13C and 1H n.m.r. study of the polyesterification of maleic anhydride and 1,2-propylene glycol

The reaction steps of the polyesterification of maleic anhydride and 1,2-propylene glycol were followed by ¹³C and ¹H n.m.r. spectroscopy. The number and structure of mono- and diesters of both maleates and fumarates in the reaction mixture are determined by the possible glycol unit configurations. The structure of the growing polyester chain reflects a statistical distribution of approximately equal numbers of symmetric and asymmetric arrangements of the polymer sequences.     

Catalytic polymerization of maleic anhydride

This study examined the polymerizations of maleic anhydride in solution and in the bulk phase catalyzed by nanocrystalline titania or sodium acetate. Through IR and ¹H‐NMR, the monomer and polymer were characterized, and the structure of the polymer was confirmed. Moreover, the polymer molecular weight was measured to be 400–800 in solution and 2000–3000 in the bulk phase. The mechanism of the catalytic polymerization was also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2868–2874, 2003     

由1,2-二氯丙烷合成1,2-丙二醇的方法

介绍了由 1 ,2 -二氯丙烷合成 1 ,2 -丙二醇的方法 ,包括在弱碱水溶液中直接水解法和经与羧酸盐反应成酯、再水解法。     

MA/EG与TBPA/EG聚酯化反应动力学

通过熔融缩聚反应对马来酸酐/乙二醇(MA/EG)和四溴邻苯二甲酸酐/乙二醇(TBPA/EG)两个聚酯化反应的动力学进行研究。考察了自催化条件下反应温度、原料配比对聚酯化反应速率的影响。在陈寿安模型的基础上,对反应级数的不同组合进行了比较研究。结果表明:1-1模型和实验结果吻合良好,且k_h[H₂O]为正值;温度越高,醇酸配比越大,则聚合反应程度越大。     

碘催化合成香兰素缩1,2-丙二醇

以单质碘为催化剂,香兰素和1,2-丙二醇经缩合反应合成了香兰素缩1,2-丙二醇。考察了醛醇物质的量比、催化剂用量、反应温度和反应时间对产品收率的影响。实验表明,较佳反应条件为:当香兰素的用量为0.1mol,1,2-丙二醇的用量为0.18mol,即n(香兰素)∶n(1,2-丙二醇)=1∶1.8,催化剂用量1.2g,反应温度60℃,反应时间20min,香兰素缩1,2-丙二醇的收率达91.3%以上。     

Radical-induced ionic polymerization in the presence of maleic anhydride. I. Mechanism of polymerization of maleic anhydride by radical initiators

Three kinds of trapped radicals are observed in poly(maleic anhydride) (Poly-MAH) which were prepared by the use of radical initiators such as AIBN or BPO. It was found that these radicals were transformed to the active species so as to initiate the cationic polymerization. The structure of these radicals was studied by the ESR and the kinetic analysis of MAH polymerization in the presence of various additives.     

1,2丙二醇国内外生产现状及发展前景

介绍了丙二醇的应用领域和国内外市场供需情况,概述了丙二醇的几种主要生产工艺,对丙二醇产品的发展前景作出了展望并针对国内丙二醇企业面临的困难提出了应对策略。     

聚乙二醇单甲醚接枝苯乙烯马来酸酐共聚物的合成

通过聚乙二醇单甲醚与苯乙烯马来酸酐共聚物的接枝反应,合成了以苯乙烯马来酸酐共聚物为主链的梳型表面活性剂(SMA-g-MPEG).研究了催化剂用量、马来酸酐和聚乙二醇单甲醚摩尔比、反应时间等因素对梳型表面活性剂收率的影响.结果表明,当对甲苯磺酸催化剂的用量为反应物总质量的4%、聚乙二醇单甲醚和马来酸酐的摩尔比为3:4、反应时间为8 h时,可以制备出优化的梳型表面活性剂,其收率为36.5%.产品由红外光谱和核磁共振谱进行表征.优化梳型表面活性剂的临界胶束浓度为1.24 g/L,最低表面张力为34.2 mN/m,显示出较高的表面活性.     

硅胶负载硫酸铁催化合成香兰素1,2-丙二醇缩醛

以香兰素和1,2-丙二醇为原料,以硅胶负载硫酸铁(Fe2(SO4)3/S iO2)为催化剂,合成了香兰素1,2-丙二醇缩醛,考察了醛醇摩尔比、反应时间、催化剂用量及其稳定性对产率的影响。实验表明,硅胶负载硫酸铁是合成香兰素1,2-丙二醇缩醛的理想催化剂,较优反应条件为:香兰素0.1 mol,n(香兰素)∶n(1,2-丙二醇)=1.0∶2.4,催化剂的用量为反应物总质量的2.5%,带水剂环己烷12 mL,回流反应3.0 h,香兰素1,2-丙二醇缩醛的收率可达86.0%以上。     

二氧化硅负载高氯酸催化合成香兰素缩1,2-丙二醇

以二氧化硅负载高氯酸(HClO4/SiO2)为催化剂,香兰素和1,2-丙二醇经缩合反应合成香兰素缩1,2-丙二醇。考察了醛醇物质的量比、催化剂用量、反应温度和反应时间对产品收率的影响。实验表明,较佳反应条件为:当香兰素的用量为0.1 mol,1,2-丙二醇的用量为0.16 mol,即n(香兰素)∶n(1,2-丙二醇)=1∶1.6,催化剂用量1.5 g,反应温度80℃,反应时间45 min,香兰素缩1,2-丙二醇的收率达87.1%以上。HClO4/SiO2是一种热稳定性好、简单易制、可循环使用的高效非均相催化剂。     

马来酸酐/苯乙烯多单体接枝低等规聚丙烯

低等规聚丙烯（LIPP）是由等规立构和间规立构组成的嵌段共聚物，具有低的结晶性能，良好的粘接性和加工性能，在胶粘剂领域有着广阔的应用前景。然而LIPP的非极性和低的机械性能限制了它的应用。本文采用溶液法，以过氧化二异丙本（DCP）为引发剂，以苯乙烯（St)作为共聚单体，将马来酸酐（MAH）接枝到低等规聚丙烯（LIPP）大分子链上，采用化学滴定法测定产物（LIPP－g-MAH-St)的接枝率（GR），并系统地研究了加料方式，单体用量，引发剂用量，反应时间等因素对GR的影响，结果表明，采用先加入引发剂的加料方式有利于马来酸酐对低等规聚丙烯的接枝反应，反应的最佳条件是：反应时间7h，MAH的加入量为9份（以100份LIPP计），引发剂DCP的加入量为0．45份。     

Step-growth polymerization of unsaturated aldehydes with diaminodiphenylmethane

Step-growth polymerization of diaminodiphenylmethane and unsaturated aldehydes (crotonaldehyde, cinnamaldehyde) proceeded easily in toluene at reflux temperature. Resins with molecular weights up to 1,500 g/mol were formed. In the first step of the reaction, the amino and the aldehyde groups reaction were predominate while the double bonds dominated to a lesser extent. The portion of unreacted monomers was under one percent. The resins consisted of oligomers with -CHNH-, -CH=N-, and -CH=CH-groups, which further reacted to form highly crosslinked resins. Kinetic data, the heat of the addition, the heat of condensation, and the activation energy were calculated. Faculty of Chemistry and Chemical Technology, Askerceva 5, 1001 Ljubjana, P.O.B. 537, Slovenia.     

Unsaturated polyesters,III. Polyester from maleic anhydride and 1,4-butylene glycol

The polyesterification reaction of maleic anhydride and 1,4-butylene glycol was carried out, using p-toluensulphonic acid as catalyst. The resulting material was characterized by IR and H¹-NMR spectroscopy, end group analysis, and gel permeation chromatography. It is shown that there is a relationship between maleate to fumarate isomerization and steric interaction among condensed groups on the one hand and the tendency of the reacting system to crosslink or gel.     

高氯酸锌催化尿素与1,2-丙二醇合成碳酸丙烯酯

针对尿素醇解合成碳酸丙烯酯工艺,系统考察了锌盐催化体系的催化反应性能。结果显示,锌盐均表现出良好的催化活性,其中高氯酸锌的催化效果最好;高氯酸根离子强的吸电性可能是高氯酸锌催化效果好的主要原因。以高氯酸锌为催化剂,考察了不同的反应时间、催化剂用量和反应温度对合成中各反应的影响。当n(1,2-丙二醇)∶n(尿素)=4∶1、反应时间3 h、催化剂质量分数1.5%、反应温度170℃时,碳酸丙烯酯的收率可以达到94.2%。催化剂的稳定性较好,具有一定的应用前景。     

球形PE粒子的合成与马来酸酐固相接枝反应

采用负载型高效球形催化剂催化乙烯淤浆聚合得到了高孔隙率的球形聚乙烯(PE)颗粒。用光学显微镜、扫描电子显微镜等方法对所得PE的形貌、结构、粒径分布等进行了表征。实验表明,PE颗粒的粒径分布窄、形貌规整、孔隙率高。以球形PE为基体,研究了马来酸酐在PE颗粒中的接枝反应,考察了反应条件对接枝率和酸值的影响。     

Vapour–liquid equilibrium data for n-butyl acetate–1,2-propylene glycol

Vapour–liquid equilibrium data for the binary system n-butyl acetate–1,2-propylene glycol have been obtained at pressures between 725 and 735 mm Hg. The activity coefficient data were correlated by Chao's modified Redlich Kister equation and van Laar's equation. The vapour composition was also correlated by the equations of Nagata and Hirata. Thermodynamic consistency was confirmed by Herington's area test.     

Step-growth polymerization of guanamines with unsaturated aldehydes

Summary In acid medium and at temperatures from 50 to 100°C the resins from three different guanamines and three different unsaturated aldehydes were synthesized. The products were red coloured resins, which were soluble in organic solvents and were able to cure with hexamethylenetetramine to form hard and almost insoluble products. Using a combination of NMR and GPC methods it was possible to predict the course and the mechanism of the reactions. The rates of the reactions depend on the reaction conditions and on the type of the monomer.     

磷钨酸绿色催化合成香兰素缩1，2-丙二醇

以磷钨酸为催化剂,通过香兰素与1,2-丙二醇反应合成了标题化合物.研究了原料配比、反应时间、催化剂的种类和用量、带水剂的种类以及催化剂重复使用后对收率的影响.并研究了磷钨酸催化其他的醛酮与醇的缩合,实验表明,磷钨酸是催化合成缩醛(酮)的理想催化剂,其较优反应条件为:n(香兰素):n(1,2-丙二醇)=1:1.3,催化剂用量为反应物总质量的0.3%,带水剂为15 mL苯,回流反应2 h,活性98%以上,收率达94.58%以上.通过GC、1HNMR、IR等数据对所合成的目标产物进行了表征.     

Step-growth polymerization of unsaturated aldehydes with aliphatic amines

The step-growth polymerization of unsaturated aldehydes (acrolein, crotonaldehyde, cinnamaldehyde) and aliphatic amines (butylamine, ethylenediamine, triethylenetetramine, diethylenetriamine, hexamethylenediamine) took place intensively in the temperature range between 50 and 90°C. The rates of individual reactions depended on the type of individual aldehydes and amines. The quantity of individual unreacted monomers was mostly under 1%. The average molecular weights of oligomers were between 290 and 710. The individual resins consisted of oligomers with free ? OH, ? NH, ? CH?N? , and ? CH?CH? groups, which are further able to cross-link the resins with three blocked isocyanate to insoluble, elastic film with high adhesion to glass and metal substratum. © 1994 John Wiley & Sons, Inc.