing well-defined, low-polydispersity graft polymers with an approximate graft density of 0.7 chains/nm². The molecular weight and polydispersity of the graft polymer were nearly equal to those of the free polymer produced in the solution, meaning that the free polymer is a good measure of the characteristics of the graft polymer. The graft polymer possessed exceptionally high stability and remarkably improved dispersibility of the magnetite nanoparticles in organic solvent.     

Effects of molecular weight on liquid-crystalline behavior of a mesogen-jacketed liquid crystal polymer synthesized by atom transfer radical polymerization

The synthesis of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) with different molecular weight and low polydispersity was achieved by atom transfer radical polymerization in methoxybenzene solution using 1-bromoethylbenzene as an initiator and CuBr/sparteine complex as a catalyst. The concentration of the living centers throughout the polymerization was found to be constant. The liquid-crystalline behavior of the polymers with M_n ranging from 3800 to 17,400 g/mol was studied using DSC and POM. Only the polymers with M_n beyond 10,200 g/mol formed a liquid-crystalline phase, which was quite stable with a high clearing point (higher than the decomposition temperature of the polymer).     

Fabrication of patterned high-density polymer graft surfaces. II. Amplification of EB-patterned initiator monolayer by surface-initiated atom transfer radical polymerization

Patterned films of a low-polydispersity polymer densely end-grafted on a silicon substrate were fabricated for the first time by the combined use of electron beam (EB) lithography and living radical polymerization; a focused EB was scanned on an initiator-immobilized substrate to selectively bombard and decompose the initiator, and then the EB-induced pattern was amplified by the atom transfer radical polymerization (ATRP) technique using Cu/ligand complexes. Ellipsometric and atomic force microscopic studies indicated that doses sufficiently larger than 2000 μC/cm² would completely decompose the monolayer of the initiator, 2-(4-chlorosulfonylphenyl)ethyltrichlorosilane, and that the surface-initiated ATRP could amplify the EB-produced fine pattern of the initiator monolayer.     

One pot,two step sequence converting atom transfer radical polymerization directly to radical trap-assisted atom transfer radical coupling

Monobrominated polystyrene (PStBr) chains were prepared using standard atom transfer radical polymerization (ATRP) procedures at 80 °C in THF, with monomer conversions allowed to proceed to approximately 40%. At this time, additional copper catalyst, reducing agent, and ligand were added to the unpurified reaction mixture, and the reaction was allowed to proceed at 50 °C in an atom transfer radical coupling (ATRC) phase. During this phase, polymerization continued to occur as well as coupling; expected due to the substantial amount of residual monomer remaining. This was confirmed using gel permeation chromatography (GPC), which showed increases in molecular weight not matching a simple doubling of the PStBr formed during ATRP, and an increase in monomer conversion after the second phase. When the radical trap 2-methyl-2-nitrosopropane (MNP) was added to the ATRC phase, no further monomer conversion occurred and the resulting product showed a doubling of peak molecular weight (M_p), consistent with a radical trap-assisted ATRC (RTA-ATRC) reaction.     

The synthesis of CDA-g-PMMA copolymers through atom transfer radical polymerization

Graft copolymer of cellulose diacetate (CDA) and PMMA was synthesized through atom transfer radical polymerization (ATRP). The residual hydroxyl groups on the diacetate cellulose reacted with 2-bromoisobutyryl bromide to yield 2-bromoisobutyryl groups known to be an efficient initiator for ATRP. Then the functional CDA was used as macroinitiator in the ATRP of MMA. The polymerization was carried out in the system of PMDETA/CuBr/1,4-dioxane under 70 °C. Kinetic study indicated that the polymerization is first order. Copolymers were characterized by ¹H NMR and GPC. The molecular weight increased without any trace of the macroinitiator, and the polydispersities were low.     

Star polymers via atom transfer radical polymerization from adamantane-based cores

A series of novel multifunctional initiators derived from adamantane-based derivatives have been used in the syntheses of various styrenic and (meth)acrylic star polymers by atom transfer radical polymerization (ATRP). Conditions were identified in each system to produce star polymers with nearly monomodal molecular distributions. These synthesized star polymers have glass transition temperatures similar to those known for high-molecular-weight linear polymers. We obtained a series of adamantane-contained star polymers covering a wide range of molecular weights by adjusting the monomer-to-initiator ratio and the solvent polarity. Because of reaction heterogeneity and inevitable termination processes, the occurrence of star-star coupling led to a lower than predicted molecular weight polydispersity. When hydrolyzed from their cores by NaOH, the values of M_w of the arms of the PMMA star polymer did not change with reaction time, at least for the first 48 h of the reaction, which implies that no significant PMMA hydrolysis occurs within this interval of time.     

A novel ligand for atom transfer radical polymerization

A ligand is a crucial element for atom transfer radical polymerization (ATRP). A new nitrogen-containing compound, 1,1’-(2,2’-(ethane-1,2-diylbis(butyl azanediyl)) -bis(ethane-2,1-diyl)) dipyrrolidin-2-one (DBBD), was synthesized and utilized as the ligand of copper halide for ATRP of methyl methacrylate (MMA) and methyl acrylate (MA). It was found that the CuBr/DBBD and Ethyl 2-bromoisobutyrate (EBIB) system could mediate the polymerization of MMA and the reaction was first-order kinetics, although the control of molecular weights was not perfect. When CuCl was used to replace CuBr, the molecular weights of obtained polymers were well controlled, which indicated the halide exchange could improve the controllability. In the polymerization of MA using Methyl 2-bromopropronate (MBP) or EBIB as initiator and CuCl/DBBD as catalyst, good control of the polymerization could be achieved and the molecular weights were very close to the predicted value.     

Synthesis of well-defined star polymers and star block copolymers from dendrimer initiators by atom transfer radical polymerization

Novel polyarylether dendrimers with 1,3,5-tri(4-hydroxyphenoxy)benzene core, polybenzylether interior, and benzyl 2-bromoisobutyrate surface group (CMGn-Br, n=1-3, with functionality of 6, 12, and 24, respectively) were prepared by convergent procedure. ATRP of tert-butyl acrylate (tBA) and styrene (St) with CMGn-Br dendrimer initiators in the presence of CuBr/pentamethyldiethylenetriamine catalytic system was investigated in detail, and a series of well-defined dendrimer-like star PtBA and PSt with precise arm numbers were synthesized under suitable conditions. The quantitative initiation of the dendrimer initiators was demonstrated by high initiation efficiency, ¹H NMR spectra, hydrolysis, and MALLS/SEC approach. Star block copolymers comprising PSt and PtBA segments with low polydispersity (1.08<M_w/M_n<1.18) were also successfully synthesized using functional macroinitiators by block copolymerization. In addition, the thermal properties of the resultant polymers were characterized by DSC and TGA.     

原子转移自由基聚合原理及应用

介绍了有关原子转移自由基聚合(ATRP)的聚合原理。最新研究表明:应用ATRP法进行聚合反应可以制备接枝聚合物、嵌段聚合物、超支化聚合物和其它有机/无机混合型聚合物等。ATRP在高分子聚合反应领域具有十分广阔的应用前景。     

Well-defined dibenzocyclooctyne end functionalized polymers from atom transfer radical polymerization

The dibenzocyclooctyne end functionalized agent 1 was designed as atom transfer radical polymerization (ATRP) initiator. The ATRP was then explored on three types of monomers widely used in free radical polymerization: methyl methacrylate, styrene, and acrylates (n-butyl acrylate and tert-butyl acrylate). The living polymerization behaviors were obtained for the methyl methacrylate and styrene monomers. The SPAAC click reactivity of dibenzocyclooctyne end group were demonstrated by successfully reacting with azide functionalized small chemical agents and polymers. Various topological polymers such as block and brush polymers were produced from strain-promoted azide-alkyne cycloaddition reaction (SPAAC) using the resultant dibenzocyclooctyne end functionalized poly(methyl methacrylate)/polystyrene as building blocks. For the acrylates, however, the polymerization did not hold the living characteristics with the dibenzocyclooctyne end functionalized ATRP initiator 1.     

Emulsion atom transfer radical polymerization of 2-ethylhexyl methacrylate

The emulsion atom transfer radical polymerization (ATRP) of 2-ethylhexyl methacrylate (EHMA) was carried out with ethyl 2-bromoisobutyrate (EBiB) as an initiator and copper bromide (CuBr)/4,4′-dinonyl-2,2′-bipyridyl (dNbpy) as a catalyst system. The effects of surfactant type and concentration, temperature, monomer/initiator ratio, and CuBr₂ addition on the system livingness, polymer molecular weight control, and latex stability were examined in detail. It was found that the polymerization systems with Tween 80 and Brij 98 as surfactants at 30 °C gave the best latex stability. The polymer samples prepared under these conditions had narrow molecular weight distributions (M_w/M_n=1.1-1.2) and linear relationships of number-average molecular weight versus monomer conversion.     

Synthesis of binary mixed homopolymer brushes by combining atom transfer radical polymerization and nitroxide-mediated radical polymerization

This communication describes a novel strategy to synthesize binary mixed homopolymer brushes from mixed self-assembled monolayers (SAMs) on silica substrates by combining atom transfer radical polymerization (ATRP) and nitroxide-mediated radical polymerization (NMRP). Mixed SAMs terminated by ATRP and NMRP initiators were prepared by coadsorption of two corresponding organotrichlorosilanes from toluene solutions. Mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes were synthesized by ATRP of MMA at 80 °C followed by NMRP of styrene at 115 °C. Corresponding ‘free’ initiators were added into the solutions to control the polymerizations. We have found that the brush thickness increases with molecular weight in a nearly linear fashion. For a series of binary brushes consisting of PMMA of molecular weight of 26,200 and PS of various molecular weights, we have observed a transition in water contact angles with increasing PS molecular weight after CH₂Cl₂ treatment. Moreover, binary mixed polymer brushes with comparable molecular weights for two grafted polymers undergo reorganization in response to environmental changes, exhibiting different wettabilities.     

原子转移自由基聚合在生物材料合成方面的应用

介绍了原子转移自由基聚合的原理及其在生物材料合成方面的应用。     

原子转移自由基聚合在合成接枝共聚物中的应用

本文综述了采用原子转移自由基聚合（ATRP）法合成接枝共聚物的研究进展。主要从大分子引发剂法和大分子单体法两方面介绍了原子转移自由基聚合在合成接枝聚合物中的应用。     

High-pressure atom transfer radical polymerization of methyl methacrylate for well-defined ultrahigh molecular-weight polymers

The feasibility of high-pressure atom transfer radical polymerization (ATRP) for synthesizing well-defined polymers of extraordinarily high molecular weights was demonstrated. ATRP of methyl methacrylate (MMA) under pressures up to 500 MPa was investigated at 60 °C. The addition of a small amount of a Cu(II)Cl₂/ligand complex along with the general benefits of high pressure of enhancing propagation and suppressing termination brought about an excellent control of polymerization even with an extremely low concentration of ATRP initiator. For example, there was produced PMMA with a number-average molecular weight M_n of 3.6 × 10⁶ and a polydispersity index of 1.24, which had never been achieved by conventional ATRP.     

Mechanistic investigation of 9-bromoanthracene photodimers as initiators in atom transfer radical polymerization

Mechanistic pathways accounting for the lack of control in polymerizations employing photodimers of 9-bromoanthracene as alkyl halide initiators in atom transfer radical polymerization (ATRP) reactions are presented. Converting the aryl bromide on the anthracene moiety into an alkyl bromide via a [4+4] cycloaddition reaction effectively generated the photodimer with two alkyl halide sites, which were investigated as potential initiating sites for the ATRP of styrene and n-butyl acrylate. Polymers synthesized using these photodimers as initiators possessed relatively broad polydispersity index (PDI) values and displayed a non-linear relationship between their number average molecular weights (M_n) and monomer consumption, consistent with slow initiation from the bridgehead alkyl halide. Reactions performed at 80 °C in bulk or THF generated polystyrene with M_n values 3-5 times higher than calculated based on monomer-to-initiator ratios. UV-vis spectrometry of the products demonstrated absorbance bands indicative of polymer-bound anthracene, caused by thermal degradation of the photodimer during the polymerization. When the initiator was introduced last into the reaction mixture in an attempt to suppress photodimer cleavage prior to initiation, PDI values and M_n values were generally lowered with the resulting polymers showing similarly high anthracene content. Composition of polystyrene and poly(n-butyl acrylate) products was also studied as a function of reaction temperature, with decreased anthracene labeling observed at lower temperatures (40 and 60 °C), further validating a model of heat-induced cleavage of the photodimer.     

Preparation of silica microtubes by surface-initiated atom transfer radical polymerization from microfiber templates

Poly(methyl methacrylate-co-vinylbenzyl chloride), P(MMA-co-VBC) microfibers (with submicron diameters) of about 1 μm in size were prepared by electrospinning. Silyl-functional groups were introduced onto the P(MMA-co-VBC) microfibers templates via surface-initiated atom transfer radical polymerization of 3-(trimethoxysilyl)propyl methacrylate. The silyl groups were then converted into a silica shell, approximately 0.25 μm thick, via a reaction with tetraethoxysilane in ethanolic ammonia. Hollow silica microfibers were finally generated by thermal decomposition of the P(MMA-co-VBC) template cores. Scanning electron microscopy and transmission electron microscopy were used to characterize the intermediate products and the hollow microtubes. Fourier-transform infrared spectroscopy results indicated that the polymer cores were completely decomposed. The microfibers were characterized by X-ray photoelectron spectroscopy, X-ray diffraction and the thermal gravimetric analysis.     

Preparation of Ni-g-polymer core–shell nanoparticles by surface-initiated atom transfer radical polymerization

Surface-initiated atom transfer radical polymerization (si-ATRP) technique was successfully employed to modify Ni nanoparticles with polymer shells. ATRP initiators were covalently bonded onto Ni nanoparticle surfaces by a combination of ligand exchange and condensation reactions. Various kinds of polymers including poly(methyl methacrylate) (PMMA) and poly(n-isopropylacrylamide) (PNIPAM) were grafted from the immobilized initiators. The grated polymer shells gave Ni nanoparticles exceptionally good dispersion and stability in solvents. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and transmission electron spectroscopy (TEM) were employed to confirm the grafting and to characterize the nanoparticle core–shell structure. Gel permeation chromatography (GPC) studies of cleaved polymer chains revealed that the grafting polymerization was well controlled. The magnetic properties of Ni-g-polymer nanoparticles were also studied.