聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/PEG嵌段共聚物的合成及性能研究

用熔融缩聚法合成了一系列聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/聚乙二醇的嵌段共聚物。用FT-IR,1H-NMR,DSC,TGA,水降解测试等方法表征了材料的结构与性能。FT-IR和1H-NMR分析表明合成得到的共聚物为预期产物;DSC分析显示,共聚聚酯随着1,3-丁二醇在共聚物中比例的增大,熔点(Tm)逐渐降低,由158.24℃下降至104.19℃,玻璃化温度(Tg)逐渐升高,由4.86℃升至24.56℃,合成得到的共聚酯趋向于无定形态;TGA分析表明1,3-丁二醇在共聚酯中比例增大会使聚酯的热稳定性下降,但合成得到的共聚酯依然具有较好的热稳定性,初始分解温度大于310℃,不需要在反应过程中添加热稳定剂;水降解测试结果表明共聚物随1,3-丁二醇比例的增加,降解速率大幅提升。     

2，2，4，4-四甲基-1，3-环丁二酮的合成方法综述

2,2,4,4-四甲基-1,3-环丁二酮（TMCD）通过催化加氢得到的2,2,4,4-四甲基-1,3-环丁二醇（CBDO）是一种重要的化工原料,主要用于共聚聚酯合成的单体.目前对于TMCD的合成,主要通过先合成二甲基烯酮这一不稳定前体再进行自聚得到.文章主要介绍了几种合成TMCD的方法,并简要分析各种方法的优劣.     

CBC-SO爪形低温流动性改进剂的合成与表征

以1,3-丁二醇、柠檬酸为原料,甲苯为溶剂,在120℃油浴中搅拌反应,当达到理论出水量的95%以上时,合成了柠檬酸-1,3-丁二醇柠檬酸(CBC)爪状物小分子,收率为73.3%。CBC进一步与硬脂酸、十八醇分别在140℃和180℃接枝,合成了多元酯类爪形大分子柠檬酸-1,3-丁二醇柠檬酸硬脂酸十八醇(CBC-SO),收率72.4%。用核磁共振波谱及红外光谱对合成的两种化合物进行了结构表征,确定CBC和CBC-SO均为爪形结构,与所设计的分子结构吻合。元素分析确定了CBC和CBC-SO的化学组成依次为C16H22O14和C106H200O15。在实验室评价和10 t柴油工业应用放大实验中,将CBC-SO按600~1 000μg/g添加到不同的轻柴油中,柴油的冷滤点可降低4~6℃。     

含侧烃基的特种低分子脂肪族二元醇

对部分已工业化生产的含侧烃基的脂肪族二元醇(包括新戊二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2-乙基-1,3-己二醇、2-甲基-1,8-辛二醇、二聚体二醇、羟基新戊酸羟基新戊醇酯、一缩二丙二醇等)进行了简要介绍。介绍了它们的性能特点和用途,特别是在高分子合成材料中的应用。     

1,3-丁二醇的应用与合成研究进展

介绍了1,3-丁二醇在化工、医药和化妆品行业的应用,综述了两种化学法生产1,3-丁二醇的工艺,包括乙醛经羟醛缩合加氢,甲醛丙烯经Prins反应缩合水解,并探讨了两种工艺今后的研究发展方向。     

5-(2-羟乙基)-2,2-二甲基-1,3-二恶烷的合成研究

2-羟甲基-1,4-丁二醇与2,2-甲氧基丙烷反应合成了5-(2-羟乙基)-2,2-二甲基-1,3-二恶烷,探究了催化剂对甲基苯磺酸用量、2,2-甲氧基丙烷的用量、溶剂对收率的影响。结果表明,最佳反应时间为10 h,产品收率达72%。     

2-亚甲基-1,3-二氧环庚烷的合成工艺研究

以溴乙醛缩二乙醇和1,4-丁二醇为初始原料,经过取代、消除反应合成重要的有机和药物合成中间体2-亚甲基-1,3-二氧环庚烷,并探索了反应温度、反应时间和催化剂等因素对中间产物收率的影响,探索了碱、后处理方式对终产物收率的影响,确定了最佳合成工艺条件。目标化合物结构经由~1HNMR进行表征确认。     

聚己二酸二元醇酯合成研究与表征

以己二酸、1,2-丙二醇、1,3-丁二醇和1,4-丁二醇为原料,钛酸四正丁酯为催化剂,2-乙基己醇为封端剂,经酯化、缩聚合成己二酸系列聚酯产品.考察了反应时间、催化剂、原料配比和封端剂用量等因素对聚己二酸类酯合成的影响.采用旋转黏度计、红外光谱仪(IR)、核磁共振仪(1H-NMR,13CNMR)、凝胶渗透色谱(GPC)和热重分析仪(TG-DSC)分别对产物的黏度、结构、分子量和热稳定性进行了系统的表征,实验表明:合适的反应条件为聚己二酸1,2-丙二醇酯原料二元醇/二元酸的摩尔比为1.14:1、催化剂为原料总量的0.03%、反应温度为200～220℃、反应时间为6 h,此时产物分子量为1.90×103 ,分布指数为1.4、聚合度n为10的聚酯.聚己二酸1,2-丙二醇酯、聚己二酸1,4-丁二醇酯和聚己二酸1,3-丁二醇酯的分解温度为334℃、349℃和358℃,产物具有较高的热稳定性.     

阿昔洛韦的合成工艺改进

设计了1条以NaHSO4为催化剂合成阿昔洛韦的新工艺,以醋酐和1,3-二氧戊环为起始原料,合成2-氧杂-1,4-丁二醇二乙酯,然后再与乙酰化后的鸟嘌呤发生缩合制得双乙酰阿昔洛韦,双乙酰阿昔洛韦在Na2CO3水溶液中水解得到目标产物阿昔洛韦。考察了该工艺中反应温度、催化剂用量、溶剂等对反应收率和产品质量的影响。结果表明,在合成关键中间体2-氧杂-1,4-丁二醇二乙酯中,反应温度宜选用60℃;合成双乙酰鸟嘌呤时n（鸟嘌呤）：n（cat）=1.0：0.1为较佳;合成双乙酰阿昔洛韦时选用甲苯作为反应的较佳溶剂。总收率达到79%,并且产物纯度较高,适合工业化生产。     

SO_4~(2-)-TiO_2/Al_2O_3超强酸催化合成新型香料

通过浸渍法制备了SO42--TiO2/Al2O3固体超强酸催化剂,用Hammett指示剂法测定了其酸强度;以乙酰乙酸乙酯和1,3-丙二醇、1,3-丁二醇为原料,合成了新型香料2-甲基-2-乙酸乙酯基-1,3-二氧六环和2,4-二甲基-2-乙酸乙酯基-1,3-二氧六环,考察了催化剂的焙烧温度、TiO2的负载量、反应温度、反应物配比、催化剂用量等因素对反应的影响以及催化剂的重复使用性。结果表明,在425～575℃温度范围内,SO42--TiO2/Al2O3体系可以形成超强酸;在新型香料的合成中具有催化活性高、催化速率快、化学稳定性好,重复使用性佳、无环境污染;在最佳条件下,两种香料的收率分别可达83.5％和83.6％,质量分数为99.1％。     

Radiation-initiated graft copolymerization of binary monomer mixtures containing acrylonitrile with cotton cellulose

By the use of the cobalt 60 postirradiation grafting technique, purified cotton cellulose fibers were graft-copolymerized with binary mixtures of acrylonitrile and other monomers, including styrene, 1,3-butylene dimethacrylate, vinylpyrrolidone, vinylidene chloride, and methyl, butyl, lauryl, glycidyl, and allyl methacrylates. The irradiated cotton fibers were immersed in solutions of the monomers at 25°C to initiate graft copolymerization. Solvents were water, methanol, dimethyl sulfoxide, and methyl ethyl ketone, alone or in several combinations. The extent of graft copolymerization and the composition of the grafted copolymer depended on the composition of the binary mixtures of monomers and on the solvent or mixtures of solvents used. For example, addition of styrene, 1,3-butylene dimethacrylate, or vinylpyrrolidone to acrylonitrile increased the extent of graft copolymerization to a maximum value; addition of vinylidene chloride or allyl methacrylate to acrylonitrile did not greatly affect the extent of graft copolymerization; and addition of methyl or glycidyl methacrylate to acrylonitrile increased the extent of graft copolymerization without passing through a maximum value. The proportion of acrylonitrile in the grafted copolymer was generally less than that in the binary mixtures. As the reaction time was increased, the extent of graft copolymerization increased to a maximum value; however, the composition of the grafted copolymer did not change significantly. Generally, the addition of water to the solutions increased the extent of graft copolymerization. The mechanisms of these graft copolymerization reactions are discussed.     

Low glass transition temperature aliphatic polyurethanes

Summary The present paper deals with the single step syntheses of a few aliphatic polyurethanes using some simple glycols like ethylene, propylene, 1,3- and 1,4-butylene glycols and two different bis(chloromethyl) compounds viz., 1,4-bis(chloromethyl)-2,5-dimethyl benzene (I), and 1,5-bis(chloromethyl)-2,4-dimethyl benzene (II). The glass transition temperatures, T_g, of these polymers were determined using dilatometric techniques and they ranged from –12 to –48°C. The polyurethanes derived from 1,4-butylene and ethylene glycols were amorphous gums with T_g well below –30°C.     

Qualitative DC-Trennung einiger Polyalkohol-Fettsäurepartialester und Identifizierung der Polyalkohol-Komponente

Qualitative TLC-Separation of a Few Polyalcohol-Fatty Acid Partial Esters and Identification of the Polyalcohol Component Using thin-layer chromatography, a few emulsifiers, such as partial esters of fatty acids with ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol and sorbitol were separated into classes of compounds. The number of TLC-fractions reveal the nature of the fatty acid ester of the polyol. In another procedure the polyols are isolated and separated by TLC. Partial esters of fatty acids with polyols can be unequivocally identified by the two TLC-separations.     

Developing the technology for producing highly concentrated iso-butylene

The technology used at Russian plants for the recovery of polymerization-grade iso-butylene is based on synthesizing tert-butanol through the hydration of iso-butylene incorporated into raw hydrocarbon fractions with the subsequent separation and decomposition of tert-butanol. The hydration of iso-butylene is performed in reactive extraction reactors with countercurrent initial reagents on a molded sulfocationite catalyst. In this paper, a version of the process performed in a flow reactor at near-stoichiometric ratios of reagents is proposed in the context of modernizing the existing technology. The dependence of iso-butylene conversion and the amount of by-products (dimers, sec-butanol) on the type of hydrocarbon feedstock and the process parameters is studied. The iso-butane-iso-butylene fraction (IIF) and the butylene-iso-butylene fraction (BIF) are used as feedstocks. It is shown that iso-butylene conversion is lower for the BIF feedstock, and the concentration of by-products is higher than for the IIF feedstock. A tert-butanol synthesis flowsheet is proposed that includes flow and reactive extraction reactors and allows us to increase the capacity of an existing plant with a simultaneous reduction in the process’s overall energy consumption due to the production of a highly concentrated tert-butanol solution at the outlet of the flow reactor, and to obtain iso-butylene with a purity of no less than 99.99 wt %.     

Toughening of aromatic diamine-cured epoxy resins by poly(butylene phthalate)s and the related copolyesters

Aromatic polyesters, prepared by the reaction of aromatic dicarboxylic acids and 1,4-butanediol, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulfone. These polyesters contained poly(butylene phthalate)s (PBP), poly(butylene phthalate-co-butylene isophthalate)s, poly(butylene phthalate-co-butylene terephthalate)s, and poly(butylene phthalate-co-butylene 2,6-naphthalene dicarboxylate)s. All aromatic polyesters used in this study were soluble in the epoxy resin without solvents and were found to be effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PBP (MW 16,300) led to a 120% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 1996 John Wiley & Sons, Inc.     

浅谈C4的综合利用

介绍了国内外C4的应用现状。主要讨论了C4综合利用技术，其中包括C4加氢生产优质蒸汽裂解原料、汽油氧化剂、分离制高纯度1—丁烯和高纯度正丁烯、三苯(苯、甲苯和二甲苯)抗氧剂BHT、车用液化气和某厂C4馏分利用流程图。C4的合理利用不仅可以有效利用石油资源，而且也是改善产品结构、提高产品质量、增加企业效益的重要途径。     

The effect of annealing on tensile properties of injection molded biopolyesters based on 2,5-furandicarboxylic acid

In this study, we investigate four polyesters based on 2,5-furandicarboxylic acid and different diols including 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexylene glycol. Poly(ethylene 2,5-furanoate), poly(propylene 2,5-furanoate), poly(butylene 2,5-furanoate), and poly(hexylene 2,5-furanoate) (PHF) were characterized by thermogravimetric analysis, X-ray diffraction, differential scanning calorimeter, and tensile tests. In addition, the influence of annealing polyesters on their thermal and mechanical properties was investigated. For these reasons samples for the tensile test were prepared by injection molding. The tensile properties of injection molded samples were compared with samples that were additionally annealed after injection molding. All studied polyesters after heating treatment showed multiple melting behavior. The increase in the degree of crystallinity significantly influenced also the mechanical properties of the samples. It was found that the length of the aliphatic chain and degree of crystallinity plays a major role in the final properties of furan-based polyesters.     

Alkylation of benzene with 1-butylene over β-zeolite modified by Fe or La

在小型固定床反应器上研究了Fe、La改性β沸石催化苯和正丁烯的烷基化反应,考察了金属负载量以及反应温度、进料质量空速比等工艺条件对改性β沸石催化性能的影响。采用XRD、BET、NH₃-TPD和TG-DTA等表征手段研究了Fe、La改性β沸石催化性能提高的机理。研究表明,Fe、La改性后β沸石表面的强、弱酸量都明显下降,相比较而言,La改性β沸石拥有较强的表面酸性,在催化苯和正丁烯的烷基化反应中显示出了更好的催化性能,具有更强的抗积炭能力,这也与BET和TG-DTA的结果一致。在以20%La/β沸石为催化剂、反应温度180℃、苯的进料空速1.2 h^-1、正丁烯的进料空速0.6 h^-1、反应6 h条件下,正丁烯的转化率为87.9%,仲丁基苯的选择性为88.2%。