ROMP based photoinitiator‐coinitiator systems with improved migration stability

Nowadays, migration stability is one of the key features for photoinitiators used in radiation curable formulations, especially when the material is in contact with food or the human body. Herein, the synthesis and characterization of statistical copolymers with covalently bound eosin and/or ethyl dimethylamino benzoate units by ring opening metathesis polymerization is presented. The prepared compounds were tested as macroinitiators for the photopolymerization of acrylates aiming at an initiator/coinitiator system which combines good polymerization activity with improved migration stability. An acrylate modified eosin derivative which is incorporated into the polymer network during the photopolymerization reaction and, therefore, less likely to leak from the polymer compound was used as reference. Photoinitiating activities of low and high molecular weight initiators and coinitiators were investigated by photo‐DSC. Moreover, leakage studies and viability tests with osteoblast‐like cells were performed to proof the suitability of this concept. The use of polymeric eosin in combination with a low molecular weight coinitiator was found to be a good compromise when aiming at a photoinitiating system with sound performance and improved migration stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3648–3661, 2008     

Initiator‐fragment incorporation radical copolymerization of divinylbenzene and N‐isopropylacrylamide with dimethyl 2,2′‐azobisisobutyrate: Formation of soluble hyperbranched polymer nanoparticle

The copolymerization of divinylbenzene (DVB) and N‐isopropylacrylamide (NIPAm) with dimethyl 2,2′‐azobisisobutyrate of a concentration as high as 0.50 mol/L proceeded homogeneously without any gelation at 80 °C in N,N‐dimethylformamide, where the concentrations of DVB and NIPAm were 0.15 and 0.50 mol/L. The copolymer yield increased with time and leveled off over 50 min. Although DVB was consumed more rapidly than NIPAm, both comonomers were completely consumed in 50 min. The homogeneous polymerization system at 80 °C involved electron spin resonance‐observable propagating polymer radicals, the total concentration of which increased with time. The resulting copolymer was soluble in tetrahydrofuran, chloroform, acetone, ethyl acetate, acetonitrile, N,N‐dimethylformamide, dimethyl sulfoxide, and methanol, but insoluble in benzene, n‐hexane, and water. The copolymer showed an upper critical solution temperature (50 °C on cooling) in a methanol–water [11:3 (v/v)] mixture. Dimethyl 2,2′‐azobisisobutyrate fragments as high as 37–45 mol % were incorporated as terminal groups in the copolymers through initiation and primary radical termination. The contents of DVB and NIPAm were 10–30 mol % and 30–50 mol %, respectively. The intrinsic viscosity of the copolymer was very low (0.09 dL/g) at 30 °C in tetrahydrofuran despite high weight‐average molecular weight (1.2 × l0⁶ by multi‐angle laser light scattering). These results indicate that the copolymer was of hyperbranched structure. By transmission electron microscopy observation, the individual copolymer molecules were visualized as nanoparticle of 6–20 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1609–1617, 2004     

The effective use of precision electroweak measurements

Bound state population dynamics in a diatom modelled by an appropriate Morse oscillator with a time-dependent well-depth is investigated perturbatively both in the absence and presence of high intensity radiation. For sinusoidally oscillating well-depth, the population of themth bound vibrational level,P _mm(t), is predicted to be a parabolic function of the amplitude of the oscillation of the well-depth (ΔD ₀) at a fixed laser intensity. For a fixed value of ΔD ₀,P _mm(t) is also predicted to be quadratic function of the field intensity (ɛ ₀). Accurate numerical calculations using a time-dependent Fourier grid Hamiltonian (TDFGH) method proposed earlier corroborate the predictions of perturbation theory. As to the dissociation dynamics, the numerical results indicate that the intensity threshold is slightly lowered if the well-depth oscillates. Possibility of the existence of pulse-shape effect on the dissociation dynamics has also been investigated.     

钝感炸药爆轰驱动研究

 对两种典型的钝感炸药（IHE）的爆轰驱动模型进行了实验研究。一种是点爆散心波驱动，另一种是滑移爆轰驱动。并在同一条件下做了非钝感炸药（HE）的爆轰驱动实验，以比较IHE和HE驱动规律的异同。对实验模型用二维数值模拟及拟合公式进行了计算，最后给出了在本实验条件下两种炸药驱动规律差异，也对计算偏差范围作了估计。     

Toward self-assembling dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible terminator multifunctional initiator

TERMINI stands for irreversible terminator multifunctional initiator and represents a new concept elaborated in our laboratory for the design of novel macromolecules with complex architecture from a diversity of commercial monomers. TERMINI is a masked multifunctional initiator that quantitatively interrupts a living polymerization. After demasking, the TERMINI-derived repeat unit provides access to a quantitative reinitiation of the same living polymerization in more than one direction, thus becoming a branching point. In this article, with a combination of self-regulated metal-catalyzed living radical polymerization and TERMINI, we demonstrate a new method for the divergent synthesis of dendritic poly(methyl methacrylate) containing a bifunctional core at its focal point. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 505–513, 2004     

ε-己内酯负离子聚合过程烷氧基锂活性种的缔合

本文以粘度法研究在苯溶剂中,ε-己内酯负离子开环聚合过程,增长链活性种烷氧基锂(—O~-Li~+)的缔合,发现己内酯活性种的缔合和一般非极性单体不同,前者在聚合过程中(单体消耗完以前)并不发生缔合。在单体消耗完以后,聚己内酯活性种才确实以缔合体的形式存在。这是由于内酯本身贡献了强的溶剂化作用。     

Dynamical symmetry analysis of ionization and harmonic generation of atoms in bichromatic laser pulses

Recently the effect of the relative phase ? in a high‐intensity (～10¹⁴ W/cm²) two‐color (bichromatic) CW laser with frequencies ω and 2ω on the high‐order harmonic generation (HHG) was studied within the framework of the non‐Hermitian quantum mechanics (NHQM) [Phys Rev A 2004, 69, 043404/1]. Here we emphasize the study of symmetries in bichromatic HHG spectra within the framework of the conventional Hermitian QM, and in particular by taking the duration of the laser pulse into consideration (an effect that has not been included in the non‐Hermitian studies due to the time asymmetry problem in NHQM). The phase dependence of HHG and intense‐field ionization probability in a 1D Xe atom with symmetric field‐free potential and symmetric initial wave function were studied numerically and analytically. From simulations based on a single‐particle response it can be seen that the HHG spectra is symmetric with respect to inversion in the relative phase between the two colors ? only if ionization is forbidden in the system and the laser pulse is an adiabatic one. The HHG spectra is symmetric with respect to a π‐shift in ? whenever the laser pulse is an adiabatic one, either for bound or open (ionized) systems. The ionization probability is symmetric both to inversion or π‐shift in ?; the component probabilities (right‐ and left‐ionization probabilities) have the same ?‐dependence, up to a shift of π. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

自由基引发的可注射PLA-b-PEG-b-PLA大分子单体和α-CD超分子结构水凝胶的合成与表征

以数均分子量为6000的聚乙二醇为引发剂,以辛酸亚锡为催化剂引发丙交酯开环,再用甲基丙烯酸酐进行封端生成大分子单体.然后将大分子单体和α-环糊精混合,分别用维生素C和硫酸亚铁与过硫酸铵组成的氧化还原引发剂引发聚合,得到了两种不同结构的超分子结构水凝胶.用1HNMR,FTIR,TGA和XRD等分析测试手段对大分子单体及形成的水凝胶进行了表征.流变仪测试结果表明,该水凝胶固化时间合适,并具有可注射性.     

含二苯酮基的大分子光敏引发剂的研究进展

简要介绍含二苯酮基的大分子光敏引发剂的合成制备、引发聚合机理及应用方面的研究进展情况。     

含偶氮聚四氢呋喃的合成及分解

<正> 本文以4,4′-偶氮二异氰基戊酰氯(ACVCl)与SbCl_5引发体系,低温下进行THF聚合,合成出主链中含有一个偶氮基的聚四氢呋喃(简称AZO-PTHF)。该聚合物中的AZO基和通常低分子偶氮化合物一样可在受热时发生分解反应,生成大分子游离基,因此可作为高分子引发剂引发乙烯基单体聚合。ESR波谱分析表明,该聚合物在40°C左右热分解产生游离基。