甲基丙烯醛氧化酯化制甲基丙烯酸甲酯

制备了用于甲基丙烯醛(MAL)一步氧化酯化为甲基丙烯酸甲酯(MMA)的新型催化剂;考察了反应温度、催化剂在反应体系中的质量分数对MAL转化率和产物选择性的影响;将离子液体[bmim]PF6用于该反应中,不仅提高了产物的选择性,还能有效防止产物的聚合。反应温度θ=50℃,催化剂在反应体系中质量分数为2 4%,pH=10 5,O2流量6mL/min,反应时间6h时,在反应体系中添加1mL离子液体[bmim]PF6,MAL的转化率为96 2%,MMA单体的选择性可达98 7%。     

对映选择性氢化法合成苯甘氨酸甲酯

以α 肟基苯乙酸甲酯为原料,硫酸奎宁为修饰剂,通过Pd/C催化氢化合成苯甘氨酸甲酯。考察了反应温度、溶剂、修饰剂的量对对映选择性的影响。最佳反应条件:25～28℃、乙醇为溶剂、氢气压力101 325kPa、n(修饰剂)∶n(底物)=1∶10,苯甘氨酸甲酯的光学产率达51 3%。     

月桂酸甲酯的合成研究

采用自制的磺化DNW 1树脂作为合成月桂酸甲酯的催化剂。考察了酯化反应中各种因素对酯化率的影响。在醇酸摩尔比20∶1,催化剂用量为月桂酸质量的15%,回流反应12h的反应条件下,酯化率可达94.6%。该方法反应条件温和,不需要加带水剂,不需要分水;催化剂可以直接过滤分离出来重复使用,大大简化了分离操作;催化剂重复使用12次以上,酯化率仍保持在94%左右,表现出良好的活性和选择性。磺化DNW 1树脂作为液固酯化反应催化剂具有显著的应用价值。     

四氯化锡催化合成β-萘甲醚

四氯化锡催化下,β 萘酚与无水甲醇反应合成β 萘甲醚,考察了甲醇用量、催化剂用量、反应时间等对产率的影响。当β 萘酚取1.8g,甲醇1.5mL,SnCl4·5H2O取0.33g时,80℃反应10h,β 萘甲醚产率可达75.3%。     

Blends of ethylene–methyl acrylate–acrylic acid terpolymers with ethylene–acrylic acid copolymers: Mechanical and thermomechanical properties

The effect of methyl acrylate content in ethylene–methyl acrylate–acrylic acid (E–MA–AA) terpolymers and acrylic acid content in ethylene–acrylic acid (E–AA) copolymers was investigated in blends of these two materials. The E–MA–AA terpolymer with 8 mol % methyl acrylate was not miscible with any E–AA material no matter what the AA content, whereas the terpolymer with only about 2 mol % methyl acrylate was miscible, at least to some extent, with the E–AA copolymer at high acrylic acid contents. Evidence supporting this conclusion derived from gloss, differential scanning calorimetry testing, and dynamic mechanical measurements. For the E–AA polymer material with the highest acid content, there was a synergistic effect for some properties at low added amounts of E–MA–AA copolymer; the tensile strength and hardness were 10% higher than values for the E–AA copolymer, even though the E–AA copolymer was much stiffer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2216–2222, 2004     

Influences of co‐monomers and electrolyte acidity on morphological structure of copper‐in‐copolymer gradient film

In this paper, the influences of composition of copolymers and acidity of electrolyte in an electrochemical reactor on morphological structure of copper‐in‐polymer gradient composite film were investigated. For binary copolymers, poly(acrylonitrile‐co‐methyl acrylate) [P(AN‐co‐MA)] and poly(acrylonitrile‐co‐sodium allyl sulfonate) [P(AN‐co‐SAS)], the charged group ? SO in P(AN‐co‐SAS) improves the swelling of the copolymer phase and copper reduction to form gradient morphology; the carboxylic ester group in P(AN‐co‐MA) is not effective because of its poor hydrophilicity, but it is a cooperating component with P(AN‐co‐SAS) to avoid excess of counterion (i.e., Na⁺) in SCF, which might severely interrupt Cu²⁺ coexistence. The swelling of the polymer phase is helpful to decrease the energy of the transfer ions in SCF and to enhance copper deposition and gradient formation. The increase of surface energy because of cluster growth raises the surface energy level of deposited Cu⁰ clusters. The conteraction between these two energy factors allows the size of clusters to be 50–100 nm. The appropriate H⁺ concentration improves active Cu²⁺ reduction and thus deposited gradient copper phase in the copolymer matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 373–380, 2004     

聚甲基乙烯基硅氧烷增韧聚苯硫醚的力学性能研究

通过熔融共混制备了聚苯硫醚/无苯基聚甲基乙烯基硅氧烷(PPS/NPMVS)共混物及聚苯硫醚/单苯基聚甲基乙烯基硅氧烷(PPS/SPMVS)共混物,并对该共混物体系的微观形貌及力学性能进行了分析表征。结果表明,弹性体在共混物中均匀分散,弹性体的加入对PPS基体起到明显的增韧效果;当弹性体的含量为3 %（质量分数,下同）时,2种共混材料的增韧性能最佳,PPS/NPMVS共混材料的断裂伸长率相对于PPS基体提高了3.9倍,PPS/SPMVS共混材料的断裂伸长率相对于PPS基体提高了2.4倍;当NPMVS含量为10 %时,PPS/NPMVS共混材料的冲击强度相对于PPS基体提高了1.8倍,当SPMVS含量为3 %时,PPS/SPMVS共混材料的冲击强度相对于PPS基体提高了1.4倍。     

可聚合甲基丙烯酰氧丙基磷酸酯的合成

以三氯氧磷、三乙胺、丙烯酸羟丙酯(HPA)等为原料,通过多步法合成了一种磷酸酯反应型乳化剂。实验对原料配比、反应时间、反应温度等进行讨论,得到最佳工艺条件,并用红外光谱对产品进行结构表征。结果表明,合成甲基丙烯酰氧丙基磷酸酯中间体,选择n(三氯氧磷)∶n(三乙胺)∶n(HPA)=1.1∶1.3∶1,反应时间为1.5h,反应温度为25℃,第二步水解反应温度0~15℃,水解物料比为n(中间体产物)∶n(三乙胺)∶n(水)=1∶1.4∶1.2时,最终产物收率最高,可达98.80%。     

共沉淀法合成正极材料LiMnPO4/C

以羧甲基纤维素(CMC)为碳源,用共沉淀法制备碳包覆磷酸锰锂(LiMnPO4/C).用XRD、SEM及恒流充放电等方法对样品进行了研究.样品具有橄榄石晶体结构,物相较纯,粒径细小且分布均匀,一次颗粒直径约为200nm.以0.05C倍率在2.0～4.5V循环,首次放电比容量为130 mAh/g,库仑效率为80％,循环20次的容量保持率为95％.     

酸性离子液体催化制备油酸甲酯

利用微波法一步合成缬氨酸氟硼酸盐酸性离子液体,并应用到油酸酯化反应中,该催化剂催化效果良好,可以替代硫酸、对甲苯磺酸等强酸,采用离子液体作催化剂具有用量少,腐蚀性低,可重复利用等优点。以缬氨酸氟硼酸离子液体作催化剂,油酸、甲醇为原料,反应物料质量比为0.008∶1∶9,反应时间为5h的反应条件下得到油酸甲酯。并通过油水分离、水相蒸馏重获催化剂,使之重复利用。重复5次实验中,其酯化转化率仍可达80.45%。