Polymeric Photoinitiators Containing Side-chain Ketoaromatic Moieties for Fast Ultraviolet Initiated Polymerisation of Acrylic Monomers

The synthesis of polymeric photoinitiators having side-chain cyclohexylphenylketone as well as benzophenone moieties at different distances from the backbone is described. Study of the activity of the former systems, in the ultraviolet initiated polymerisation of acrylic monomers, indicates that a remarkable increase in the polymerisation rate is observed when the cyclohexylphenylketone chromophore is attached to the main chain through an ethereal linkage rather than an ester group. In the case of the latter systems, considerable improvement is observed in the photoinitiating activity with respect to the corresponding low molecular weight model compounds in the polymerisation of acrylic monomers. Moreover, in general the copolymers of benzophenone-containing monomers show higher activity than the corresponding homopolymers. These results are discussed in terms of photoexcitation energy migration along the polymer chain, as well as of intramolecular hydrogen abstraction from both main and side chains. This last occurrence seems to be the main activation process, as suggested by a strict correlation between activity and hydrogen-donating properties of the co-units in the copolymers, Photophysical evidence supporting this point is also reported. Finally, the synthesis of polymeric photoinitiators, containing both benzophenone and tertiary amine groups in the same macromolecule, has been accomplished via copolymerisation of 4-acryloxybenzophenone with 4-(N,N-dimethylamino)styrene. Preliminary data concerning photoinitiating activity of these last copolymers indicate that conformational mobility affects the formation capability of exciplexes and then the activity itself.     

基于复合功能单体噻菌灵印迹传感器的制备及应用

目的：快速检测食品中噻菌灵残留量。方法：通过紫外光谱法筛选邻氨基苯酚和邻苯二胺作为复合功能单体,采用电化学分析法研究了聚合条件、洗脱条件,对传感器性能进行了评价,建立了食品中噻菌灵残留的快速检测方法。结果：在最佳条件下,该印迹传感器对噻菌灵及其结构类似物具有特异吸附性能,且对噻菌灵的选择性最强;该方法的线性范围在1×10^-8～1×10^-4 mol/L,检出限为3.3×10^-9 mol/L,样品加标平均回收率为88.16%～100.73%,相对标准偏差（RSD）≤2.63%。结论：该传感器具有优异的印迹效应以及良好的选择性、重现性与稳定性,可用于食品中噻菌灵残留的快速检测。     

Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)

Living free radical polymerization technology (macromolecular design via the interchange of xanthates (MADIX)) was applied to give accesses to chain length and conversion dependent termination rate coefficients of vinyl acetate (VAc) at 80 °C using the MADIX agent 2-ethoxythiocarbonylsulfanyl-propionic acid methyl ester (EPAME). The kinetic data were verified and probed by simulations using the PREDICI^® modelling package. The reversible addition-fragmentation transfer (RAFT) chain length dependent termination (CLD-T) methodology can be applied using a monomer reaction order of unity, since VAc displays significantly lower monomer reaction orders than those observed in acrylate systems (ω(VAc, 80 °C)=1.17±0.05). The observed monomer reaction order for VAc is assigned to chain length dependent termination and a low presence of transfer reactions. The α value for the chain length regime of log(i)=1.25−3.25 (in the often employed expression ) reads 0.09±0.05 at low monomer to polymer conversion (10%) and increases significantly towards larger conversions (α=0.55±0.05 at 80%). Concomitantly with a lesser amount of midchain radicals, the chain length dependence of k_t is significantly less pronounced in the VAc system than in the corresponding acrylate systems under identical reaction conditions. The RAFT(MADIX)-CLD-T technique also allows for mapping of k_t as a function of conversion at constant chain lengths. Similar to observations made earlier with methyl acrylate, the decrease of k_t with conversion is more pronounced at increased chain lengths, with a strong decrease in k_t exceeding two logarithmic units from 10 to 80% conversion at chain lengths exceeding 1800.     

醋-丙共聚乳液胶粘剂的制备

采用预乳化半连续种子乳液聚合工艺对改性醋酸乙烯酯-丙烯酸丁酯共聚乳液胶粘剂的制备工艺进行了研究。实验中具体考察了聚合方式、单体配比、功能单体、乳化剂、引发剂、聚合温度、保护胶体等因素对乳液胶粘剂制备及性能的影响,确定了最佳工艺条件,并对所合成乳液胶粘剂的性能进行了测试与表征。当醋酸乙烯酯和丙烯酸丁酯的比例为1∶1时,共聚乳液具有最佳的粘接性能。功能性单体丙烯酸的加入可显著提高乳液的内聚力。聚合反应的最佳工艺条件是乳化剂的用量3%~5%,引发剂用量1%~3%,温度80℃。该工艺得到的改性醋-丙共聚乳液粒径分布均匀,机械稳定性好,并具有良好的纸塑粘接性能。     

Structural test of precast polymer concrete

This study was performed to check the feasibility of concrete polymer manhole through a development test of high strength polymer concrete and prepare fundamental data for design to solve the problems of the existing cement concrete manhole. The lower absorption capacity (0.39%) of polymer concrete will be more advantageous in installing manhole in an area with subsurface water. Also long working‐life (63 minutes) will be enough to establish manholes. Conclusively, the high strength polymer concrete that is the most important issue in development of polymer concrete manhole could be made. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants

This paper describes the synthesis of long‐chain fatty esters of corn starch (starch laurate and starch stearate) with a broad range in degree of substitution (DS = 0.24−2.96). The fatty esters were prepared by reacting the starch with vinyl laurate or vinyl stearate in the presence of basic catalysts (Na₂HPO₄, K₂CO₃, and Na acetate) in DMSO at 110°C. The yellowish products were characterized by ¹H‐, ¹³C‐NMR and FT‐IR. The DS of the products is a function of the carbon number of the fatty acid chain, vinyl ester to starch ratio and the type of catalyst. When performing the reactions using Na₂HPO₄ as the catalyst, the DS for the starch laurate compounds is higher than for the corresponding starch stearates. For low vinyl ester to starch ratios, an increase in the vinyl ester concentration leads to higher product DS values. At higher ratios, the DS decreases, presumably due to a reduction of the polarity of the reaction medium. K₂CO₃ and Na acetate are superior catalysts with respect to activity compared to Na₂HPO₄ and products with DS values close to 3 were obtained.     

Nanoenergetic Composites of CuO Nanorods,Nanowires, and Al‐Nanoparticles

This paper reports on the synthesis of the nanoenergetic composites containing CuO nanorods and nanowires, and Al‐nanoparticles. Nanorods and nanowires were synthesized using poly(ethylene glycol) templating method and combined with Al‐nanoparticles using ultrasonic mixing and self‐assembly methods. Poly(4‐vinylpyridine) was used for the self‐assembly of Al‐nanoparticles around the nanorods. At the optimized values of equivalence ratio, sonication time, and Al‐particle size, the combustion wave speed of 1650 m s⁻¹ was obtained for the nanorods‐based energetics. For the composite of nanowires and Al‐nanoparticles the speed was increased to 1900 m s⁻¹. The maximum combustion wave speed of 2400 m s⁻¹ was achieved for the self‐assembled composite, which is the highest known so far among the nanoenergetic materials. It is possible that in the self‐assembled composites, the interfacial contact between the oxidizer and fuel is higher and resistance to overall diffusional process is lower, thus enhancing the performance.     

Post‐polymerization modification of bio‐based polymers: maximizing the high functionality of polymers derived from biomass

The renaissance of the bio‐based chemical industry over the last 20 years has seen an ever growing interest in the synthesis of new bio‐based polymers. The building blocks of these new polymers, so called platform molecules, contain significantly more chemical functionality than their petrochemical counterparts (such as ethene, propene and para‐xylene). As a result bio‐based polymers often contain greater residual chemical functionality in their chains, with groups such as alkenes and hydroxyls commonly observed. These functional groups can act as sites for post‐polymerization modification (PPM), thus further extending the range of applications for bio‐based polymers by tailoring the polymers' final properties. This mini‐review highlights some of the most recent and compelling examples of how to make use of bio‐based polymers with residual functional groups for PPM. It also looks at how the emerging interdisciplinary field of enzymatic polymer synthesis allows for increased functionality in polymers by avoiding side‐reactions as a result of milder reaction conditions, and additionally offers an alternative means of polymer surface modification. © 2018 Society of Chemical Industry     

Structure-scratch properties relationships of acrylate photo-polymerizable protective coatings for thermoplastic substrates

The relationships between the composition and the scratch resistance of clear photo-polymerized protective coatings for thermoplastic substrates were studied in relation with their thermomechanical properties. For this purpose, dynamic mechanical analyses of free-standing films were compared to micro-scratch tests of thick or thin coatings deposited on polycarbonate. In these experiments, the depth indented by the tip, the elastic recovery of the material, the residual depth of the scratch, and the load at which the first crack appears, were analyzed. Different coatings close in formulation were studied. First, the proportion of a specific difunctional monomer featuring a hard structure was varied in order to change the crosslinking density of the polymer network. The thermomechanical properties were consequently modified at high temperature, but remained similar at 23 °C, whereas at this temperature, the scratch properties of the coating evolved with its composition. The addition of 5 wt% alumina or silica nanoparticles did not modify the thermomechanical properties or the scratch resistance of the coatings, even if a more concentrated filler layer was observed near the surface of the coating. Nevertheless, the consequent incorporation of a new diacrylate monomer in the polymer matrix delayed the ductile-brittle transition. Finally the substitution of petro-based monomers by slightly different bio-based compounds led to a change of the scratch behavior of the thickest coatings (150 μm-thick), and increased the critical load for the thinnest coatings (15 μm-thick). It comes out that micro-scratch tests allow a finer comparison of the samples.     

On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers

In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges.