ATRP of acrylonitrile catalyzed by FeCl2/succinic acid under microwave irradiation

A single‐pot atom‐transfer radical polymerization (ATRP) under microwave irradiation was first used to successfully synthesize polyacrylonitrile. This was achieved by using FeCl₂/succinic acid as the catalyst and 2‐chloropropionitrile as the initiator. Using the same experimental conditions, the apparent rate constant under microwave irradiation was found to be higher than that under conventional heating. The FeCl₂/succinic acid ratio of 1 : 2 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. When FeCl₂ was replaced with CuCl, ATRP of AN does not show an obvious living characteristics. To demonstrate the active nature of the polymer chain end, the polymers were used as macroinitiators to proceed the chain‐extension polymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1598–1601, 2006     

AGET ATRP of methyl methacrylate catalyzed by FeCl3/iminodiacetic acid in the presence of air

The recently developed living free-radical polymerization system, atom transfer radical polymerization using activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP), was used for methyl methacrylate (MMA) polymerization in the presence of a limited amount of air, using a novel catalyst system based on iron (FeCl₃) complexes with iminodiacetic acid (IDA) and using ascorbic acid (VC) as a reducing agent. The kinetics of AGET ATRPs of MMA with different amounts of VC in the presence of air was investigated. The results of the polymerizations demonstrated the features of “living”/controlled free-radical polymerization such as the number-average molecular weights increasing linearly with monomer conversion and narrow molecular weight distributions (M_w/M_n = 1.31–1.44).     

Reverse atom‐transfer radical polymerization of acrylonitrile catalyzed by FeCl3/iminodiacetic acid

FeCl₃ coordinated by iminodiacetic acid (IMA) was Changed used for the first time as the catalyst in azobisisobutyronitrile‐initiated reverse atom‐transfer radical polymerization (ATRP) of acrylonitrile (AN). An FeCl₃ to IMA ratio of 1:2 not only gave the best control of molecular weight and its distribution but also provided a rather rapid reaction rate. The effects of solvents on the polymerization of AN were also investigated. The rate of the polymerization in N,N‐dimethylformamide (DMF) was faster than in propylene carbonate or toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in DMF. The rate of polymerization increased with increasing polymerization temperature and the apparent activation energy was calculated to be 54.8 kJ mol⁻¹. The reverse ATRP of AN did not show obvious living characteristics with CuCl₂ instead of FeCl₃. Copyright © 2005 Society of Chemical Industry     

Double‐miniemulsion preparation of Fe3O4/poly(methyl methacrylate) magnetic latex

Magnetic poly(methyl methacrylate) (PMMA) microspheres were prepared by double‐miniemulsion polymerization. First, oleic acid coated magnetite particles synthesized by means of coprecipitation were dispersed into octane to obtain a ferrofluid. The ferrofluid and MMA were emulsified to form O/W emulsion, respectively. Subsequently two miniemulsions were mixed together for polymerization. The obtained magnetic polymer particles were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, X‐ray powder diffraction, and thermogravimetry. The results showed that oleic acid coated magnetite particles were well encapsulated in PMMA. The effects of initiator dosage and monomer concentration on the conversion of MMA were also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

FeCl2/亚氨基二乙酸催化的原子转移自由基聚合制备苯乙烯/甲基丙烯酸甲酯嵌段共聚物

将催化剂FeCl2/亚氨基二乙酸用于原子转移自由基聚合制备PS-b-PMMA嵌段共聚物.大分子引发剂和嵌段共聚物的相对分子质量及其分布用GPC测定,共聚物的结构用红外光谱表征,玻璃化转变温度用DSC测定.     

Synthesis and Properties of Bi2Fe4O9 with FeCl2·6H2O Addition

Single‐phase Bi₂Fe₄O₉ is synthesized successfully by the solid‐state reaction technique with FeCl₂·6H₂O additives. The two optical band gaps, and the iron ion's chemical valence state both decrease with the addition of FeCl₂·6H₂O, which may be attributed to the decrease in the split energy of iron 3d orbital.     

How penultimate monomer unit effects and initiator influence ICAR ATRP of n‐butyl acrylate and methyl methacrylate

The relevance of penultimate monomer unit (PMU) effects and the selection of the correct initiator species under typical reversible deactivation radical copolymerization conditions is illustrated, using matrix‐based kinetic Monte Carlo simulations allowing the visualization of all monomer sequences along individual chains. Initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) is selected as illustrative polymerization technique with n‐butyl acrylate and methyl methacrylate as comonomers, aiming at the synthesis of well‐defined gradient copolymers. Using literature based model parameters, in particular temperature dependent monomer and radical reactivity ratios, it is demonstrated that PMU effects on propagation and ATRP (de)activation cannot be ignored to identify the most suited ICAR ATRP reactants (e.g., tertiary ATRP initiator) and reaction conditions (e.g., feeding rates under fed‐batch conditions). The formulated insights highlight the need for further research on PMU effects on all reaction steps in radical polymerization. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

甲基丙烯酸甲酯/丙烯酸/水反相无皂微乳液体系的聚合

采用滴定法描绘了甲基丙烯酸甲酯（MMA）/丙烯酸（AA）/H₂O无皂微乳液体系的三元相图,用电导率法对单相微乳液区域进行了类型划分.在相图研究的基础上,考察了引发剂（AIBN）用量、体系AA含量和水含量对MMA/AA/H₂O反相无皂微乳液体系聚合速率的影响.结果表明,聚合速率随引发剂用量和AA含量的增加逐步加快,随体系水含量的提高出现极大值.得到动力学关系,表明AA的乳化促进作用显著,聚合在连续相进行的同时亦在分散相液滴内进行.此外,环境扫描电镜的测试结果表明,所得聚合产物具有明显的孔穴结构.     

Atom transfer radical suspension polymerization of methyl methacrylate catalyzed by CuCl/bpy

Atom transfer radical suspension polymerization (suspension ATRP) of methyl methacrylate (MMA) was carried out using 1-chloro-1-phenylethane (1-PECl) as initiator, copper chloride/bipyridine (CuCl/bpy) as catalyst. The polymerization was accomplished with a mechanical agitator under the protection of nitrogen atmosphere. Apart from the dispersing agent (1% PVA), NaCl was also used in the water phase to decrease the diffusion of CuCl/bpy to water and the influence of the concentration of NaCl was investigated. Subsequently, the kinetic behavior of the suspension ATRP of MMA at different temperatures was studied. At 90 and 95 °C, the polymerization showed first order with respect to monomer concentration until high conversion. The molecular weight (M_n) of the polymer increased with monomer conversion. However, at lower temperatures, different levels of autoacceleration was observed. The polymerization deviated from first order with respect to monomer concentration when the conversion was up to some degree. The lower the temperature was, the more the deviation displayed. On comparison with bulk ATRP of MMA, the rate of suspension ATRP was much faster.     

含［N,O］配体的镍配合物/烷基铝催化甲基丙烯酸甲酯的聚合

制备了两种镍配合物二［N-(2-氧基-1-萘甲醛)缩-2,6-二异丙基苯胺］合镍［Ni(L₁)₂］和二［N-(2-氧基-1-萘甲醛)缩-邻甲基苯胺］合镍［Ni(L₂)₂］。研究了它们以普通烷基铝为助催化剂催化甲基丙烯酸甲酯(MMA)的聚合。结果表明,镍配合物的结构、聚合条件如单体浓度、Al与Ni物质的量比、聚合温度和聚合时间等对甲基丙烯酸甲酯聚合反应活性有很大的影响，当甲基丙烯酸甲酯浓度为0.8 mol·L^-1、n(Al)∶n(Ni)=400、温度为0 ℃时,催化活性达到110.7 kg-PMMA·(mol-Ni·h)^-1。随着聚合时间的延长，催化活性下降，而转化率则随着聚合时间的延长而缓慢增加。     

Polymerization of epoxides catalyzed by a mixed‐valent iron trifluoroacetate [Fe3O(O2CCF3)6(H2O)3]

The readily available mixed‐valent iron trifluoroacetate complex [Fe₂^IIIFe^II(µ₃‐O)(O₂CCF₃)₆(H₂O)₃] is an effective catalyst for the polymerization of epoxides. A very small amount of the catalyst (1.0–0.01 mol%) could initiate the polymerization of cyclohexene oxide, cyclopentene oxide and epichlorohydrin. Based on quantitative end‐group analysis by ¹⁹F NMR spectroscopy, a Lewis acid (LA^⊕) catalyzed anionic reaction mechanism is proposed. Copyright © 2012 Society of Chemical Industry     

Polymerization of methyl methacrylate catalyzed by mono-/bis-salicylaldiminato nickel(II) complexes and methylaluminoxane

Two types of salicylaldiminato-based nickel complexes, mono-ligated Ni(II) complexes ([O-C₆H₄-o- C(H)=N-Ar]Ni(PPh₃)(Ph) (5), [O-(3,5-Br₂)C₆H₂-o-C(H)=N-Ar]Ni(PPh₃)(Ph) (6), [O-(3-t-Bu)C₆H₃-o-C(H)=N-Ar]Ni(PPh₃)(Ph) (7)) and bis-ligated Ni(II) complexes ([O-(3,5-Br₂)C₆H₂-o-C(H)=N-Ar]₂Ni (8), [O-(3,5-Br₂)C₆H₂-o-C(H)=N-2-C₆H₄(PhO)]₂Ni (9), Ar=2,6-C₆H₃(i-Pr)₂) were synthesized and characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), mass spectrography (MS) and elemental analysis (EA). In the presence of methylaluminoxane (MAO) as cocatalyst, all the nickel complexes exhibited high activities for the polymerization of methyl methacrylate (MMA) and syndiotactic-rich poly(methyl methacrylate) (PMMA) was obtained. The complexes with less bulky substituents on salicylaldiminato framework possessed higher activities, while with the same salicylaldiminato, the mono-ligated nickel complexes showed higher catalytic activity than bis-ligated ones.     

Photopolymerization of methyl methacrylate by 2,2′‐dithiodiethanol: Effect of reaction conditions

The photopolymerization of methyl methacrylate (MMA) through the use of a novel disulphide, 2,2′‐dithiodiethanol (DDE), was studied. This photoinitiator is of special interest because of its possible use in the synthesis of polyurethane macrophotoinitiator. The photopolymerization was carried out in the Heber multilamp photochemical reactor (COMPACT‐LP‐MP88) at 254 nm. The effects of reaction conditions on the polymerization of MMA were studied. It was observed that the percentage conversion and molecular weight increased with the increases of monomer concentration and reaction time. However, for the initiator to monomer molar ratio, there was a critical molar ratio for maximum conversion. The results suggested the living radical nature of the photoinitiator, which was further investigated by the preparation of block copolymer with acrylonitrile. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1601–1606, 2006     

Polymerization of methyl methacrylate catalyzed by macromolecule–copper (II) complex in sodium sulfite aqueous system

Vinyl polymerization initiated by a copper complex immobilized on a novel polymer and characterization has been studied. Monomer, 4‐aldehyde‐3‐hydroxy phenyl acrylate (Ahpa), and its homopolymer, poly(4‐aldehyde‐3‐hydroxy phenyl acrylate) (PAhpa), were synthesized and characterized using IR, elemental analysis, ¹H NMR, TOF MS, etc. The side chain of the polymer can further coordinate with transition metal ions. Its polymeric Cu(II) complex in Na₂SO₃ system is proved to be another useful catalyst in polymerization of methyl methacrylate (MMA) at room temperature. The obtained poly(methyl methacrylate) (PMMA) is similar to those determined by conventional free radical polymerization at the same conditions. Moreover, the catalytic mechanism studied was a “Coordination Hydrogen‐Transfer” process, which is different from that of CuCl₂/Na₂SO₃ system, but analogous with that of PVAm‐Cu(II)/Na₂SO₃ (PVAm = polyvinylamine) system, was speculated and testified. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1285–1290, 2007     

Thermal analysis and NMR studies of methyl methacrylate (MMA)–methacrylic acid copolymers synthesized by an unusual polymerization of MMA

Methyl methacrylate–methacrylic acid (MMA–MAA) copolymers were prepared from the polymerization reaction of the methyl methacrylate (MMA) monomer with concentrated nitric acid (65% HNO₃) at different reaction times in the absence of other reagents in the reaction mixture. The hydrolysis degrees of the MMA–MAA (sodium salts) copolymers estimated by thermogravimetry (TG) corroborated the data obtained by chemical titration. By calorimetry (DSC), a relationship between the glass transition temperature (T_g) and the hydrolysis degree was obtained. The results presented a deviation from linear behavior and it was related to the strength of the interactions involved in the copolymer chains. The equation that relates the glass transition temperature to the interaction parameter, χ, for miscible binary polymer blends was applied for the MMA–MAA copolymers and demonstrated the composition dependence of χ. The molecular mobility was determined by nuclear magnetic resonance (NMR) in the solid state and through the proton spin‐lattice relaxation time in the rotating frame. The NMR data were in a good agreement with the results obtained by calorimetry. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 495–507, 2000     

MCM-41负载异丙醇合三氯化钕催化异戊二烯聚合

报道了用MCM 41负载异丙醇合三氯化钕(NdCl3·3i C3H7OH)的稀土催化剂,催化异戊二烯(Ip)聚合。发现MCM 41负载NdCl3·3i C3H7OH催化剂对Ip有良好的催化活性,而且聚合物重均相对分子质量( MW)高、分子质量分布( MW/ Mn)窄、cis-1,4含量高。其有利的聚合条件是:三异丁基铝(Ali Bu3)为助催化剂;n(Al)/n(Nd)=80;n(Ip)/n(Nd)=1000;聚合温度为50℃;甲苯作溶剂;聚合时间为6h。     

Synthesis of polyacrylonitrile via reverse ATRP initiated by 1,1,2,2‐tetraphenyl‐1,2‐ethanediol/CuCl2/2,2′‐bipyridine

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living‐radical polymerization of acrylonitrile (AN). 1,1,2,2‐Tetraphenyl‐1,2‐ethanediol (TPED) was first used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 53.2 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3529–3533, 2007     

Wet oxidation of acetic acid by H2O2 catalyzed by transition metal-exchanged NaY zeolites

During the wet oxidation of contaminated wastewaters, the destruction of low molecular weight carboxylic acid intermediates such as acetic, glyoxalic, and oxalic acids is often the rate-controlling step. Oxidation of acetic acid, a very recalcitrant intermediate, requires compelling treatment severity. Heterogeneous catalytic wet oxidation of model acetic acid aqueous solutions was conducted under mild conditions (below the normal boiling point of water) using hydrogen peroxide over various transition metal-exchanged NaY zeolites. Treatment of Cu²⁺–NaY with oxalic acid [OA] led to a catalyst, Cu²⁺–NaY [OA], with significantly improved properties in terms of total organic carbon (TOC) removal efficiency and catalyst stability against leaching. This catalyst outperformed homogeneous Cu²⁺ by a factor of 2–2·5 times. Continuous feeding of H₂O₂ reduced its undesirable decomposition. Improvement of the TOC-degradation performance by Cu²⁺–NaY [OA] was tentatively attributed to the removal of sodium and possibly aluminium in the zeolite. © 1998 Society of Chemical Industry     

Neubestimmung der Laktonringkonformation in der Kristallstruktur des Strophanthidin C23H32O6 · 1/2 H2O

A New Determination of the Conformation of the Lactonering in the Crystal Structure of Strophanthidin C₂₃H₃₂O₆ · 1/2 H₂O By partial difference-Fourier-synthesis a fixed conformation of the lactone ring of the molecule B was established and geometrical parameters were determined. The reason for the occurrence of two symmetrical independent molecules was interpreted by insertion of one water molecule in the crystal structure and by different conformations of both lactone rings. Another H-bridges-system in the crystal structure was deduced.     

微波辅助Fe_3O_4/H_2O_2类Fenton法处理罗丹明B废水

采用纳米Fe3O4作为催化剂,H2O2为氧化剂,组成多相类Fenton试剂,与微波联合处理罗丹明B(Rh B)染料废水。反应在300W微波反应器中进行,系统研究了H2O2浓度,Fe3O4用量,反应时间,反应温度及催化剂循环使用等条件对罗丹明B脱色率的影响。结果表明,在pH值为4,罗丹明B浓度为100 mg/L,反应温度为80℃,反应时间为5min,H2O2用量为5.0 mL/L,Fe3O4用量为1.25 g/L时,微波辅助条件下罗丹明B脱色率达到100%。此外,催化剂六次循环实验表明,磁性催化剂非常稳定,可重复使用,且易回收。实验表明微波加热与Fe3O4/H2O2类Fenton反应的联合产生了良好的协同效果,该联合工艺可大大提高废水中有机物的处理效果。