RI/VI联用测定聚乙烯相对分子质量及其分布

150℃测试温度下，以1，2，4-三氯苯为溶剂，采用示差折光指数器，毛细管黏度计双检测器联用凝胶渗透色谱技术测定了聚乙烯的相对分子质量及其分布。与常规凝胶渗透色谱法对比，该方法不仅能直接得到聚乙烯较精确的相对分子质量和分布形态，同时可以得到聚乙烯的特性黏数分布。     

Photochemical reduction of molecular weight and number of double bonds in natural rubber film

Natural rubber (NR) can be degraded depending on various factors such as heat, mechanical force, chemical reaction, and light. Light is a very interesting factor because it can cause the NR to degrade under low temperature and pressure. The photo-degradation of NR films was carried out to investigate the effects of the light and the temperature on the reduction of the weight-average molecular weight (Mw) and the double bonds in the NR films. The NR films, with and without catalysts, titanium dioxide (TiO₂), and potassium persulfate (K₂S₂O₈), were exposed to light from a mercury light bulb at 7,000 and 36,000 lux, and at the temperature of 25 °C and 80 °C for 192 hrs. After exposure, the Mw of the NR films was analyzed by gel permeation chromatography (GPC). Changes in the Mw were used to construct a kinetic model for the process, (1/Mw)=(1/Mw₀)+(kt/2M₀) where k is the rate constant, and M₀ is the Mw of the monomer unit. The linear relationship between 1/Mw and time suggested pseudo first-order processes with random scission. The Mw distribution information from the GPC was used to calculate the number of double bonds in the NR films. The trend of the double bonds reduction curves was quite similar to the result obtained from the calculation from the FTIR spectra. This indicated that this calculation method might possibly be another alternative way to obtain the number of double bonds in the NR.     

香豆胶衍生物的化学结构及稳定性研究

将市售商品溶于水,用异丙醇沉析提纯,溶于0.1 mol/L NaNO3纯水溶液中,经0.5μm滤膜过滤后用水相凝胶渗透色谱法(GPC)测定,测得香豆胶(FG)、羟丙基香豆胶(HPFG)、阳离子香豆胶(CFG)的数均、重均相对分子质量Mn、Mw分别为:1.19×105、3.36×105,8.52×104、2.85×105,9.33×104、2.87×105。用甘露聚糖链在碱性条件下醚化时发生降解,解释两种改性FG的相对分子质量较FG低而多分散性(Mw/Mn)较FG高的测试结果。认为商品FG的1%水溶液黏度(1300 mPa.s)高于商品HPFG和CFG(分别为705和610 mPa.s)的原因是前者相对分子质量较高且残渣含量也较高(~10%,后二者为1%~2%)。HPFG的取代度为0.12,根据文献发表的13C-NMR数据确认HPFG分子链上羟丙基取代位置为C6。讨论了香豆胶(半乳甘露聚糖)的化学结构。热重分析法测定的热稳定性,HPFG高于CFG,CFG又高于FG。图6表3参13。     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of phenol–formaldehyde resol resins by lignin,starch, and urea

Lignin‐based chemicals, starch, and urea were used as modifiers for phenol–formaldehyde resol resins. The effects of the addition stage of the modifiers used in the synthesis of the resins and the type of modification reagent on the structures of the resins and their molar masses and reactivities were investigated. The modifications with corn starch and lignin promoted condensation; this was verified by increased molar masses and high ratios of methylene bridges to the sum of free ortho and para aromatic groups with respect to the corresponding reference resin without a modification reagent. The later the modifier was added to the resin condensation mixture, the more methylene bridges were formed with respect to the amounts of free ortho and para aromatic groups. In addition, when urea or wheat starch was added in the later condensation stage, the final condensation also reached high stages. The modifications with lignosulfonate and starch, as well as the early addition of urea, enhanced p–p′ bridge structures. The lowest condensation stage and, therefore, the highest reactivity were found when wheat starch was added with the starting reagents. The curing heat of the wheat‐starch‐modified resins decreased according to the deferred addition point of starch. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 582–588, 2003     

Studies on polyacrylates containing pendant ligand with carbonyl and hydroxyl functions and their divalent metal complexes

A series of monomers were prepared by reacting (meth)acryloyl chloride with 2,4‐dihydroxybenzophenone, 2,4‐dihydroxybenzaldehyde, and 2,4‐dihydroxyacetophenone, respectively. The monomers were polymerized in dimethylformamide (DMF) at 70°C using benzoyl peroxide as an initiator. Polymer–metal complexes were obtained from DMF solutions of polymers with an aqueous solution of metal ions. The polymers and polymer–metal complexes were characterized by elemental analysis and spectral studies. The IR spectra of these complexes suggest that the metals are coordinated through the oxygen of the carbonyl group and the oxygen of the phenolic–OH group. The electronic spectra, electron paramagnetic resonance (EPR) spectra, and magnetic moments of polychelates showed an octahedral and square planar structure for Ni(II) and Cu(II) complexes, respectively. X‐ray diffraction studies revealed that polychelates are highly crystalline. The thermal and electrical properties, catalytic activity, and structure–property relationships are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2083–2090, 2003     

聚天冬氨酸的合成与表征

介绍了以L -天冬氨酸为原料 ,热缩合成聚天冬氨酸酐 ,水解得到聚天冬氨酸的合成工艺。采用凝胶色谱法测定了聚天冬氨酸的分子量 ,并用核磁共振对其进行了表征。     

聚天冬氨酸的合成与表征

以L-天冬氨酸为原料,热缩合成聚天冬氨酸酐,水解得到聚天冬氨酸。采用凝胶色谱法(GPC)测定了聚天冬氨酸的分子量,并用核磁共振(NMR)对其进行了表征。     

Kinetics of microwave‐assisted polymerization of ϵ‐caprolactone

The kinetics of polymerization of ?‐caprolactone (CL) in bulk was studied by irradiating with microwave of 350 W and frequency of 2.45 GHz with different cycle‐heating periods (30–50 s). The molecular weight distributions were determined as a function of reaction time by gel permeation chromatography. Because the temperature of the system continuously varied with reaction time, a model based on continuous distribution kinetics with time/temperature‐dependent rate coefficients was proposed. To quantify the effect of microwave on polymerization, experiments were conducted under thermal heating. The polymerization was also investigated with thermal and microwave heating in the presence of zinc catalyst. The activation energies determined from temperature‐dependent rate coefficients for pure thermal heating, thermally aided catalytic polymerization, and microwave‐aided catalytic polymerization were 24.3, 13.4, and 5.7 kcal/mol, respectively. This indicates that microwaves increase the polymerization rate by lowering the activation energy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1450–1456, 2004     

Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp

Multi‐angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N‐dimethylacetamide and separated by size exclusion chromatography (SEC). The weight‐average and number‐average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct‐standard‐calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose‐equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003