Stereocontrol during photo-initiated controlled/living radical polymerization of acrylamide in the presence of Lewis acids

Poly(acrylamide) (PAM) with controlled molecular weight and tacticity was prepared by UV-irradiation-initiated controlled/living radical polymerization in the presence of dibenzyl trithiocarbonate (DBTTC) and Y(OTf)₃. The rapid and facile photo-initiated controlled/living polymerization at ambient temperature led to controlled molecular weight and narrow polydispersity (M_w/M_n = 1.12-1.24) of PAM. The coordination of Y(OTf)₃ with the last two amide groups in the growing chain radical effectively enhanced isotacticity of PAM. The isotactic sequence of dyads (m), triads (mm) and pentads (mmmm) in PAM were 70.32%, 50.95%, and 29.97%, respectively, which were determined by the resonance of methine (CH) groups in PAM under ¹³C NMR experiment. Factors affecting stereocontrol during the polymerization were studied, including the type of Lewis acids, concentration of Y(OTf)₃, and monomer conversion. It is intriguing that the meso tacticity increased gradually with chain propagation and quite higher isotacticity (m = 93.01%, mm = 86.57%) was obtained in the later polymerization stage (conversion 65-85%).     

BaFCl∶Eu~（2＋）中F色心的浓度和光激励截面与温度和紫外线的辐照波长的关系

本文研究了ＢａＦＣｌ∶ＥＵ（２＋）在不同波长的紫外线辐照和不同的测定温度下的光激励发光性质．通过改变激励方式及激励光的扫描方向，给出了ＢａＦＣｌ∶Ｅｕ（２＋）光激励发光过程中，两种Ｆ色心的浓度比值和光激励截面比值与紫外线辐照波长和测定温度的关系．同时我们还研究了在激励读出过程中，对应两种Ｆ色心的光激励发光强度与激励温度的关系，并且给出了相应于Ｆ（Ｃｌ－）心的热激活能．     

The Effect of UV-Irradiation on Poly(vinyl alcohol) Composites with Bacterial Cellulose

The development of biodegradable packaging materials, especially from renewable resources is a constant preoccupation of nowadays, because of the environmental problems caused by synthetic polymers. The combination of cellulose with other polymeric materials could be an ecologic alternative and a way to use renewable resources for food packaging. Bacterial cellulose which is produced by microbial fermentation is also a promising material which can be used not only in biomedical application, but also as food packaging material. In this research different composite films between poly(vinyl alcohol)-bacterial cellulose (PVA-BC) were obtained by casting method. The obtained films were UV irradiated for different periods of times from 1 to 10 hours, using a mercury lamp, Philips TUV-30, emitting light mainly at 254 nm. Changes in FT-IR spectra before and after UV irradiation and the modification of transparency and of the swelling characteristics of the films were observed. As it was expected the composites materials are sensitive at UV exposure.     

紫外接枝聚合聚乙二醇甲基丙烯酸甲酯制备抗污染聚砜超滤膜

以二苯甲酮(BP)为紫外引发剂,将聚乙二醇甲基丙烯酸甲酯(PEGMA)接枝在聚砜超滤膜表面以提高膜的抗污染性能.在二苯甲酮存在的条件下,波长较长(λ300nm)的紫外光(UV)辐射下发生提氢反应,可以有效防止聚砜分子主链的剪切,保持改性膜的分离性能.考察了PEGMA浓度、UV辐射时间和BP浓度对改性超滤膜接枝度、亲水性和抗污染性能的影响.用表面全反射红外光谱(ATR/FTIR)表征改性前后膜表面化学组成的变化.表面改性膜的纯水通量略有降低而牛血清白蛋白(BSA)截留率有所提高.随着接枝度的提高,PEGMA接枝改性膜的抗污染性能增加.     

紫外辐射接枝法修饰聚乳酸表面及其细胞相容性

通过紫外辐射接枝在聚乳酸膜表面引入聚丙烯酸的方法使聚乳酸材料表面的亲水性和细胞相容性得到改善,研究了各种处理条件对材料表面的羧基密度、表面形态和表面接触角的影响,同时还考察了紫外辐射接枝聚丙烯酸的聚乳酸表面的成骨细胞相容性.红外光谱分析和羧基密度测定结果表明:通过紫外光引发接枝,聚丙烯酸被成功接枝到聚乳酸表面,而且接枝密度受接枝时间和聚丙烯酸质量分数的影响很大.接触角和原子力显微镜研究结果表明:接枝聚丙烯酸后的聚乳酸表面的亲水性和粗糙度明显增加,能够促进成骨细胞的生长.     

Effects of UV-irradiation on the thermo-mechanical properties of optical grade poly(methyl methacrylate)

We studied the evolution of the thermo-mechanical properties of poly(methyl methacrylate) (PMMA) materials exposed to ultra-violet (UV) light. To do so we measured important mechanical parameters including the fracture strength, the stress-strain relation, and Young's modulus as a function of the UV-irradiation dose. We concluded that the mechanical properties of PMMA are affected by UV light. The ductility disappears and the strength and strain at rupture strongly decrease (over 30%). The evolution of the Young's modulus is discussed as a function of the cross-linking degree of the materials. Moreover we observed the occurrence of surface damage, which in its turn enhances the degradation of these mechanical parameters.     

Air plasma or UV-irradiation applied to surface modification of pectin/poly(vinyl alcohol) blends

Poly(vinyl alcohol), pectin and their blends with different components ratio were exposed to low-temperature air plasma or high energy UV-irradiation (λ = 254 nm) for the purpose of surface modification. The physico-chemical changes in surface properties have been studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and contact angle measurements. Surface free energy of polymeric films, its polar and dispersive components have been calculated by Owens-Wendt method. Moreover, the work of adhesion was estimated and the recovery of hydrophobic properties of modified films after storage have been also studied.The few seconds air-plasma treatment caused more effective surface modification than 5-6 h UV-irradiation. The observed changes were partially reversible, contrary to these caused by photo-modification.It was found that pectin/PVA (50:50) blend was characterised by larger susceptibility to plasma modification compared to pure pectin and pure PVA, whereas the photosensitivity to radiation of 254 nm wavelength was the lowest for this specimen in comparison to other studied samples.     

Polymerization Behaviour of Organically Modified Titanium Alkoxides in Solution

Modified titanium alkoxides with polymerizable organic ligands allow the synthesis of copolymers consisting of hybrid organic/inorganic networks. In this work titanium based-precursors were characterized in relation to the polymerization behaviour of the organic matrix. Alkoxide sols were prepared by reaction of methacrylic acid, itaconic acid anhydride, isoeugenol, p-vinylbezoic acid, p-vinylphenylacetic acid, and acetoxyacetomethacrylate with titanium tetraisopropoxide and titanium tetraethoxide. Polymerization reactions were carried out in solution using UV-irradiation and a redox-system of dibenzoylperoxide/N, N-dimethyl-p-toluidine as radical initiators. Especially for chemical activation some complexes showed high reactivity similar to silica-based methacrylates. The systems investigated are capable of acting as adhesive promoters between metal and polymer in dental applications.     

Influence of chemical crosslinking on the creep behavior of ultra-high molecular weight polyethylene fibers

In this study, the effect of chemical crosslinking on the creep behavior of high-strength fibers, obtained by gel-spinning and subsequent hot-drawing of ultra-high molecular weight polyethylene (UHMWPE), is examined. In the first part of the paper, the general aspects of the creep behavior of these fibers are discussed. The second part deals with UHMWPE fibers that are crosslinked by means of a) chlorosulfonation and b) dicumyl peroxide treatment followed by UV irradiation. The latter technique leads to an improvement of the creep resistance of the UHMWPE fibers without affecting their high tensile strengths. In spite of the fact that the network formation is fairly high, the creep cannot be completely removed. The results indicate that the creep process in UHMWPE fibers is associated with a deformation mechanism in the crystalline regions of the fiber, which are not affected by chemical crosslinking.