裂解C_5馏分中二烯烃热二聚过程的研究

用封管实验方法考察了二聚反应温度、反应停留时间和不同环戊二烯(CPD)含量对C5馏分热二聚过程中各二烯烃组分反应行为的影响。结果表明,当反应温度在115~125℃、停留时间2~3h、CPD质量分数大于17%时,CPD的转化率不小于92%,异戊二烯(IP)、间戊二烯和1,3丁二烯的转化率分别在7%、1.5%和13%左右,双环戊二烯(DCPD)的收率接近80%,未知共二聚物的总生成量在2.6%左右。C5原料中CPD的含量高,其转化率和DCPD收率也高。C5原料存放一段时间,CPD含量降低后,IP的共二聚反应损失将略有减少。实验数据为工业上热二聚反应分离装置的设计提供了支撑。     

釜式反应器中热二聚法分离C5混合物中的环戊二烯

采用釜式间歇反应器对石油裂解C5混合原料中的环戊二烯（CPD）进行热二聚，生成双环戊二烯（DCPD）后进行分离，研究了CPD浓度，反应温度和反应时间以及C6含量等因素对反应过程的影响。     

梳状支链水性聚氨酯的结构与性能

用梳状支链结构的聚合物二醇(CPD)和聚己内酯二醇(PCLD)共同作软段,制备了含有梳状支链结构的水性聚氨酯(CWPU),着重研究了CPD含量和梳状支链结构对CWPU力学性能、粘接性能和耐水性的影响。研究表明,随着聚合物多元醇中w(H-CPD)从0%增加到100%,CWPU的拉伸强度从46.1MPa降低到15.9MPa,断裂伸长率从651%降低到433%,吸水率从18.4%增加到49.6%,CWPU对PVC的T-剥离强度在w(H-CPD)=40%时最大,达9.58N/mm。保持聚合物多元醇中w(CPD)=40%时,随着CPD梳状支链末端烷基碳原子数从4增加到18,CWPU的T-剥离强度从7.65N/mm增加到8.21N/mm;在H-CPD/C18-CPD/PCLD为软段体系中,随着w(C18-CPD)从0%增加到40%,CWPU的粘接性能略微下降,吸水率从21.3%降低到13.1%。     

热二聚法分离C5混合物中的环戊二烯

采用管式连续反应器及釜式间歇反应器对石油裂解C5混合原料中的环戊二烯（CPD）进行热二聚，生成双环戊二烯（DCPD）后进行分离。深入研究了CPD浓度，反应温度和反应时间以及C6含量等因素对反应的影响，提出了不同情况下选择使用的反应条件和反应器型。     

含环戊二烯基的丙烯酸衍生物的合成和表征

以丙烯酸(AA)和环戊二烯(CPD)为起始原料,首先合成了丙烯酰氯(AC)和环戊二烯基乙醇(CPDE)两种中间体,通过酰氯与醇或活泼氢化合物之间典型的消除反应,合成了丙烯酸环戊二烯基乙酯(CEA)和环戊二烯—丙烯酸加合物(CPD—AA)。并对其结构进行了表征。     

甲基环戊二烯的合成实验研究

以环戊二烯(CPD)、氢氧化钠和一氯甲烷为原料,合成甲基环戊二烯,最佳反应温度为8℃,CPD与氢氧化钠摩尔比为4.2,CPD加入速度为6.0 m L/min。此时甲基环戊二烯的收率达85.2%。     

双环戊二烯的生产和应用

双环戊二烯(DCPD),分子式为C_(10)H_(12), 分子量为132.21。该品是环戊二烯(CPD) 的二聚体,将CPD置于室温下容易二聚化作 用生成二聚体环戊二烯(DCPD),将本品 加热到140～160℃,能发生可逆反应,解聚 成CPD,反应式如下:     

甲基环戊二烯的合成实验研究

以环戊二烯(CPD)、氢氧化钠和一氯甲烷为原料,合成甲基环戊二烯,最佳反应温度为8℃,CPD与氢氧化钠摩尔比为4.2,CPD加入速度为6.0 m L/min。此时甲基环戊二烯的收率达85.2%。     

阻聚剂在C_5馏分热二聚过程中的应用

为减少C5馏分环戊二烯(CPD)热二聚过程中异戊二烯(IP)的聚合损失,采用封管实验方法考察了添加阻聚剂二乙基羟胺(DEHA)、对叔丁基邻苯二酚(TBC)、邻硝基苯酚(ONP)对热二聚过程中各二烯烃组分聚合程度的影响。结果表明,阻聚剂的加入不影响CPD的二聚,但减少了IP、间戊二烯(PD)的聚合损失。就阻聚效果而言,DEHA优于TBC和ONP。通过正交实验,考察了热二聚温度、时间以及DEHA质量分数等因素对双环戊二烯(DCPD)收率和IP聚合损失的影响。较佳工艺条件是热二聚温度120℃,反应时间3 h,DEHA质量分数500×10-6。该条件下DCPD的收率达到80%左右,IP的聚合损失可控制在8%以内。     

二茂铁合成新方法的研究

以环戊二烯 (CPD)、氯化亚铁 (FeCl2 ·4H2 O)、氢氧化钠 (NaOH)为原料 ,以二甲基亚砜为溶剂合成了二茂铁 ,n(CPD)∶n(NaOH)∶n(FeCl2 ·4H2 O) =1∶2∶0 5 ,产率为 93%。     

环戊二烯及双环戊二烯对裂解汽油全馏分加氢装置运行的影响

介绍了裂解汽油全馏分加氢过程中发生的环戊二烯热二聚及双环戊二烯热分解反应。该转化反应导致了二段加氢反应器双烯值高于一段出料的双烯值,并缩短了二段加氢反应催化剂的运行周期,提出了降低影响的措施。     

A kinetic model of the cycloaddition reactions between cyclopentadiene and 1,3-butadiene for synthesis of 5-vinyl-2-norbornene

Under high temperature and pressure, a continuous tubular reactor was successfully utilized to investigate the kinetics of 5-vinyl-2-norbornene (VNB) production. The process involved multiple cycloaddition reactions between cyclopentadiene (CPD) and 1,3-butadiene (BD). The results, spanning a wide range of operating conditions, indicate that higher temperature (180°C) and proper residence time (72 min) were conducive to efficient synthesis of VNB. The apparent kinetic parameters, including activation energies and pre-exponential factors, were acquired by fitting experimental data under integral operating conditions. The kinetic model was proven effective from a practical point of view in predicting the concentration changes of each product in the range 140 to 180°C and 30 to 80 wt.% concentration. This work provides a solid basis for the optimization of the VNB synthesis process.     

FD模型应用于煤热解过程的数值模拟

为将煤热解FD模型引入对煤热解实际过程的数值计算与分析,提出了适用于煤热解实际过程的数值计算方法。分别对3种不同的煤在热管反应器中的热解过程进行了数值计算,并与实验结果以及已有的FG-DVC模型、CPD模型的数值计算结果进行了对比分析。并分析了热解温度、颗粒粒径对煤热解产物的影响。结果表明,与FG-DVC模型、CPD模型相比,FD模型的计算精度更高,能更好地用于数值计算煤热解的实际过程;随着热解温度的升高,气体产量先快速增大,当热解温度高于1373 K时,气体产量的变化很小;而随着热解温度的升高,焦油产量一直逐渐减小,且达到焦油产量最大值所需的时间也缩短;随着颗粒粒径的增大,气体与焦油的产量都逐渐减小,而达到焦油产量最大值所需的时间却延长。     

从C5和C9中分离CPD、DCPD以及二者聚合的动力学和热力学研究进展

介绍了从C5和C9馏分中分离CPD、DCPD以及二者聚合时，动力学和热力学理论方面的研究进展。     

Cationic copolymerization of 1,3-pentadiene with 1,3-cyclopentadiene

Copolymerizations of 1,3-pentadiene (PD) with 1,3-cyclopentadiene (CPD) initiated by aluminium trichloride were carried out in toluene. The addition of CPD in the PD polymerization system does not affect the molecular weight but greatly increases the softening point of the polymer due to the introduction of cyclic structures. The Gardner color scale of the polymer is also raised by introduction of unsaturated rings of CPD. The copolymerization gives a complete conversion but generates insoluble crosslinked gels at high CPD content due to the high crosslinking reactivity of CPD. The integral intensities of unsaturated protons from PD and CPD segments of the copolymer chain on the ¹H-NMR spectrum give a perfect correlation with the copolymer compositions. The low-conversion experiments were carried out with small amounts of CPD in order to determine the reactivity ratio in this copolymerization system (M₁ = PD and M₂ = CPD). The result of r₁ = k₁₁/k₁₂ = 0.46 demonstrates that CPD has a higher reactivity than PD toward PD growing carbocations, and hence the copolymer shows a higher CPD proportion than the corresponding comonomer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1883–1887, 1997     

Homogeneous Catalytic Cleavage of Saturated Carbon-Nitrogen Bonds

An evaluation of the catalytic reactivity of [CPD (CO)₂RuH]₂ (1) and (CPD)(CO)₃Ru (2) (where CPD = tetraphenylcyclopentadienone) with amines suggests that these complexes catalyze C-N bond cleavage by activating C-H bonds alpha to the nitrogen atom of tertiary, secondary and primary amines at ca. 140° C. When two different amines are used, transalkylation takes place. With secondary and primary amines, ammonia and tertiary amines are formed. A series of amine complexes (CPD)(CO)₂Ru.NR₃ (R = alkyl/H) was isolated from stoichiometric reactions of 1 or 2 with primary and secondary amines. It was found that tertiary amines do not generate complexes of the above type but rather unexpectedly give secondary amine complexes by cleavage of an alkyl group. The only isolatable tertiary amine complex is the moderately stable (CPD)(CO)₂RuNMe₃. All amine complexes were characterized by spectral and elemental analyses. Catalytic aspects of C-N bond cleavage were studied. Complexes (1) and (2) were found to react with primary, secondary and tertiary amines to generate imminium or eneamine species which subsequently undergo hydrolysis with water. This is in contrast to the Ru carbene mechanism previously proposed for cluster catalyzed C-N bond activation and cleavage. The two reactions are compared with respect to D for H exchange (with D₂O), water requirement and production of trace products during catalysis. A primary alcohol was found to substitute alkyl groups of a tertiary amine under the catalytic action of 1. A catalytic reaction cycle is proposed.     

Antagonism between cloud point and cold filter plugging point depressants in a diesel fuel

Differential scanning calorimetry (d.s.c.) and thermomicroscopy were used to provide a better understanding of the antagonistic effect on cold filter plugging point (CFPP) when cloud point depressants (CPD) and CFPP additives are mixed into a diesel fuel. It is shown that the CFPP achieved by using only CFPP additive can be attained in the presence of CPD if a small, homogeneous size of crystals of paraffins is again obtained. Two ways are proposed to obtain this result: modification of the chemical structure of the CPD, and optimization of the concentration of each component of the blend. In either case a decrease in efficiency of the CPD is observed, but the antagonism disappears. It is possible to predict the efficiency of CFPP additives in a diesel fuel containing CPD by evaluation of T_g of the hydrocarbon matrix and determination of the percentage of light n-alkanes by d.s.c.