常压下环氧环己烷-环己酮-环己醇三元系汽液平衡

H2O2氧化环己烯制备环氧环己烷时有环己酮、环己醇等很多副产物产生。为了获得较纯的环氧环己烷需采用精馏进行分离,精馏提纯需要相关体系的汽液平衡数据,因此采用改进的EC-2汽液平衡釜测定常压(101.33 k Pa)下环己酮-环己醇二元体系和环氧环己烷-环己酮-环己醇三元体系汽液平衡数据。利用二元系汽液平衡数据拟合得到的Wilson方程配偶参数预测该三元体系的汽液平衡数据,并以汽相组成的误差平方和作为目标函数,用Wilson方程关联实验数据,结果表明预测值及关联值与实验值偏差较小,可满足工程上分离设计的需要。     

常压下环己烯-环氧环己烷-环己酮三元系汽液平衡的测定、预测及关联

H2O2氧化环己烯制备环氧环己烷时会产生环己酮等副产物,同时还有未反应完的环己烯。为了获得较纯的环氧环己烷需采用精馏将副产物和环己烯分离出来,精馏提纯需要相关体系的汽液平衡数据,因此采用改进的EC-2汽液平衡釜测定常压(101.33k Pa)下环己烯-环氧环己烷-环己酮三元体系汽液平衡数据。利用二元系汽液平衡数据拟合得到的Wilson方程配偶参数预测该三元体系的汽液平衡数据,并以汽相组成的误差平方和作为目标函数,用Wilson方程关联实验数据,结果表明预测值及关联值与实验值偏差较小,可满足工程上分离设计的需要。     

常压下环己烷-环氧环己烷二元体系汽液平衡研究

合成环氧环己烷的反应液中常含有环己烷,为获得高纯度的环氧环己烷产品,可采用精馏方法进行分离。而精馏设计计算需要环氧环己烷-环己烷二元体系汽液平衡数据,为此用改进的Rose汽液平衡釜在常压(101.3 kPa)下测定该二元体系的汽液平衡数据,并对所测得的数据进行热力学一致性检验,结果表明实验数据符合热力学一致性。以汽相组成的误差平方和作为目标函数,分别用Wilson方程和NRTL方程关联实验数据,得到分子交互作用能量参数,并对汽液平衡计算值与实验值进行比较,发现二者偏差较小,可以满足工程上分离设计的需要。     

常压下环己烯-环氧环己烷二元汽液平衡数据的测定和关联

用分子氧对环己烯直接进行环氧化涉及到的内容之一是环己烯与环氧环己烷的分离.为了为二者的分离提供基础物性数据,采用了改进的EC-2型汽液平衡釜测定了常压下(101.33kPa)环己烯(1)-环氧环己烷(2)二元体系的汽液平衡数据,所得结果经检验符合热力学一致性.用Wilson方程对所测的汽液平衡数据进行了关联,求出了Wilson方程交互作用参数,并对汽液平衡的计算值与实验值进行了比较,发现二者偏差较小,可以满足工程上环己烯、环氧环己烷分离设计的需要.     

减压下正丁醇对甲基环己烷-甲苯系汽液平衡的影响

本文使用Rose-Williams平衡装置,测定了甲基环己烷—甲苯,甲基环己烷—正丁醇,甲苯—正丁醇三组二元体系在300和500mmHg下的汽液平衡数据,用Herington经验方法对所测数据进行了恒压下的热力学一致性检验。采用Wilson方程对三组二元系的汽液平衡数据进行了热力学关联,并用Wilson方程和UNIFAC方程推算了甲基环己烷—甲苯—正丁醇三元系在300和500mmHg下的汽液平衡数据。讨论了正丁醇对甲基环己烷—甲苯系汽液平衡的影响     

碳酸二甲酯-碳酸二乙酯-甲醇三元体系相平衡数据的推算

采用双循环汽液平衡釜测定了常压下碳酸二甲酯-碳酸二乙酯、碳酸二甲酯-甲醇、碳酸二乙酯-甲醇三组二元体系的汽液平衡数据,实验数据经Herington面积积分法检验符合热力学一致性。用Wilson模型分别对实验数据进行了关联,利用关联出的模型参数计算相应的汽相组成,并与实验值比较,二者符合良好。利用二元体系的汽液平衡数据,由Wilson方程推算了碳酸二甲酯-碳酸二乙酯-甲醇三元体系的汽液平衡数据。为建立碳酸二乙酯和碳酸二甲酯、甲醇的精馏分离数学模型提供了基础数据。     

常压下环己烯-环己酮二元体系汽液平衡研究

H2O2氧化环己烯合成环氧环己烷有很多副产物生成,如环己酮、环己醇等,为了获得较纯的环氧环己烷需采用精馏提纯的方法将副产物分离出来.而精馏提纯需要相关体系的汽液平衡数据,为此用改进的Rose汽液平衡釜测定常压下环己烯-环己酮二元体系汽液平衡数据,并对数据进行热力学一致性检验,结果表明实验数据符合热力学一致性.以汽相组成...     

四氢呋喃-环己烷二元物系常压汽液平衡数据的测定和关联

为了常压分离四氢呋喃-环己烷二元物系,利用CE-2型汽液平衡装置测定了四氢呋喃-环己烷二元物系的常压(100 k Pa)汽液平衡数据。实验结果表明:四氢呋喃和环己烷形成最低共沸物。实验汽液平衡数据通过了Herington半经验法热力学一致性校验。通过Margules,Van Laar,Wilson和NRTL活度系数模型对实验数据进行关联和估算,得到了模型的参数值。对模型计算值和实验值进行比较得到汽相摩尔分数和泡点温度的最大绝对平均偏差。通过比较可以看出,Vanlaar和Wilson活度系数模型更适合于四氢呋喃(1)-环己烷(2)二元体系汽液平衡数据的关联。     

环己烯、1,2-环氧环己烷和2-环己烯-1-酮二元和三元系的等压汽液平衡

作者采用改进的EC-2型汽液平衡釜测定了常压下(101.33kPa)环己烯、1,2-环氧环己烷、2-环己烯-1-酮3组二元系和1组三元系的等压汽液平衡(VLE)数据。对二元的等压汽液平衡实验数据作了热力学一致性检验和Wilson方程关联,求出了相应的Wilson方程配偶参数,用求得的参数推算了相应二元及三元系的VLE数据,并将其与实验值进行了比较,结果令人满意,可以满足工程上环己烯与其氧化产物分离设计的需要。     

环己烷-正丁醇-甲苯三元体系加压相平衡研究

研究了环己烷、正丁醇、甲苯这类醇烃体系的加压汽液平衡行为.根据环己烷、正丁醇、甲苯有关二元体系求得的Wilson能量参数及统一关联式,预测了环己烷-正丁醇-甲苯三元体系在101～911kPa5个压力下的汽液平衡数据,与实测值符合良好.     

Nickel (salen) / methylaluminoxane catalyzed polymerization of norbornene

Summary Nickel (salen) in conjunction with methylaluminoxane (MAO) catalyzes the polymerization of norbornene to poly (2,3-bicyclo [2.2.1] hept-2-ene) [poly (norbornene)]. Methylaluminoxane (MAO) was used as cocatalyst as such (MAO-I) and after distilling off free trimethylaluminium (MAO-II). The catalyst system was very active in chlorobenzene at room temperature. It was also found that MAO-II gave higher activity as compared to MAO-I. The samples of polynorbornene were soluble in 1,2,4-trichlorobenzene. The poly (norbomene)s were characterized by intrinsic viscosity and thermal properties. Received: 4 November 1999/Revised version: 25 January 2000/Accepted: 31 January 2000     

UNIFAC模型预测乙烯基环己烯-乙烯基降冰片烯气液相平衡数据

以乙烯基环己烯一乙烯基降冰片烯为体系,在低压下,将气相视为理想气体,液相为非理想溶液的情况下,用UNIFAC模型估算了液相活度系数,得到了在8．0kPa下此二元体系的气液平衡数据,并与文献值比较,拟合结果较好。结果表明在缺乏此体系的气液平衡数据时,可以用UNIFAC模型估算作为基础数据,以便顺利进行工程设计。     

Amphiphilic macromolecular nanostructure materials derived from 5-(octanoate methyl)bicyclo[2.2.1]hept-2-ene and 5-(phthalimide methyl)bicyclo[2.2.1]hept-2-ene via ring-opening metathesis copolymerization

Novel highly stable polynorbornenes with self-assembling amphiphilic architecture containing hydrophilic ammonium salt and hydrophobic alkyl ester group were obtained via ring-opening metathesis polymerization (ROMP) of 5-(octanoate methyl)bicyclo[2.2.1]hept-2-ene (NBMO) and 5-(phthalimide methyl)bicyclo[2.2.1]hept-2-ene (NBMPI), hydrogenation, hydrazinolysis, and subsequent quaternization. Polymeric micelles of such amphiphilic random and block polynorbornenes formed in solvents by varying the content of ammonium salts were investigated. Amphiphilic block copolymers exhibited perfect spherical morphology. Nanoscale polymeric micelles of random copolymers with 50-75 mol% of ammonium salts were roughly spherical in shape, while the morphologies of micelles transferred into network-like aggregates as hydrophilic contents of the random copolymers are higher than 80 mol%. The formation and fine structures of micelles were investigated by dynamic light scattering (DLS), TEM, and fluorescence technique using pyrene as fluorescence probe.     

Evidence of isomerization of 5-methylenebicyclo[2.2.1] hept-2-ene cation by13C NMR spectroscopy

Summary Cations obtained by reaction of various protonic acids with 5-Methylenebicyclo [2.2.1] hept-2-ene (5-methylene-2-norbornene) have been studied by C NMR spectroscopy. The isomerization of initial carbocation has been pointed out. A correlation of these results with the structure of the corresponding polymers has been establishedThe cationic polymerization of 5-Methylenebicyclo [2.2.1] hept2-ene (5-methylene-2-norbornene) has been investigated several times and KENNEDY (1974) published a review on this topic. A structure of the polymer obtained by classical cationic initiation has been suggested; this results from infrared and X.R. diffraction studies.In a recent work IVIN et al. (1980) reported the¹³C NMR spectrum of a poly[5-methylenebicyclo [2.2.1] hept-2-ene] resulting from a Ziegler-Natta initiation. We obtained the same¹³C NMR spectrum as IVIN et al. when the initiator were TiCl₄, CF₃ COOH, CCl₃COOH and concentrated H₂SO₄ (see fig.1). Chemical shifts and coupling constants fit with the generally accepted structure of the polymers: KENNEDY and MAKOWSKY (1967) suggested an isomerization of the active species:     

UNIFAC模型预测含α-蒎烯体系的汽液平衡数据

α-蒎烯具有一个特殊的双环双键结构。为更准确地预测含α-蒎烯体系的汽液平衡数据,利用UNIFAC模型原理对α-蒎烯进行基团重新划分,可得到一个大基团双环[3.1.1]-2-庚烯基与3个CH₃。通过对含α-蒎烯二元汽液平衡数据进行拟合,得到新基团双环[3.1.1]-2-庚烯基与CH₃、C=C、ACH、ACCH₃基团间的相互作用参数,扩大了UNIFAC模型的应用范围。与原始UNIFAC模型仅利用CH₃、C=C、ACH、ACCH₃基团预测出的含α-蒎烯三元体系汽液平衡数据进行比较,新基团模型预测的气相组成平均偏差以及温度平均偏差比原始基团模型的偏差要更小,说明新基团的划分更为合理。     

Ring-opening polymerization of 1 -ethylbicyclo[2.2.1] hept-2-ene

1-Ethylbicyclo[2.2.1]hept-2-ene has been polymerized using a range of metathesis catalysts and the structure of the polymers determined by ¹³C n.m.r. spectroscopy. For a given catalyst the cis double bond content was lower and the head-tail bias greater than for polymers of the 1-methyl analogue. This is interpreted in terms of enhanced steric and polar effects brought about by the ethyl substituent.     

Addition polymerisation vs. ROMP on cyclic and strained olefins with the Mo(CO)5PPh3/alkylaluminums catalysts

The polymerisation of cyclic and strained monomers such as bicyclo[2.2.1]hept-2-ene (norbornene, NBE) and bicyclo[2.2.1]hepta-2,5-diene (norbornadiene, NBDE) with the catalytic systems Mo(CO)₅PPh₃/alkylaluminums was studied. From the polymers produced we demonstrate the existence of an antagonism between the ROMP (Ring-Opening-Metathesis-Polymerisation) mecanism and the olefin addition polymerisation mecanism. In addition ROMP mecanism is affected by the solvent. These catalysts also promotes the isomerisation of double bonds, as indicated by the ESR signal observed for the conjugated crosslinked polyNBDE produced by ROMP. Received: 5 August 1996/Revised version: 22 October 1996/Accepted: 25 October 1996     

Poly(2,5-(3,4-bis(methoxymethyl)furanylene)vinylene)s prepared by aqueous ring opening metathesis polymerisation

Summary Poly(2,5-(3,4-bis(methoxymethyl)furanylene)vinylene)s of various microstructures, prepared by aqueous Ring Opening Metathesis Polymerisation (ROMP) of exo,exo-5,6-bis(methoxymethyl)-7-oxabicylo[2.2.1]hept-2-ene, were characterised by high field NMR.     

Metathesis ring opening polymerization of 5,6-dimethylenebicyclo[2.2.1]hept-2-ene

5,6-Dimethylenebicyclo[2.2.1]hept-2-ene ( I ) polymerizes in the presence of the two-component ring opening metathesis polymerization (ROMP) initiators WCl₆/(CH₃)4Sn and MoCl₅/(CH₃)4Sn. The product polymers were insoluble in all of many solvents investigated and are presumably cross-linked. The product polymers were investigated by IR and solid state ¹³C NMR spectroscopy, which established that the material consisted predominantly of poly(1,4-(2,3-dimethylene-cyclopentylene)vinylene) ( II ). A possible alternative route to II via thermal dehydrochlorination of poly(1,4-(2,3-bis(chloromethyl)cyclopentylene) vinylene) ( IV ) was also examined.     

UV reactive polymers for refractive index modulation based on the photo-Fries rearrangement

In this study we report on the synthesis and characterization of photoreactive polymers which display large changes in their refractive index upon UV irradiation. These polymers contain aromatic ester groups which undergo a photo-Fries rearrangement from aryl esters to hydroxyketones. The polymers under investigation were poly(4-acetoxystyrene) and two derivatives of polynorbornene, poly(bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, phenyl ester) and poly(bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenyl ester). The kinetics of the photoreaction was studied by FTIR spectroscopy. Ellipsometric measurements of thin films showed that the photo-Fries rearrangement causes a large increase of the refractive indices in these polymers (between +0.03 and +0.05). The modulation of the refractive index is of interest for applications in the field of optics and data storage. The photoreaction also leads to an increase in surface energy as evidenced by contact angle measurements with water and diiodomethane as test liquids.