可降解温敏型共聚物PLGA-PEG-PLGA的合成及辐照法分子量调整

合成了不同嵌段的可降解的温敏型聚乙交酯丙交酯-聚乙二醇-聚乙交酯丙交酯共聚物（DL—lactide—co—glycolide-b-ethylene glycol—b—DL—lactide—co—glycolide，PLGA-PEG—PLGA）。用红外、核磁共振、凝胶渗透色谱等表征了其化学结构、分子量及分子量分布，研究了其相变过程。用辐照法成功地进行了PLGA—PEG—PLGA分子量调整。实验结果表明，在反应温度150℃催化剂辛酸亚锡0．04g反应8h，5．08g乙交酯与12．61g丙交酯（摩尔比为1：2）的条件下，产物溶于水后得到的水凝胶具有明显的相变过程。不同分子量的共聚物相变温度不同，在同定聚乙二醇分子量且共聚物溶液浓度相同条件下，共聚物中丙交酯与乙交酯比例越高，共聚物分子量越大，相同浓度下的分子量越大的共聚物形成的溶胶，凝胶转变温度越低，凝胶-溶胶转变温度越高。当辐照20kGy样品的分子量分布最大，从而改变凝胶的相变温度。     

已二醇二丙烯酸酯对真丝的接枝改性研究

研究了用二醇二丙烯酸酯为接枝单体、过硫酸铵（APS）为引发剂对真丝的接枝共聚反应，分析了接枝率的影响素，并测试了改性真丝的主要应用性能。结果表明：乳液和乙醇/水为溶剂的2种体系都能在真丝上获得较高接枝率。对于乙醇/水体系v(乙醇）：v(H2O）=1:1，接枝单体20～30g/L,2%甲酸4ml，引发剂APS 0.5g/L,65～70℃接枝60min的接枝率高。改性后真丝的断裂强度、延伸度、吸湿性能都可获得改善，对酸、碱的溶解性提高，但染色性能提高不明显，对泛黄性改善一般。     

Preparation of an anion‐exchange adsorbent by the radiation‐induced grafting of vinylbenzyltrimethylammonium chloride onto cotton cellulose and its application for protein adsorption

Poly(vinylbenzyltrimethylammonium chloride)‐graft‐cotton cellulose, an anion‐exchange matrix, was synthesized by a mutual radiation‐induced grafting technique with a ⁶⁰Co γ‐radiation source. The grafted matrix was characterized by grafting yield estimation, elemental analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The grafting yield decreased with the increase in the dose rate. However, the grafting yield and nitrogen content of grafted samples increased almost linearly with an increase in the total irradiation dose. To evaluate the performance of the grafted anion‐exchange matrix, the protein adsorption and elution behavior were investigated in a continuous column process under various experimental conditions, with bovine serum albumin used as a model protein. The binding and elution behavior of the anion‐exchange matrix depended on different experimental parameters, such as the grafting yield, ionic strength, pH of the medium, and amount of protein loaded. From a breakthrough curve, the equilibrium binding capacity and elution percentage of the grafted anion‐exchange matrix were estimated to be 40 mg/g and 94%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5512–5521, 2006     

Examination of the role of oxygen in the photografting of methacrylic acid on a polyethylene film with a mixed solvent consisting of water and organic solvents

The photografting of methacrylic acid (MAA) on a linear low‐density polyethylene film (thickness = 30 μm) under air and nitrogen atmospheres was investigated at 60°C in mixed solvents consisting of water and an organic solvent, with xanthone as a photoinitiator. The organic solvents used were acetone, methanol, tetrahydrofuran, and dioxane. A maximum percentage of grafting occurred at a certain concentration of the organic solvent in the mixed solvent. This was observed for the systems under both air and nitrogen. The grafting reaction under air exhibited an induction period, but the rate of grafting after the period was greater than that under nitrogen. The formation of poly(ethylene peroxide)s by photoirradiation seemed to be a factor for the accelerated photografting under air. On the basis of attenuated total reflection infrared spectroscopy and scanning electron microscopy of the grafted film, the MAA‐grafted chains of the sample prepared under air tended to penetrate more deeply inside the film than those of the sample prepared under nitrogen. The resulting grafted films exhibited a pH‐responsive character: the grafted films shrank in an acidic medium but swelled in alkaline medium. This was evaluated from measurements of dimensional changes in the grafted films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 992–998, 2003     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

A Micellar Route to Ordered Arrays of Magnetic Nanoparticles: From Size‐Selected Pure Cobalt Dots to Cobalt–Cobalt Oxide Core–Shell Systems

Starting with Co‐salt‐loaded inverse micelles, which form if the diblock copolymer polystyrene‐block‐poly(2‐vinylpyridine) is dissolved in a selective solvent like toluene and CoCl₂ is added to the solution, monomicellar arrays of such micelles exhibiting a significant hexagonal order can be prepared on top of various substrates with tailored intermicellar distances and structure heights. In order to remove the polymer matrix and to finally obtain arrays of pure Co nanoparticles, the micelles are first exposed to an oxygen plasma, followed by a treatment in a hydrogen plasma. Applying in‐situ X‐ray photoelectron spectroscopy, it is demonstrated that: 1) The oxygen plasma completely removes the polymer, though conserving the original order of the micellar array. Furthermore, the resulting nanoparticles are entirely oxidized with a chemical shift of the Co 2p_3/2 line pointing to the formation of Co₃O₄. 2) By the subsequent hydrogen plasma treatment the nanoparticles are fully reduced to metallic Co. 3) By exposing the pure Co nanoparticles for 100 s to various oxygen partial pressures pequation/tex2gif-inf-5.gif, a stepwise oxidation is observed with a still metallic Co core surrounded by an oxide shell. The data allow the extraction of the thickness of the oxide shell as a function of the total exposure to oxygen (pequation/tex2gif-inf-7.gif × time), thus giving the opportunity to control the ferromagnetic–antiferromagnetic composition of an exchange‐biased magnetic system.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Grafting of maleic anhydride onto polyethylene through a green chemistry approach

The grafting of a polymer can lead to the improvement and modification of the polymer and thus expand its applications. Grafting methods include solution grafting in organic solvents, melt grafting at high temperatures, and light grafting with radioactive sources. These methods have their advantages and disadvantages. The disadvantages include waste treatment, consumption of energy, and so on. In this study, a hydrothermal process which is called the green approach, was developed to prepare graft copolymers. The effect of various factors on the grafting degree was investigated in detail. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone) grafted sodium alginate hydrogel beads for the controlled release of indomethacin

Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.