原子转移自由基细乳液聚合*

本文从正向、反向、同时正向/反向、电子转移活化剂等不同原子转移自由基聚合（ATRP）细乳液引发体系的角度,综述了近年来国内外关于ATRP细乳液聚合的研究进展。在细乳液体系中进行正向ATRP,聚合可控性不理想,反向ATRP相对适合于细乳液体系,其缺点是表面活性剂用量较大。同时正向/反向引发体系的ATRP中催化剂用量大为减少,并且聚合具有良好的可控性;电子转移活化剂（AGET）ATRP是通过电子转移反应来还原过渡金属的氧化态,克服了同时正向/反向ATRP中需要引入自由基引发剂的缺点。     

二苯酮-可聚合胺引发1,6-己二醇二丙烯酸酯的光聚合研究

以UV-Vis分光光度计法和Photo-DSC法分别研究了合成的3种可聚合胺类助引发剂DMPDA、EGDPM、EGMPM与二苯甲酮(BP)组成的引发体系的光化学初级过程及引发1,6-己二醇二丙烯酸酯(HDDA)的紫外光聚合动力学.考察了助引发剂胺的含量对BP的光化学初级过程和对引发HDDA光聚合动力学的影响,以及光强和温度对聚合动力学的影响.结果表明,随着胺含量的增加,BP的光化学初级反应速率增加,从而使体系的聚合反应速率增加.随着温度和光强的增加,单体最终转化率、最大反应速率增大,达到最大反应速率所需的时间减小.     

氧化-还原低温引发苯乙烯/丙烯酸丁酯细乳液聚合粒度分布和成核机理的研究

用氧化还原引发剂(NH₄)₂S₂O₈/NaHSO₃研究了苯乙烯(St)/丙烯酸丁酯(BA)低温下的细乳液共聚合,细乳液单体液滴在亚微米级(100～400nm).测定了聚合过程中粒子大小及分布的变化,发现细乳液聚合随引发剂、乳化剂和共乳化剂浓度的增加,乳胶粒子尺寸变小,分布变宽,并且比相同条件下传统乳液聚合的粒子大.计算了聚合过程中粒子数变化规律及乳化剂覆盖率,讨论了细乳液与传统乳液中引发剂、乳化剂对反应过程的影响及成核机理的差异.     

Elementary Steps of Initiation and Termination Processes in Radical Polymerization

Investigations into the kinetics of primary radicals produced in photochemically and thermally induced decomposition of peroxides of type R₁C(O)O-OR₂ are presented. The correlation of peroxide structure with decomposition rate and with initiator efficiency in radical polymerizations is discussed. Termination rate coefficients, k_t, as a function of temperature, pressure, polymer content, and of chain length may be deduced from two types of time-resolved experiments in which, after applying an excimer laser pulse, either monomer conversion is measured via near-infrared spectroscopy or the decay in radical concentration is monitored via electron spin resonance.     

Functionalization of Living Polymers via Ethoxysilane Based Compounds: Synthesis and Interaction with Silica Particles

To optimize the reaction of ω-carbanionic styrene or butadiene/styrene polymers with ethoxysilane based compounds, the influence of several experimental parameters on the orientation of the functionalization reaction and its yield was examined. The resulting end-functionalized polymers were systematically investigated by SEC, ¹H NMR and elementary analysis. The orientation of the reaction was found to be directly depending on the chemical nature of the chain end and / or on the type of additive (ethers, LiCl). Best results were obtained with tetraethoxysilane, provided the functionalization is conducted around 5°C, and the active chain end of isoprenyl type. These reactions were extended to bifunctional polymers, the reaction product of butyllithium with m-diisopropenylbenzene being used as an initiator. The efficiency of this initiator for the synthesis of well-defined bifunctionalized polydienes almost quantitatively fitted with three alkoxy functions at both chain ends was demonstrated. Some preliminary results on the mechanical properties of mixtures of functionalized polymers with silica were mentioned.     

Alkylamines‐intercalated α‐zirconium phosphate as latent thermal anionic initiators

The reaction of glycidyl phenyl ether (GPE) with 1‐aminoalkanes‐intercalated α‐zirconium phosphate (α‐ZrP·1‐aminoalkane): 1‐aminoalkanes 1‐aminopropane (α‐ZrP·Pr), 1‐aminobutane (α‐ZrP·Bu), 1‐aminooctane (α‐ZrP·Oct), and 1‐aminohexadecane (α‐ZrP·Hed) was carried out at varying temperatures for 1 h periods. Reaction progress was not observed until the reactants were heated to 80 °C or above. On increasing the temperature, the conversion factors increased such that, at 140 °C, conversions of 62% (α‐ZrP·Pr), 60% (α‐ZrP·Bu), 67% (α‐ZrP·Oct), and 64% (α‐ZrP·Hed) were obtained. The thermal stabilities as latent initiators were tested: GPEs reacted with α‐ZrP·Pr, α‐ZrP·Bu, and α‐ZrP·Oct at 40 °C for 360 h achieved conversions of 83, 55, and 59%, respectively. In contrast, the reaction in the presence of α‐ZrP·Hed did not proceed at 40 °C. The order of the thermal stability of GPE in the presence of α‐ZrP·1‐aminoalkane intercalation compounds was: α‐ZrP·Hed > α‐ZrP·Bu ≈ α‐ZrP·Oct > α‐ZrP·Pr. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1854–1861     

Symmetrical polymer systems prepared using a degradable bifunctional atom transfer radical polymerization initiator: Synthesis,characterization, and cleavage

Linear (co)polymers and dimethacrylate‐end‐linked polymer networks of methyl methacrylate with 2‐(dimethylamino)ethyl methacrylate, cleavable in the middle of the polymer chain, either under thermolysis or alkaline hydrolysis conditions, were prepared via atom transfer radical polymerization (ATRP) using a specially designed bifunctional degradable initiator. This initiator was 2,6‐pyridinediethanol di(2‐bromo‐2‐methyl propanoate) (PyDEDBrMeP), bearing two 2‐(pyridin‐2‐yl)ethyl ester moieties, known for their thermal and hydrolytic (alkaline conditions) lability. As a control, a more stable bifunctional ATRP initiator, 2,6‐pyridinedimethanol di(2‐bromo‐2‐methyl propanoate) (PyDMDBrMeP), was also synthesized together with the corresponding linear polymers and polymer networks prepared from it. Thermal or hydrolytic treatment of the polymers prepared using PyDEDBrMeP led to a reduction in the molecular weights of the linear polymers by a factor of two, and to the conversion of the polymer networks to soluble branched (star) structures, consistent with the expected cleavage of the initiator residue located in the middle of the polymer chain. Thermal treatment of the polymers prepared using PyDMDBrMeP did not affect their molecular weight due to the thermal stability of the (pyridin‐2‐yl)methyl ester group, while treatment under alkaline hydrolysis conditions resulted in complete cleavage, similar to the PyDEDBrMeP‐prepared polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2342–2355     

Initiator‐free atom transfer radical polymerization of methyl methacrylate based on FeBr3(PPh3)n system

A tricomponent system, constituting monomer (methyl methacrylate, MMA), higher oxidation state transition‐metal catalyst (FeBr₃) and a ligand (triphenylphosphine, PPh₃), MMA/FeBr₃/PPh₃ system without external initiator (alkyl halide) has been studied extensively with different spectroscopic analyses. To figure out the mechanism, a series of explicit model reactions were conducted with a molar ratio of [MMA]₀/[FeBr₃]₀/[PPh₃]₀ = 200/1/n (n = 0.1–3.0) at 80 °C, and the corresponding polymerization behaviors were investigated. Combined with theoretical deduction and spectroscopic evidences, the composition of the in‐situ generated initiators was gradually confirmed, which were redox products of FeBr₃ and PPh₃. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3842–3850     

含聚联烯的三嵌段共聚物的合成

聚联烯由于其特殊的结构而使其具有一些独特的应用,但聚合方法的局限性限制了聚联烯共聚物的研究.合成了一种偶氮-TEMPO（2,2,6,6-四甲基哌啶氮氧自由基）双官能团引发剂,通过苯基联烯醚单体的自由基聚合和苯乙烯的NMRP（氮氧调控自由基聚合）活性聚合,制备了聚苯乙烯-b-聚联烯-b-聚苯乙烯三嵌段共聚物.通过这种机理...     

Preparation and characterization of pure polyacrylate polymer colloid through emulsion polymerization using a novel initiator

A series of acrylic polymer colloids were prepared via semi-continuous seeded emulsion polymerization of BA and MMA in water phase when OP-10 and AIBI is used to be emulsifier and initiator, respectively. FTIR spectrum identifies the formation of copolymers of P (MMA-co-BA). DSC confirms that the colloid is a kind of random copolymer and the consistency among the chain segment is fairly good. The emulsion polymerization conditions of preparing acrylic polymer colloid are optimized. Results show that the conversion rate is high and the coagulum is low and the particle size of the acrylic polymer colloids is small when the amount of AIBI is 0.75 g. The polymerization temperature is 70 °C, which is lower than the one that the emulsion polymerization is initiated with the persulfate.