氧化还原引发降解天然橡胶与丙烯酸酯共聚的研究

研究了降解天然橡胶胶乳与丙烯酸甲酯、丙烯酸丁酯的聚合，以过氧化苯甲酰—N，N—三甲基苯胺(BP0—DMA)为氧化还原引发剂，考察了不同反应温度、引发剂配比、乳化剂用量及加料方式对单体转化率和接枝率的影响；用红外光谱对共聚物进行了表征。结果表明，采用乳化还原引发剂可使聚合反应低温快速进行，过量还原剂起阻聚作用，采用复合乳化剂可提高聚合反应速度和乳液稳定性，补加料可提高接技率。     

羧基偏氯乙烯丁苯胶乳粒子的相态结构和应用性能

以过硫酸铵为引发剂，十二烷基硫酸钠为乳化剂，采用种子聚合工艺，合成了偏氯乙烯质量分数为２３％～４３％的羧基偏氯乙烯丁苯胶乳。通过电镜观察到所合成的胶乳粒子具有核－壳结构。通过测定胶闰子表面层的羧基数量，研究了羧基的分布，结果表明，羧酸种类对羧基在胶乳粒子中及在聚合体系中的分布有重要影响，该胶乳作为地毯背衬粘合剂，具有粘合力高，极限氧指数高的特点，是一种较好的阻燃性粘合剂。     

Copolymerization of phenylacetylene with various acetylenes by W- and Mo-based catalysts

In the copolymerization of phenylacetylene with various acetylenes catalysed by WCl₆·Ph₄Sn, the relative reactivity of monomer decreased with increasing steric effect of monomer, e.g. HC  Cn-Bu, HC  Cn-Hex > HC  CPh, HC  Cs-Bu > HC  Ct-Bu, MeCCPh, CICCPh. While 1-chloro-2-phenylacetylene (a disubstituted acetylene) showed high reactivity in the homopolymerization by Mobased catalysts, the reactivity was remarkably depressed in the presence of phenylacetylene as comonomer. Based on these results, the relative reactivity of the acetylenic monomers in copolymerization was explained in terms of competitive coordination of monomers to the propagating end.     

MA-AM-AA三元共聚物的制备及阻垢性能

以马来酸酐(MA)、丙烯酸(AA)和丙烯酰胺(AM)为原料,研制出环保型三元共聚阻垢剂PMAA,并通过研究其阻垢性能确定了产品的最佳工艺配方。实验结果表明,当单体的质量配比m(AA)∶m(AM)∶m(MA)=2∶3∶0·5,引发剂用量为单体总质量的1.5%,反应温度为80℃,单体质量分数为15%时,得到的聚合物PMAA的用量为5mg/L时,用国标法测得其对碳酸钙的阻垢率达94·15%,对磷酸钙的阻垢率达80·93%。     

固相接枝共聚法制备PP—g—PS

用固相接枝共聚方法制备了聚丙烯接枝苯乙烯(PP-g-PS),详细地考察了聚丙烯与引发剂的品种、反应温度、苯乙烯及引发剂的浓度等因素对接枝率和接枝效率的影响。研究结果表明:PP-g-PS具有较高的接技率,应用于聚丙烯/聚苯乙烯(PP/PS)共混物中,能降低分散相PS的粒径,提高PP/PS的相容性。     

Studies on grafting of acrylic acid onto polypropylene melt‐blown nonwovens induced by electron‐beam preirradiation

We report the graft copolymerization of acrylic acid onto the polypropylene (PP) melt‐blown nonwovens induced by electron beam (EB) preirradiation in this article. The occurrence of the graft copolymerization was confirmed by means of XPS, FTIR, and SEM. The effects of preirradiation dose, monomer concentration, bath ratio, reaction time, and temperature on the graft ratio were investigated. The water conservation, water absorption rate, and K⁺ exchange capacity were also determined on the grafted PP melt‐blown nonwovens, which showed that EB preirradiation‐induced grafting was an effective way to improve the hydrophicility of PP melt‐blown nonwovens. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4971–4977, 2006     

Graft copolymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto carboxymethylcellulose (sodium salt) by H2O2/Fe+2 redox pair

The effect of the reaction conditions on the grafting parameters during grafting of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto sodium carboxymethylcellulose using H₂O₂/Fe⁺² redox pair are studied at 30°C. The grafting ratio, add on, and conversion initially increase with the H₂O₂ concentration in the range of (10.0–15.0) × 10^?2 mol dm^?3. Thereafter, these parameters decrease with the H₂O₂ concentration. The grafting ratio, add on, and conversion increase when increasing the ferrous ion concentration from (0.5 to 4.0) × 10^?2 mol dm^?3 and decrease with a further increase in the concentration. It is observed that the grafting ratio and add on increase with the monomer concentration, whereas the conversion decrease. The hydrogen ions seem to be facilitating the grafting reaction up to a certain concentration and after this concentration seem to be retarding the process. The grafting ratio, add on, and conversion decrease with the sodium carboxymethylcellulose concentration. When increasing the time period from 60 to 90 min, the grafting parameters increase but decrease thereafter. Similarly, when increasing the temperature from 25 to 30°C, the grafting parameters increase and decrease thereafter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4819–4825, 2006     

A promising copolymer of aniline and m-aminophenol: Chemical preparation, novel electric properties and characterization

A copolymer, poly(aniline-co-m-aminophenol), was synthesized chemically. The monomer concentration ratio strongly affects the copolymerization rate and the properties of the copolymer. A solution consisting 0.34 M aniline, 0.012 M m-aminophenol, 0.47 M ammonium peroxydisulfate and 2 M H₂SO₄ was found to be an optimum mixture for the chemical copolymerization. The visible spectra show that a high concentration ratio of m-aminophenol/aniline in the mixture inhibits the chain growth of the copolymer. The spectra of IR and ¹H NMR demonstrate that m-aminophenol units are included in the copolymer chain, which play a key role in extending usable pH region of the copolymer. The result of cyclic voltammograms in a wide potential region of −0.20-0.80 V (vs. SCE) indicates that the copolymer prepared under the optimum condition still held 52.7% of the electrochemical activity when the copolymer electrode was transferred from a solution of pH 4.0 to a solution of pH 11.0, which is much better than that of polyaniline. The X-ray diffraction spectra and images of the copolymers reveal a fact that the changes in the crystal structure and morphology of the copolymers are as a function of the monomer ratio in the mixture. The conductivity of the copolymer prepared under the optimum condition is 2.3 S cm⁻¹ and slightly depends on the pH value.     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006