亲水性PET共混材料的制备及性能研究

以机械共混法制备亲水性聚对苯二甲酸乙二醇酯（PET）共混材料，并通过接触角测定仪、差示扫描量热仪(DSC)和电子万能材料试验机等对共混材料的亲水性能、热性能和力学性能等进行研究与分析。结果表明，亲水处理剂聚乙二醇（PEG）、聚丙烯酸钠（PAAS）、聚乙烯吡咯烷酮（PVP）均能改善PET的亲水性能，影响PET的结晶性能，但亲水处理剂对PET的力学性能影响较小，其中PET/PEG共混材料的亲水性最优；随着PEG含量的增加，PET/PEG共混材料的亲水性先逐渐增强，当PEG含量高于5 %后，共混材料的亲水性变化很小；且PET的结晶度随着PEG的加入呈现先增大后减小的趋势。     

Preparation,structural elucidation,molecular weight determination,and molecular recognition of first‐ and second‐tier dendrimer molecules

1,3,5‐Triglyceratetriazine [first tier (G₁)] and tri(1,3,5‐triglycerate) triazine [second tier (G₂)] dendrimers were prepared with 1,3,5‐trichlorotriazine and sodium glycerate in a 1 : 3 mass ratio in an ethanolic medium.G₁ and G₂ were amorphous, white, solid substances. Their structures were elucidated with IR, ¹H‐NMR, and ¹³C‐NMR, and their thermal stability was studied with thermogravimetric analysis. The activation energy was calculated with the Freeman–Carroll model. Densities, viscosities, and surface tensions for 0.01–0.08 mol/kg aqueous solutions increased at 0.01 mol/kg for sodium glycerate, 1,3,5‐trichlorotriazine, 1,3,5‐triazine triglycerate chloride, G₁, and G₂. These values were measured at 298.15 K. The apparent molal volume, reduced viscosity, and inherent viscosity were calculated from the densities and viscosities, respectively. The data were regressed for the limiting densities, limiting apparent molal volumes, intrinsic viscosities, limiting inherent viscosities, and limiting surface tensions for solute–solvent interactions. The positive limiting apparent molal volume values were noted in the order of G₂ > 1,3,5‐triazine triglycerate chloride > G₁ > 1,3,5‐trichlorotriazine > sodium glycerate, with weaker hydrophilic intermolecular interactions of G₂. The higher intrinsic viscosity and limiting inherent viscosity values for G₂ implied stronger G₂–H₂O hydrophilic interactions, and the higher limiting apparent molal volume of G₂ indicated slightly higher dynamic conformational changes in comparison with G₁, with stronger structural activities. © 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     

血液过滤用熔喷PBT非织造布紫外辐照接枝改性研究

研究了血液过滤用熔喷PBT非织造布的紫外辐照气相接枝改性方法。通过实验选择了丙烯酸(AAc)为接枝单体 ,探讨光照时间、预辐照时间、单体温度、引发剂浓度、氮气压力对接枝率和表面润湿张力的影响 ,结果得到最佳的紫外辐照接枝条件为 :室温下 ,光距 2 0cm ,预浸 10min ,二苯甲酮 (BP) 0 .0 37mol/L ,冲入单体的氮气流量 87.5h/L ,反应时间 30min。PBT非织造布AAc紫外辐照接枝后表面润湿张力可以达到 85mN/m左右 ,且表面润湿张力随接枝率的提高而增加     

Effect of the nature and degree of crosslinking on the Rose Bengal uptake by DVB‐, NNMBA‐, HDODA‐, and TTEGDA‐crosslinked aminopolyacrylamides

Polyacrylamides with 2–20 mol % divinyl benzene (DVB), N,N′‐methylene‐bisacrylamide (NNMBA), 1,6‐hexanediol diacrylate (HDODA), and tetraethyleneglycol diacrylate (TTEGDA) crosslinking and without crosslinking were prepared by free radical solution polymerization. Amino functions were incorporated into these polymers by transamidation with excess ethylenediamine. The dye uptake of nonprotonated and protonated aminopolyacrylamides was followed by batch equilibration method towards Rose Bengal (RB), Methyl Orange (MO), Methyl Red (MR), and Methylene Blue (MB). RB uptake by the polyacrylamide‐supported systems is higher than other dyes. Generally the dye uptake by the protonated systems is higher than the nonprotonated systems. To optimize the conditions of dye uptake, the effect of the concentration of RB solutions, temperature, and pH were followed. Kinetic studies showed that the uptake of RB by both nonprotonated and protonated crosslinked aminopolyacrylamides is a phase boundary process followed by three‐dimensional diffusion. The extent of RB uptake by the various systems depends on the nature and degree of crosslinking, and the relative rigidity/flexibility ofthe polyacrylamide support. Thus, the dye uptake followed the order: linear > NNMBA‐ > DVB‐ > TTEGDA‐ > HDODA‐crosslinked system. The dye uptake followed the same trend as the variation of amino capacity with degree of crosslinking in the respective crosslinked system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

混合催化剂合成水性环氧丙烯酸酯的研究

通过环氧丙烯酸树脂和双羟基化合物反应,获得具有亲水性链段的水性环氧丙烯酸酯。研究了催化剂用量和反应温度对转化率的影响,确定了以混合催化剂的最佳反应条件。采用FT-IR红外光谱对所合成的数值进行了表征,实验结果表明可以获得目的产物。     

Pb2+ binding by polyaspartyl polymers and their application to Pb2+ removal from glycyrrhizin

Polyaspartate is an excellent Pb²⁺‐binding agent in comparison with some polyaspartamide derivatives with different side chains, in that it possesses a higher Pb²⁺ uptake and a lower Pb²⁺ equilibrium concentration. Equilibrium sorption data for Pb²⁺ on polyaspartate can be well fitted with the Freundlich and Langmuir models. Experimental results show that a crosslinked polyaspartate hydrogel is superior to poly(acrylic acid)‐based resins and polystyrene‐based chelating resins. IR spectra and X‐ray photoelectron spectra reveal that the polyaspartate hydrogel binds Pb²⁺ by both an ion‐exchange mechanism and a chelating mechanism. The polyaspartate hydrogel is also an effective agent for the removal of Pb²⁺ from glycyrrhizin. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2215–2220, 2005     

Poly(L‐lactide). X. Enhanced surface hydrophilicity and chain‐scission mechanisms of poly(L‐lactide) film in enzymatic,alkaline, and phosphate‐buffered solutions

Attempts were carried out to enhance the surface hydrophilicity of poly(L ‐lactide), that is, poly(L ‐lactic acid) (PLLA) film, utilizing enzymatic, alkaline, and autocatalytic hydrolyses in a proteinase K/Tris–HCL buffered solution system (37°C), in a 0.01N NaOH solution (37°C), and in a phosphate‐buffered solution (100°C), respectively. Moreover, its chain‐scission mechanisms in these different media were studied. The advancing contact‐angle (θ_a) value of the amorphous‐made PLLA film decreased monotonically with the hydrolysis time from 100° to 75° and 80° without a significant molecular weight decrease, when enzymatic and alkaline hydrolyses were continued for 60 min and 8 h, respectively. In contrast, a negligible change in the θ_a value was observed for the PLLA films even after the autocatalytic hydrolysis was continured for 16 h, when their bulk M_n decreased from 1.2 × 10⁵ to 2.2 × 10⁴ g mol^?1 or the number of hydrophilic terminal groups per unit weight increased from 1.7 × 10^?5 to 9.1 × 10^?5 mol g^?1. These findings, together with the result of gravimetry, revealed that the enzymatic and alkaline hydrolyses are powerful enough to enhance the practical surface hydrophilicity of the PLLA films because of their surface‐erosion mechanisms and that its practical surface hydrophilicity is controllable by varying the hydrolysis time. Moreover, autocatalytic hydrolysis is inappropriate to enhance the surface hydrophilicity, because of its bulk‐erosion mechanism. Alkaline hydrolysis is the best to enhance the hydrophilicity of the PLLA films without hydrolysis of the film cores, while the enzymatic hydrolysis is appropriate and inappropriate to enhance the surface hydrophilicity of bulky and thin PLLA materials, respectively, because a significant weight loss occurs before saturation of θ_a value. The changes in the weight loss and θ_a values during hydrolysis showed that exo chain scission as well as endo chain scission occurs in the presence of proteinase K, while in the alkaline and phosphate‐buffered solutions, hydrolysis proceeds via endo chain scission. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1628–1633, 2003     

水性丙烯酸树脂的合成研究

以甲基丙烯酸甲酯、丙烯酸丁酯为主要单体,以过氧化苯甲酰为引发剂,通过引入亲水性基团羧基和羟基,制备了水性丙烯酸树脂。确定了最佳反应条件,讨论了水性基团的用量对树脂性能的影响,并用红外光谱(FT-IR)和差示扫描量热分析(DSC)对所合成树脂的结构进行了分析和表征。     

Oxygen plasma modification of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) film surfaces for tissue engineering purposes

Plasma glow‐discharge application is known as a technique to coat or modify the surfaces of various materials. In this study, the influence of oxygen rf‐plasma treatment on surface and bulk properties of a biological polyester, poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), were studied by determining water content and water contact angle, and by using X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The plasma‐treated films absorbed more water than the untreated film, and the absorbance increased with the total power applied. The water contact angles decreased and O/C atomic ratio increased on treatment, indicating that the material became more hydrophilic due to increases in the oxygen‐containing functional groups on the surface of the polymer. A direct relation could be observed when the O/C ratio was plotted against the total power applied (treatment duration × treatment power). SEM revealed a visual record of surface modification, the extent of which increased with increased total power. It was thus possible to alter the surface chemistry and relevant properties of the polymer film using oxygen plasma as a tool. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1285–1289, 2003