2,5-二氧-1,4-环己烷二甲酸二甲酯合成工艺研究

采用过量的丁二酸二甲酯作为反应溶剂 ,以甲醇钠与丁二酸二甲酯合成 2 ,5 二氧 1,4 环己烷二甲酸二甲酯的合成工艺 ,研究了原料配比、反应温度及反应时间对产品收率的影响。在n(丁二酸二甲酯 )∶n(甲醇钠 ) =4 3∶1 0、反应温度 10 0℃及回流反应时间 2 5～ 30min的最佳合成工艺条件下 ,得到质量分数为 97 5 %的 2 ,5 二氧 1,4 环己烷二甲酸二甲酯 ,以甲醇钠计其收率为 88 1%。     

2,2-二甲基丙二酸二甲酯的合成

以丙二酸二甲酯和碘甲烷为原料、甲醇钠为催化剂合成了2,2-二甲基丙二酸二甲酯.考察了影响反应的因素,采用正交实验法优化了反应条件,总收率可达81.3％,产品纯度为99.96％.反应的最优条件为:n(丙二酸二甲酯)∶n(碘甲烷)=1.0∶2.6,n(碘甲烷)∶n(甲醇钠)=1.0∶1.0,在80 mL溶剂中回流反应6h....     

噻吩-2，5-二甲酸及其酯的催化合成

以醋酸亚铁为催化剂,以噻吩、四氯化碳、甲醇或乙醇为原料回流反应合成了噻吩-2,5-二甲酸二甲酯(Ⅰa)或噻吩-2,5-二甲酸二乙酯(Ⅰb),较佳的反应条件是:n(噻吩)∶n(四氯化碳)∶n(醋酸亚铁)=1∶2.5∶0.01,在过量的醇中回流6 h,收率依次为91.5%和95.2%。化合物Ⅰa或Ⅰb经碱性条件下水解、酸化合成了噻吩-2,5-二甲酸(Ⅱ),较佳的反应条件是:n(噻吩-2,5-二甲酸酯)∶n(氢氧化钠)=1∶2.5,在V(甲醇)∶V(水)=1∶2的溶剂中回流5 h,收率为90.5%～92.0%。     

富马酸二甲酯的合成新工艺研究

研究了以糠醛为原料,以KClO3为氧化剂,V2O5为催化剂制备富马酸,在固载杂多酸PW12/C催化下,富马酸和甲醇经过酯化反应合成富马酸二甲酯。考察了催化剂用量、氧化剂用量、反应时间和醇酸比对反应的影响,确定了最佳工艺条件。m(KClO3)∶m(糠醛)=1.8∶1,反应温度105℃,催化剂用量为0.2g时,反应时间4h,富马酸产率为80.7%;酯化反应中n(甲醇)∶n(富马酸)=7∶1,m(PW12/C)∶m(富马酸)=6∶100,回流反应6h,富马酸二甲酯产率达88.1%。     

2,2’-偶氮二异丁酸二甲酯的制备

以丙酮氰醇(ACH)、水合肼、Cl2、甲醇(CH3OH)和HCl为原料,经缩合、氧化、Pinner反应、水解反应制备2,2’-偶氮二异丁酸二甲酯,对反应条件进行了优化。确定反应的最佳工艺条件为n(ACH)∶n(水合肼)∶n(四甲基溴化铵)=1∶0.53∶0.0052、n(偶氮二异丁腈肼)∶n(Cl2)∶n(HCl)∶n(CH3OH)=1∶1.1∶0.8∶2.6、缩合反应温度25～30℃、反应2 h、氰醇化反应温度10～15℃、反应24 h,产品纯度在98%以上,总收率大于90%。     

丁二酸二甲酯催化加氢制备γ-丁内酯的工艺研究

在微型固定床反应器中,丁二酸二甲酯在复合铜基催化剂Cu-ZnO-ZrO2/A12O3作用下,催化加氢制备了γ-丁内酯。实验中考察了催化剂组成、反应温度、压力、氢酯摩尔比、溶剂比和液时空速等因素对加氢反应的影响。结果显示,在反应温度为220℃、压力为3.0 MPa、n(H2)∶n(丁二酸二甲酯)=150∶1、V(CH3OH)∶V(丁二酸二甲酯)=4∶1、床层液时空速为0.25 h-1的条件下,丁二酸二甲酯的转化率达到100%,γ-丁内酯的选择性达到90%。     

连续流微反应器合成亚磷酸二甲酯的研究

以三氯化磷和甲醇为原料,在无溶剂的条件下,研究了在具有特殊微结构的金属微通道反应器中酯化合成亚磷酸二甲酯的连续流工艺。考察了n(三氯化磷)∶n(无水甲醇)比、反应温度和停留时间等因素对亚磷酸二甲酯合成的影响。最佳工艺结果为:n(三氯化磷)∶n(无水甲醇)=1∶3.2、反应温度30℃、停留时间3 min条件下,三氯化磷转化率为95.4%,亚磷酸二甲酯选择性为97.0%,亚磷酸二甲酯收率为92.6%。连续流金属高通量微通道反应器与间歇反应相比,具有停留时间短、强传质传热的特点,大大缩短了反应时间,提高了反应效率,解决了传统反应器由于反应剧烈、放热量大而带来的本质安全问题,实现了亚磷酸二甲酯的绿色安全高效合成。     

2-甲基-6-丙酰基萘液相氧化制备2,6-萘二甲酸研究

以2-甲基-6-丙酰基萘为原料,在Co-Mn-Br催化体系中液相氧化制备2,6-萘二甲酸,考察了催化剂质量分数、助催化剂比例、反应温度、反应压力、原料与溶剂质量比、反应时间、空气流量等因素对反应的影响。利用HPLC、IR、¹HNMR、pH计对产物进行定性分析。得出制备2,6-萘二甲酸的适宜反应条件为：温度为190℃、时间为45 min、m(Co)∶m(Mn)∶m(Br)=1∶2∶5、m(MPN)∶m(HAc)=1∶15、压力为2.0 MPa、空气流量为1.4 L/min。在此条件下,2,6-萘二甲酸收率和纯度分别为83.47%和91.94%,可达到减少重结晶等提纯步骤、简化工艺流程、降低氧化反应原料成本。     

衣康酸二甲酯的合成

以衣康酸和甲醇为原料在酸催化剂存在下合成了衣康酸二甲酯。产品经FT -IR鉴定 ,谱图与标准谱一致 ,从而确定了其结构。气相色谱及化学分析表明 ,产品质量分数达到 98%。合成衣康酸二甲酯的比较适宜条件是 :n(衣康酸 )∶n(甲醇 ) =1∶10 ,w(硫酸 )∶w(衣康酸 ) =1∶10 0 ,反应温度 12 0℃ ,反应时间 10h ,反应压力 16 2kPa ,收率可达 87%     

β晶型成核剂2,6-二(环戊基酰胺基)萘的合成

用萘二甲酸和环戊胺合成了聚丙烯β晶型成核剂2,6-二(环戊基酰胺基)萘,通过正交试验和单因素试验对其小试工艺条件进行了系统研究,得出最佳反应条件:n(环戊环)∶m(萘二甲酸)为1∶2.4,反应时间2.5h,反应温度108℃,催化剂与萘二甲酸物质的量添加比为1.3∶1,溶剂加入量为21.7mL/g(按萘二甲酸投料量)。在此条件下该成核剂的平均收率为91.8%。加入自制产品与进口产品的PP试样,其Izod缺口冲击强度和热变形温度基本相同,而其弯曲模量则略高于进口样品。     

PET-PEN共聚酯的合成研究

以2,6-萘二甲酸(NDA)、对苯二甲酸或2,6-萘二甲酸二甲酯(NDC)、对苯二甲酸二甲酯与乙二醇为原料,在2 L聚合反应装置上,采用直接酯化法或酯交换法合成聚对苯二甲酸乙二酯(PET)-聚2,6-萘二甲酸乙二酯(PEN)共聚酯(PETN),探讨了PETN的合成反应条件。结果表明:直接酯化法较酯交换法更加可行易控;直接酯化法反应条件:酸/醇摩尔比为1:(1.3～1.5),NDA摩尔分数(相对于酸的总量)为28%,酯化阶段无需催化剂,酯化反应温度220～250℃,缩聚反应温度280～295℃,合成的PETN特性黏数达0.65～0.85 dL/g;钛系催化剂的催化活性优于锑系催化剂,且添加比例小,添加量为8～50μg/g时,即可得到高特性黏数的PETN。     

Preparation of High‐Purity 2,6‐Naphthalenedicarboxylic Acid from Coal Tar Distillate

Using coal tar distillate as the starting material, a novel high‐purity 2,6‐naphthalenedicarboxylic acid (2,6‐NDA) preparation method was developed. Firstly, the 2,6‐dimethylnaphthalene (2,6‐DMN) precursor was separated by successive vacuum distillation, melt crystallization, and solvent crystallization from the 250–270 °C fraction of the coal tar distillate. Then, over Co‐Mn‐Br as catalysts, oxidation of 2,6‐DMN was carried out in acetic acid to produce crude 2,6‐NDA with molecular oxygen. By high‐temperature hydrogenation, the crude 2,6‐NDA was further purified to obtain high‐purity 2,6‐NDA. From the coal tar distillate to pure 2,6‐NDA, the operation parameters and reaction conditions of each process were optimized and evaluated, indicating that the proposed 2,6‐NDA synthesis method has great potential for industrial application to create cheap feedstock in viable yields.     

PEN合成中NDC与EG酯交换反应工艺及动力学研究

以2,6-萘二甲酸二甲醇酯(NDC)和乙二醇(EG)为原料,以金属盐类为催化剂,在一定条件下,研究了NDC与EG的酯交换反应,探讨了NDC与EG的酯交换反应工艺及动力学规律,不同反应温度下,NDC与EG酯交换反应遵循二级反应动力学规律,反应表观活化能为92.89 kJ/mol。     

碳酸二甲酯甲氧基羰基化法合成1,5-萘二氨基甲酸甲酯

考察了六水合硝酸锌、四水合磷酸锌、七水合硫酸锌、氧化锌、碳酸锌、碱式碳酸锌、氢氧化锌、甲酸锌、二水合乙酸锌、二水合环己烷丁酸锌(ZCHBDH)以及二水合硬脂酸锌,在1,5-萘二胺(NDA)与碳酸二甲酯(DMC)甲氧基羰基化合成1,5-萘二氨基甲酸甲酯(NDC)反应中的催化性能。结果表明,六水合硝酸锌和氧化锌等无机锌盐对该甲氧基羰基化反应没有催化作用,而二水合乙酸锌、ZCHBDH以及二水合硬脂酸锌对该甲氧基羰基化反应却有催化活性。当该甲氧基羰基化反应在n(DMC)∶n(ZCHBDH)∶n(NDA)=37∶0.03∶1的条件下于150℃反应5 h,NDA的转化率为100%,NDC的选择性达99%。     

Depolymerization of poly(ethylene naphthalate) in fused silica capillary reactor and autoclave reactor from 240 to 280°C in subcritical water

Depolymerization of poly(ethylene naphthalate) (PEN) in subcritical water was performed in a fused silica capillary reactor (FSCR) and an autoclave reactor. The phase behaviors of PEN in water during the heating‐cooling process in the FSCR were observed under microscope and images were captured by digital camera. Reaction conditions for PEN hydrolysis in the autoclave reactor were chosen based on the experimental results obtained from the FSCR. Under autogenous pressures in the autoclave reactor, the effects of the water/PEN mass ratio (8.0 g/1.0 g to 16.0 g/1.0 g), reaction temperature (240–280°C) and reaction time (5–60 min) on the depolymerization yield and products yields were investigated. The main products of depolymerization were identified and quantified as 2,6‐naphthalene dicarboxylic acid (2,6‐NDA) and ethylene glycol (EG). PEN was completely depolymerized at 260°C in 60 min with an optimal water/PEN mass ratio of 12.0 g/1.0 g (12:1). The yields of 2,6‐NDA and EG were optimized to 83.1% and 79.7%, respectively. Reaction kinetics analysis showed that the PEN depolymerization in subcritical water was first‐order and the activation energy was 95 kJ mol^?1. Additionally, a reaction pathway was proposed based on the experimental results. POLYM. ENG. SCI., 57:1382–1388, 2017. © 2017 Society of Plastics Engineers     

PEN原料及中间体技术进展

新型高性能聚酯聚萘二甲酸乙二醇酯（PEN）等以其卓越的品质受到人们越来越广泛的关注。2，6－二甲基萘（2，6－DMN），2，6－萘二甲酸（2，6－NDCA）和2，6－萘二甲酸二甲酯（2，6－NDC）是生产PEN等聚合物的重要原料和中间体，本文介绍了这些用于新型高分子材料萘系衍生物的生产技术和研究开发趋势，指出解决生产2，6－NDC的原料和成本问题是工业化生产PEN的关键。     

Synthesis and properties of polyamides and copolyamides based on 2,6-naphthalene dicarboxylic acid

A number of polyamides based on 2,6-naphthalene dicarboxylic acid (NDA) and various aromatic diamines were synthesized in N-methyl pyrrolidone (NMP) containing lithium chloride (LiCl) or calcium chloride (CaCl₂) by direct polycondensation using triphenyl phosphite and pyridine. The best reaction conditions for polycondensation were determined in terms of factors such as the amount of the solvency-promoting reagent such as LiCl or CaCl₂ and the initial reactant concentration. Thus, almost all polyamides were obtained with inherent viscosities above 1.0 and up to 3.28 dL/g. Similarly, high molecular weight copolyamides with inherent viscosities of 1.76–3.61 dL/g were prepared from 4,4′-oxydianiline (ODA) and mixed dicarboxylic acids of NDA/terephthalic acid (TPA) or NDA/isophthalic acid (IPA). The solubility of NDA homopolyamides depended on the diamine components. The polyamides derived from meta-, sulfone-, or alkylene-linked diamine showed increased solubility. Copolymerization of ODA with NDA/IPA led to a significant increase in solubility, whereas with NDA/TPA, it gave a limited improvement. All the homopolyamides and copolyamides showed an amorphous X-ray diffraction pattern. Almost all the polymers soluble in aprotic solvents can be solution-cast into strong and tough films. Glass transition shifts of some NDA polyamides can be observed in the differential scanning calorimetry (DSC) curves ranging from 243 to 345°C. Most NDA/IPA–ODA copolyamides also showed clear transitions in the range of 255–268°C. In nitrogen, all the polymers showed no significant weight loss up to 400°C, and their 10% weight loss temperatures were recorded in the range of 434–541°C. © 1994 John Wiley & Sons, Inc.     

2，6-二甲基吗啉的制备研究

采用二氧化硅负载的磷钨钼杂多酸催化剂,以二异丙醇胺和浓磷酸为原料合成了2．6-二甲基吗啉,研究了浓磷酸用量、反应温度、反应时间对2,6-二甲基吗啉收率及顺式异构体含量的影响．优化工艺条件为：n（浓磷酸）：n（二异丙醇胺）=1．5：1,反应温度140℃,反应时间20h,优化条件下产品收率达到93．8％．顺式异构体含量达到95．8％,反应条件温和、环境友好。产品化学结构经IR、MS、^1H NMR分析确证。     

2,6-二叔丁基对硝基苯酚的合成与表征

以2,6-二叔丁基苯酚为原料,石油醚为溶剂,通过硝化反应合成了抗氧剂中间体2,6-二叔丁基对硝基苯酚,并采用元素分析和红外光谱对其结构进行表征。通过条件实验得出2,6-二叔丁基对硝基苯酚的最佳合成条件为:硝酸浓度为30%,反应原料摩尔比为1∶1.5,反应时间为10 h,此条件下,2,6-二叔丁基对硝基苯酚的产率为81.6%,熔点为156.9~157.8℃。     

Amorphous copolyesters based on 1,3/1,4‐cyclohexanedimethanol: Synthesis,characterization and properties

Two series of amorphous copolyesters, PETGN and PETGS, were synthesized by the copolymerization of 2,6‐naphthalene dicarboxylic acid (NDA) (0–40%), succinic acid (SA) (0–40%), 1,3/1,4‐cyclohexanedimethanol (1,3/1,4‐CHDM) (10–50%), ethylene glycol (EG), and terephthalic acid (TPA). The compositions and molecular weights of the copolyesters were determined by ¹H NMR spectroscopy and viscometry, respectively. The thermal behaviors were studied over the entire range of copolymer compositions, using DSC and TGA. The optical characteristics, heat‐shrinkable effects and tensile properties of these polymers were also determined. Experimental results indicated that the thermal, optical, tensile, and shrinkage properties of PETGN and PETGS were functions of NDA or SA content. DSC and X‐ray analysis demonstrated that both PETGN and PETGS series were amorphous. Incorporating NDA and SA influenced the T_g values of those polymers, from about 37°C for PETG₃₀S₄₀ to 89°C for PETG₃₀N₄₀. Furthermore, the shrinkage of these amorphous copolyesters was more than 40% when the heating temperature was higher than the corresponding T_g. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008