液相催化调聚合成卤代烃的催化剂研究进展

综述了卤代烷与烯烃调聚合成卤代烃的催化剂体系，包括铜催化剂、铁催化剂、镍催化剂和复合金属催化剂等无载体型催化剂和负载型催化剂。     

氟代醇的合成研究进展

氟代醇作为一类重要的脂肪族含氧中间体,广泛应用于溶剂、农药、医药合成和染料合成等领域,综述了氟代醇的合成方法,包括加氢还原法、氧化法、水解法、调聚法等。     

催化调聚法生产全氟碘辛烷的研究与改进

全氟碘代烷是生产含氟整理剂、含氟表面活性剂及其他含氟精细化学品的关键中间体,我国也因国外的垄断而几乎完全依赖进口,严重制约了我国有机氟精细化工的发展。对国外生产全氟碘代烷的方法进行分析,通过对已有催化调聚法的研究,提出了合理化的改进措施和合成工艺。     

Synthesis and properties of N-(α-carboxyalkyl)acrylamide telomer-type surfactants having multihydrocarbon chains

N-(α-Carboxyalkyl)acrylamide telomer-type surfactants (xC _n−1 AmAc where n is alkyl chain length=6, 8, 10, 12; and x is degree of polymerization=3.3–13.1) were synthesized by the telomerization of monomer (C _n−1 AmAc) in the presence of the corresponding alkanethiol as a chain transfer agent and then investigated for their surface-active properties. xC _n−1 AmAc telomers lowered the surface tension of aqueous solutions that were at pH 9–10. The critical micelle concentrations (CMC) of the telomers were lower than those of the monomers with the same alkyl chain length, and the CMC values shifted to lower concentrations with both increasing alkyl chain length and polymerization degree. xC₉AmAc with x=3.3–6.3 gave the highest efficiencies in lowering the surface tension. The cross-sectional molecular areas per molecule of xC _n−1 AmAc telomers were smaller than the values estimated on the assumption that they are assemblies of C _n−1 AmAc monomer units. The foaming abilities and the foam stabilities were both in the orders of xC₇AmAc>xC₉AmAc>xC₅AmAc>xC₁₁AmAc. Mixtures of aqueous solutions of xC _n−1 AmAc telomers and toluene formed oil-in-water emulsions. The emulsion-stabilizing abilities were in the orders of xC₇AmAc>xC₅AmAc>xC₉AmAc=xC₁₁AmAc. The addition of Ca²⁺ to the mixed solutions of telomers and toluene resulted in formation of water-in-oil type emulsions. Thus, the surface-active properties of the telomers were influenced significantly by the alkyl chain length and the polymerization degree of the telomers. In addition, these properties could be correlated with the hydrophilic-lipophilic balance (HLB); the highest surface activities were observed by using xC _n−1 AmAc with HLB of 14–18.     

Telomerization of Butyl Methacrylate and 1‐Octadecanethiol by Reactive Extrusion

Butyl methacrylate and 1‐octadecanethiol telomers were prepared by radical reactive extrusion. The main advantages of the use of this processing technique are that mass reactions can be conducted and continuous production is achieved within a reduced reaction time and a correct temperature control. Preliminary studies concerned the choice of the reactants for the telomerization reaction and the adaptation of the telomerization reaction to the reactive extrusion process. The transfer constant to C₁₈H₃₇SH was measured, and then experimental studies were conducted to verify that the hypothesis and approximations made for kinetic modeling are realistic. Particularly, it was shown that the use of relatively high chain‐transfer agent to monomer concentration ratio had no perceptible effect on the monomer conversion kinetic. These results allowed the choice of reactive extrusion conditions. Telomers were prepared using a laboratory co‐rotating twin‐screw extruder. The effect of reaction conditions (temperature, 1‐octadecanethiol to monomer concentration ratio) and of processing conditions (throughput, screw rotation speed) on the residence time distributions, molar mass and monomer conversions were examined. This study allowed the continuous synthesis of butyl methacrylate telomers having variable controlled molar masses and complete monomer conversion.

Screw profile used in reactive extrusion telomerization.     

Solvent free telomerization of butadiene with water into octadienols in the presence of nonionic surfactant: efficient micellar catalysis

Telomerization of butadiene with water into 2,7-octadien-1-ol using a palladiumhydrosoluble phosphine system was investigated. The reaction was carried out without solvent in the presence of carbon dioxide and a nonionic surfactant. Promoted effect of neutral surfactant appeared above the critical micelle concentration and the conversion and the selectivity depended on the structure of nonionic surfactant hydrophilic part. The role of the nonionic surfactant is discussed.     

四氟乙烯等的水相沉淀调聚反应的聚合度方程及其模拟

对于非衰减或弱衰减的＂理想链转移体系＂,考虑生成的聚合物对气相空间的压缩作用,导出了采用稀水溶液沉淀聚合工艺（俗称的分散聚合和悬浮聚合）制备低分子质量聚四氟乙烯等一类调聚反应中的瞬时和累积数（质）均聚合度随聚合转化率变化的方程,并进行了讨论和模拟。结果显示：在恒压聚合期,聚合度可以呈逐渐升高的趋势,但也可以维持恒定或逐渐降低,链转移剂浓度则呈与此相反的变化;阐明了此类反应的链转移剂或聚合压力的选择原则为：CS/[M]g=Mr,M/ρp,一般CS〈〈1;降压聚合期间,因CS〈〈1,链转移剂相对含量大幅度提高,聚合度急剧下降。贯穿整个聚合周期生成的聚合物粒子呈一种内外分子质量有别的核壳结构。结果有望对此类低分子质量聚合物的合成起到一定的理论指导作用,但对强衰减链转移体系可能误差较大。     

六氟丁醇的合成及应用研究进展

2,2,3,4,4,4-六氟丁醇是一种重要的含氟有机中间体,可广泛用作溶剂和农药、染料以及含氟特种表面活性剂的制备原料.通过机理分析和对不同引发条件下的自由基加成反应的比较,认为过氧化物引发自由基加成反应制备六氟丁醇具有工业化前景.此外,对六氟丁醇的应用作了简要介绍.     

Palladium‐Catalyzed Telomerization of Butadiene with Starch

In order to modify the hydrophilic properties of native starch for its incorporation in polymers, the telomerization of butadiene with native starch was investigated. Low to moderate degrees of substitution (DS=0.04–0.52) were obtained depending upon experimental conditions, particularly, reaction time, temperature and solvent. With 0.3‰ water‐soluble palladium catalyst (Pd/TPPTS), the reaction occurred in i‐PrOH/NaOH 0.1 N solvent mixture even at 50 °C and after 3 h reaction the DS reached 0.08, a value suitable for the application.