高缩醛度聚乙烯醇缩丁醛工艺研究

采用水-乙醇混合溶剂法以PVA、丁醛、盐酸为原料,合成了高缩醛度聚乙烯醇缩丁醛(PVB),利用单因素试验法研究了乙醇加入量、二步丁醛加入温度、丁醛加入量、盐酸加入量因素对PVB缩醛度及产量的影响,研究结果表明,最佳的合成工艺为:乙醇与水的质量比为1∶10,在二步丁醛加入温度,15℃,丁醛与PVA质量比为0.7,盐酸与PVA质量比为0.55时,得到的PVB缩醛度为83.1%。     

混合溶剂法制备高聚合度聚乙烯醇研究

以醋酸乙烯为原料,碳酸二甲酯和甲醇为混合溶剂,进行溶液聚合反应制备了高聚合度聚乙烯醇。考察了搅拌转速、甲醇的加入时间、引发剂质量分数、混合溶剂体积分数、溶剂体积比和聚合时间对醋酸乙烯聚合反应的影响,采用正交试验法对醋酸乙烯溶液聚合的反应条件进行了筛选。并通过傅里叶红外光谱和凝胶色谱对最优条件下制得的产品进行确认和分析。结果表明,最佳的聚合条件为:引发剂质量分数为0.01%,混合溶剂体积分数为10%,溶剂体积比V(DMC)∶V(MeOH)为4∶1,聚合时间为2.5 h,所得产品的聚合度为3 557;在最优条件下制备的产品结构未发生变化,且得到了高聚合度、相对分子质量分布较窄的产品。     

制备聚乙烯醇缩醛胶的新配方

报道了一种制备聚乙烯醇缩醛胶的新配方。常规的制备方法是通过甲醛和聚乙烯醇的缩合反应来实现的。作者发现,在反应中加入适量乙醛代替部分甲醛、可明显提高缩醛胶的性能。     

缩醛度的准确计算法

在已有的计算缩醛度的公式中，忽略了聚乙烯醇（ＰＶＡ）母体上原来的酯基，这将给缩醛度的计算带来误差。本文通过缩醛基的测定，从聚乙烯醇缩醛样品中恢复ＰＶＡ母体的质量，在考虑到酯基存在的条件下，推导出计算缩醛度的公式。     

混合溶剂法合成高分子量PAN树脂

优质ＰＡＮ原丝是生产高性能碳纤维的前提，采用高分子量聚丙烯腈共聚树脂进行干喷湿纺是提高原丝性能的有效途径之一。本文采用混合溶剂法合成了分子量为５．２×１０＾５～３．１４×１０＾６的ＰＡＮ共聚树脂，系统地讨论了实验条件对聚合结果的影响，并对反应机理进行了初步探讨，对合成的树脂进行热分析时发现树脂的热行为更适合预氧化反应。     

聚乙烯醇缩醛—环氧结构胶粘剂

介绍了一种新型结构胶——聚乙烯醇缩醛——环氧胶粘剂,它是由聚乙烯醇缩醛、环氧树脂、固化剂、混合溶剂及其他配合剂制成。在飞机及宇航工业中,可广泛用于金属蜂窝结构件的制造。     

聚乙烯醇胶粘剂的缩醛化研究

首先研究了聚乙烯醇与甲醛的缩醛化反应条件,然后用乙醛代替部分甲醛进行改性研究,发现用乙醛代替部分甲醛后,在胶粘剂的各项性能上都有很大改善。     

混合溶剂相分离法制备高通量高截留PES膜

选用DMAc和辛烷作为非溶剂致相分离法(NIPS)的混合溶剂制备聚醚砜(PES)膜,利用两种溶剂在高温下互溶、低温下相分离的特点,制备得到具备高孔隙率和纳米级表面孔径的PES膜。为进一步优化膜的结构性能,研究了辛烷加入量和预蒸发时间对膜性能的影响,最终制备得到孔径为12.50 nm、孔隙率高达89%的海绵状截面结构PES膜,其渗透通量可达65.23 L/(m²hbar),较优化前提升了160%;而对牛血清白蛋白(BSA)的截留率始终维持在95%以上,对同时实现膜的高渗透性和高选择性具有深刻意义。     

醇溶剂法制备高脱乙酰度壳聚糖

采用戊醇-氢氧化钠反应体系,通过对投料比、反应温度、反应时间等影响因素研究了甲壳素的脱乙酰反应,结果表明在四流温度．反应时间1．5h,壳聚糖：NaOH：醇=1：5：11(质量比)条件下制得脱乙酰度为99．7％的壳聚糖,而传统水溶剂脱乙酰度小于50％。     

聚乙烯醇缩甲乙醛制备条件的研究

研究了用聚乙烯醇（ＰＶＡ）、甲醛、乙醛为原料，在盐酸催化作用下，制备聚乙烯醇缩甲乙醛的各种影响因素，探索出了原料用量比、反应时间、反应温度、溶液ｐＨ值、ＰＶＡ浓度、加料方式等最佳反应条件。     

Effects of mixed solvent on gelation of poly(vinyl alcohol) solutions

The relationship between the polymer–solvent interaction and gelation behavior of poly(vinyl alcohol) (PVA) solutions prepared from ethylene glycol/water (EG/water) mixed solvents was investigated using a viscometer, light scattering, FTIR, X‐ray, and pulsed NMR analyses. The viscometric result showed that the affinity to PVA for water is higher than that for EG. The light scattering result showed that the spinodal decomposition rate of the PVA solution decreases rapidly as the water content in the EG/water mixed solvent is increased. On the other hand, the FTIR and X‐ray results both indicated that the crystallinity of the PVA gel decreases with water content. These results imply that the water molecules must improve the affinity of the solvent to PVA to inhibit the aggregation or crystallization of PVA chains. The pulsed NMR measurement results showed that the spin–spin relaxation times related to the polymer‐rich and polymer‐poor phases of the PVA gel increase, and the fractional amount of the polymer‐poor phase increases while that of the polymer‐rich phase decreases with increasing water content. These facts indicated that the increase in the mobility of PVA chains must give rise to the difficulty in chain aggregation of PVA solutions with increasing water content. Two transition temperatures were found in the phase transition of the polymer‐rich phase. The lower transition temperature was attributed to the destruction of the denser chain entanglements in the polymer‐rich phase and the higher transition temperature was mainly concerned with the melting of the crystallites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1113–1120, 2001     

混合溶剂法生产氯磺化聚乙烯实验初探

将高密度聚乙烯（HDPE）树脂溶于混合溶剂中,以偶氮二异丁腈为引发剂,在装有搅拌的搪玻璃反应釜中用氯气进行氯化,用氯气和二氧化硫的混合气体进行氯磺酰化反应后制得氯磺化聚乙烯（CSM）溶液,经后部凝聚、挤压脱水后生产氯磺化聚乙烯。通过实验过程中的数据积累,掌握实验过程中的一些特殊现象,并且对异常现象加以分析和解决,为下一步装置改造创造条件。     

高沸醇木质素的研究进展

高沸醇木质素是采用高沸醇溶剂法从植物原料中提取的木质素,具有纯度高、化学活性强等特点。介绍了高沸醇木质素的制备、结构以及应用基础研究的最新成果,尤其是高沸醇木质素环氧树脂、聚氨酯和聚合物改性材料方面的进展,展望了高沸醇木质素的应用前景。     

Casting solvent effect on crystallization behavior of poly(vinyl acetate)/poly(ethylene oxide) blends: DSC study

Poly(vinyl acetate) (PVAc)/poly(ethylene oxide) (PEO) blends were prepared by casting from either benzene or chloroform. The solvent effects on the crystallization behavior and thermodynamic properties of the blends were studied by the differential scanning calorimeter (DSC). Two grades of PEO with different molecular weights (PEO200 with M_w = 200,000 g/mol and PEO2 with M_n = 2000 g/mol) were used in this work. The thermal analysis revealed that the blends cast from either benzene or chloroform were miscible in the molten state. The crystallization of PEO in the benzene-cast blends was more easily suppressed than it was in the chloroform-cast blends. Furthermore, the benzene-cast blends showed a greater negative value of Flory-Huggins interaction parameter than those cast from chloroform in the PVAc/PEO200 poly-blend system. It was supposed that the benzene-cast blends had more homogeneous morphology. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 411–421, 1997     

Manufacture of modified poly(vinyl acetal) showing fluorescence and molecular recognition

Poly(vinyl acetal) from poly(vinyl alcohol) and 4-dimethylaminobenzaldehyde (DMAB) is synthesized. Fluorescence behavior of the polymer is investigated in acetic acid glacial (HAc), dimethylsulfoxide (DMSO), and dimethylformamide (DMF) solvents. Fluorescence emission intensities of the polymer solutions are different with the change of concentration. The result suggests that the maximum fluorescence emission intensities of the polymer solutions depend on the optimal concentration of the polymer. It has been found that the fluorescence intensity of DMAB is dramatically lower than that of the polymer in the same chromophore concentration, and such phenomenon is termed as structural self-quenching effect (SSQE). The strong fluorescence of the polymer can be quenched by adding electron-deficient monomers which have no chromophore moieties such as lactic acid, adenine, etc., and their Stern–Volmer constants are determined. It is observed that the higher the electron deficiencies of the quenchers, the higher the Stern–Volmer constants, which means stronger quenching effect. The result indicates that the polymer can recognize these biologic small molecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2385–2390, 1999     

Adhesion properties of eco-friendly PVAc emulsion adhesive using nonphthalate plasticizer

An eco-friendly poly (vinyl acetate) emulsion adhesive was synthesized without phthalate. Four types of eco-friendly plasticizers for use in these adhesives were selected to confirm their primary properties by injecting the eco-friendly plasticizer without any prior change to its processing or cost. The four types of eco-friendly plasticizers used were dibutyl phthalate DBP-based product, dialkyl ester, acetyl tributyl citrate, and pentandiol-di-isobutyrate. Their properties were determined by comparison with the existing (DBP)-based product. As a result, an emulsion adhesive was produced without addition of phthalate or need for additional additives, resulting in a significant decrease in cost. However, the low temperature characteristics of the eco-friendly plasticizers were slightly inferior to those of DBP. These adhesives containing eco-friendly plasticizer were studied and their characteristics for adhesion strength, water resistance, ability for low temperature film formation, excellent storage stability, and lack of volatile organic compounds productions (including phthalate) were confirmed.     

低聚合度、低醇解度聚乙烯醇的合成与性能研究——I.低聚合度聚醋酸乙烯酯的合成

以甲醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,采用自由基聚合方法合成了低聚合度聚醋酸乙烯酯,并对其结构进行了表征。讨论了聚合时间、引发剂用量、物料配比、聚合温度等因素对聚合率的影响,获得了相对较佳的工艺参数。     

Synthesis of high-molecular weight poly(vinyl alcohol) by low-temperature emulsifier-free emulsion polymerization of vinyl acetate and saponification

High-molecular weight (HMW) poly(vinyl alcohol) (PVA) was prepared via an emulsifier-free emulsion polymerization of vinyl acetate (VAc) using a redox initiation system in low temperatures, and the subsequent saponification with potassium hydroxide in methanol. The effect of the polymerization conditions on the conversion, molecular weight, and branching degree was investigated. PVA with maximum viscosity-average degree of polymerization (DP) of 8270 could be prepared by saponification of poly(vinyl acetate) (PVAc), with DP of 10,660 obtained at temperature of 10°C, monomer concentration of 30%, potassium persulfate molar ratio to monomer of 1/2000, agitation speed of 160 rpm. The conversion was above 90%. From the emulsifier-free emulsion polymerization of VAc in low temperature, PVAc with HMW and high linearity was effectively prepared, which might be useful for the preparation of high-strength and high-modulus PVA fiber. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fibrous membranes of cellulose acetate and poly(vinyl pyrrolidone) by electrospinning method: Preparation and characterization

Fibrous membranes of cellulose acetate (CA), poly(vinyl pyrrolidone) (PVP) and composite membranes of these polymers, were obtained by the electrospinning method. Using systematic method, the optimal conditions for preparation of fibrous membranes were found. Both CA and PVP a concentration of 8% weight was found. The CA was dissolved in a acetone:water solution, volume ratio 80 : 20 and the PVP is dissolved in ethanol:water solution, ratio volume 85 : 15. The flow rate for both polymers was 1.5 mL h^?1. The same applied voltage value and the distance between the needle and collection plate were for polymer both, 15 kV and 15 cm respectively. The morphology of fibrous membranes and composite membranes were evaluated by scanning electron microscopy (SEM). The CA fibers showed ribon morphology, while the PVP fibers were cilindric, in both cases with diameters in the micrometer range. Thermogravimetric analysis showed that CA had a complete degradation to 445°C, while the fibrous membranes PVP required a value of temperature for degradation of up to 571°C. Fibrous composite membrane PVP/CA/PVP shows a higher value of strain at break (%), and a lower value of tensile strength (MPa) compared to CA/PVP/CA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Semicontinuous emulsion polymerization of vinyl acetate: Effect of ethoxylation degree of nonionic emulsifiers

Poly(vinyl acetate) latices were prepared in the presence of an ammonium persulfate initiator, 10–50 mol of an ethoxylated nonylphenol nonionic emulsifier, and a poly(vinyl alcohol) colloid stabilizer by applying semicontinuous emulsion polymerization (delayed monomer and initiator addition process) in a laboratory scale similar to industrial practice. Two approaches were applied: the molar concentration of the nonionic emulsifier was kept constant and the weight ratios in the polymerization recipe varied or the weight ratios were kept constant. The effects of the change in the ethoxylation degree of the emulsifier to the final latex viscosity, average polymer molecular weight, polymer grafting degree, surface tension of the latex, and the surface free energy of the dried films were investigated. It was determined that the resultant latex viscosity decreases and the viscosity‐average polymer molecular weight increases with increase of the nonionic emulsifier ethoxylation degree. The increase of the ethoxylation degree does not seriously affect the surface tension of the resultant latex or the surface free energy of the dried poly(vinyl acetate) films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 844–851, 2002