Synthesis of Novel Ionic Liquid ([C_4 CNmim]^+ PF_6^-) and Application to Preparation of Polyketone

N-valeronitrile-N'-methylimidazolium hexafluorophosphate ([C 4 CNmim]+ PF 6),as a novel ionic liquid with polar nitrile functional group,was prepared.The structure of the ionic liquid was characterized by using IR and 1 H NMR.As a medium,the ionic liquid plays an important role in copolymerization of carbon monoxide (CO) with styrene (St).Some synthetic conditions were determined,including the usage of ionic liquid,palladium composite catalyst and methanol,CO pressure,reaction time and reaction temperature.The influence of these factors on catalytic activity was analyzed.The results show that the catalytic activity has reached 1 724.1 gStCO/(gPd·h) and the catalyst could be reused 5 times under the optimal condition:composite catalyst 0.015 mmol,ionic liquid 3 mL,methanol 0.75 mL,CO pressure 2MPa,reaction time 2 h and reaction temperature 70℃.This CO/St copolymerization within [C 4 CNmim]+ PF 6 system could facilitate ionic liquids with efficient and economical applications to polymeric materials.

Synthesis of Polyketone by Copolymerization of Styrene and CO Using Carbon Nanotube-Complex Pd^(2+) Catalyst

The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst(Pd/CNT) for the copolymerization of carbon monoxide(CO) and styrene(ST) towards the formation of polyketone(PK).The Pd/CNT was characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM).The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy(FTIR),13C-nuclear magnetic resonance(NMR) and XRD,respectively.The catalyst showed excellent activity and reusability in promoting the fabrication of PK.It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%.The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene.

POLYKETONE FROM ETHYLENE WITH CARBON MONOXIDE CATALYZED BY NOVEL CATALYST SYSTEMS BASED ON COPPER WITH BIDENTATE PHOSPHORUS CHELATING LIGANDS

Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with carbonmonoxide, in which the ligand was a bidentate phosphorus chelating ligand. The experimental results showed that this kindof Cu catalyst system exhibited high activity. When DPPP (1, 3-bis(diphenylphosphine)propane) and CH_3COOH were usedas ligand and acid, the corresponding catalyst system had the best activity of 108.1 g copolymer/(gCu·h). The novel Cu catalyst system had the advantages of high stability and low cost.

POLYKETONE FROM CO AND STYRENE: A USEFUL COPOLYMER CATALYZED BY A HIGHLY ACTIVE AND STABLE PALLADIUM CATALYST WITH 5-NITRO-1,10-PHENANTHROLINE LIGAND

A novel coordinated complex [(5-nitrophen)Pd(CF3CO2)2] (5-nitrophen = 5-nitro-1,10-phenanthroline) was first synthesized. By using XPS, IR, and 1H-NMR, its coordination unit was studied in comparison with those of complexes [(N-N)Pd(CH3CO2)2] and [(N-N)Pd(CF3CO2)2]. The H2,9 proton signals of 1H-NMR spectra of the complexes are excellent probes to monitor the evolution of the environment of the palladium atom. The state of anionic coordination was confirmed by the presence of IR absorption peaks of COO in complexes ([(N — N)Pd(CH3CO2)2] and [(N — N)Pd(CF3CO2)2]). Bonding energies of N1s and Pd3d5 obtained from XPS data testified to the strength of the N-Pd coordinating bond. The conclusion can be drawn by analyzing these data from IR, XPS and 1H-NMR that it is the unsymmetrical substitution of the 1,10-phenanthroline (phen) that makes the [(5-nitrophen)Pd(CF3CO2)2] more active. Experimental results showed that [(5-nitrophen)Pd(CF3CO2)2] exhibits much higher activity than [(bipy)Pd(CF3CO2)2] (1,1'- bipyridine = bipy) and [(phen)Pd(CF3CO2)2] under the same conditions.

Synthesis of Polyketone STCO Promoted by Rare Earth Catalyst

To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copolymerization of carbon monoxide （CO） and styrene （ST） to synthesize aliphatic polyketone STCO. The catalytic system was composed of rare earth neodymium acetate, yttrium acetate, 2,2＇-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1 ,4-benzoquinone. The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectroscopy respectively. The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copolymerization were investigated. The results show that the proposed rare earth has distinct catalytic activity in the copolymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/（mol·h）.

Use of Ionic Liquids in Recycle of Palladium Catalysts for Synthesis of Polyketone

Room temperature ionic liquids as solvents for palladium-catalyzed copolymerization of carbon monoxide and styrene were prepared by reaction of aqueous lead tetrafluoroborate with correspond-ing chloride or bromide salts. The recyclability of palladium composite catalyst in various ionic liquids was investigated. [Pd(bipy)2][BF4]2 showed a lower catalytic activity than [Pd(bipy)2][PF6]2 in similar conditions, although the catalytic activity of each composite catalyst in ionic liquids still existed after 4 successive recycles. It was shown the catalytic activity of palladium composite catalyst was higher than that of the catalyst formed in situ from palladium acetate, 2,2′-bipyridyl, and HA (A=PF6-, BF4-) in ionic liquids. The effects of volume of ionic liquids, reaction time, and the dosage of benzoquinone on the copolymerization were also studied.

稠油井内衬保温油管热损失分析及开采参数优化

针对塔河油田稠油开采过程中原油热量损失大、资源浪费的问题,开展内衬保温油管开采技术研究。基于井筒稳态热传递与地层非稳态热传递理论,建立了稠油井井筒热传递数学模型,评价了不同内衬材料油管的保温性能,揭示了含水率、日产液量及内衬保温油管下深对井筒温度的影响规律。研究表明:内衬聚酮防腐层与气凝胶保温层的保温油管保温性能最佳,日产液量和保温油管下深对井口温度影响较大,含水率对井口温度的影响较小;日产液量大于72 t/d且保温油管下深大于3 500 m时,可满足稠油开采的温度要求。该研究明确了内衬保温油管保温的可行性,可为油田保温油管内衬的选材、稠油开采工艺参数的制订提供技术依据。

聚乳酸/聚酮共混织物的开发与设计

采用聚乳酸/聚酮共混纤维设计小提花织物,从织物风格、舒适性能、外观保持性等方面探讨两种不同聚酮纤维含量共混纤维织物的性能。结果表明,两种织物厚度和面密度基本相同,随着聚酮纤维含量的提高,织物的折皱回复性、悬垂性变好,而耐磨性下降,透气性变差。设计的纯纺小提花织物轻薄、光泽感强、耐磨性好、透气性好,适用于夏季轻薄织物、女士裙装、童装、男士衬衣等。

某油井聚酮材料内衬油管失效分析

[目的]塔河油田某油井的聚酮材料(POK)内衬TP110S油管现场应用105 d后发生腐蚀穿孔。[方法]通过形貌观察、化学成分测定、金相组织分析、硬度测试和拉伸试验,对油管基材进行失效分析,采用维卡软化温度和氧化诱导时间来评价POK内衬材料的理化性能和热学性能。[结果]内衬管基材穿孔失效的原因在于油管基材的Cr含量低,在高温环境下受CO_(2)和Cl-的协同腐蚀作用。POK内衬失效的原因是起管过程中受到井内高温至井口低温的温度变化影响,同时内衬材料脆化严重,导致部分POK内衬在起井过程中脱落,而温变产生的轴向拉伸应力和翻边预紧力导致个别内衬回缩明显。[结论]后期进一步规范油管上、卸扣作业过程,降低轴向应力,并改进POK材料,以提升内衬的抗温变能力。

新型绿色工程塑料聚酮(POK)的研究进展

聚酮(POK)是一种由一氧化碳和不饱和烃共聚而成的高性能工程塑料,具有优异的力学、化学和热稳定性,还能在紫外线下光降解。聚酮的研究和开发顺应了“碳中和、碳达峰”与“环境友好材料”两大热点要求。本文概述了聚酮的发展前景、研究历程、聚合工艺与催化体系、特性与应用。最后,分析了国内POK产业面临的困境,并对POK行业的未来发展进行了展望。

脂肪族聚酮的加工性能

以2种不同相对分子质量的脂肪族聚酮(POK)树脂作为研究对象,利用毛细管流变仪、拉伸流变仪、旋转流变仪、差示扫描量热仪(DSC)和热重分析仪(TGA)研究了POK1和POK2的挤出特性、熔体强度和加工稳定性。结果表明,在相同温度下,与POK1相比,POK2的幂律指数较高,同时当剪切速率小于600 s^(-1)时,与POL2相比,POK1的黏流活化能较低,当剪切速率大于600 s^(-1)时,二者保持一致。拉伸黏度测试表明,POK1和POK2的熔体强度分别为15和40 m N。加工稳定性方面,在小幅震荡流变测试中,POK1和POK2分别在16.6和4.7 min处出现分子间环化和交联现象,2种POK树脂的熔点和结晶温度均降低。并且,交联后2种树脂的热失重残炭率由30.3%和28.4%提升至32.6%和30.8%,这表明,此时POK树脂出现了降解交联,影响其结晶性能和可加工性。

红豆杉内生真菌Trichoderma sp.次生代谢产物及其抗菌活性研究

目的从红豆杉内生木霉属真菌MPT-009的次生代谢产物中发现具有抗菌活性的单体化合物。方法采用硅胶、ODS、Sephadex-LH20柱层析和半制备高效液相等方法进行分离,利用高分辨率质谱、NMR波谱数据和电子圆二色谱(ECD)计算等方法确定化合物结构,通过二倍稀释法评价化合物对8种临床耐药性细菌和7种植物病原真菌的抗菌活性。结果从木霉属真菌MPT-009大米发酵产物中共分离得到了一个新的聚酮化合物trichoketide F(1)和6个已知化合物10-deacetylkoningiopisin D(2)、koninginin A(3)、koninginin B(4)、koninginin D(5)、koninginin E(6)、isoharziandione(7)。化合物1对马铃薯黄萎病菌、水稻纹枯病菌、油菜菌核菌、棉花枯萎病菌、草莓黑斑病菌、玉米小斑病菌显示一定的抑制活性,MIC值为12.5~50μg/mL。结论本文对红豆杉内生真菌Trichoderma sp.的次生代谢产物进行了深入研究,分离得到1个新化合物,丰富了木霉属真菌代谢产物,且该化合物对油菜菌核病菌具有较好的抑制活性,MIC值为12.5μg/mL。

Chain-Length-Dependent Hydrogen-Bonded Self-Assembly of Terminally Functionalized Discrete Polyketones

Here,we report the synthesis and the chain-lengthdependent self-assembling behaviors of discrete di-,tetra-,and hexaketones terminally functionalized with hydrogen-bonding carboxyl(C1,C2,and C3)and 3-acylaminopyridine groups(P1,P2,and P3).These polyketones were prepared by the coupling reactions of silylated analogues of 3,3-dimethylpentane-2,4-dione and t-butyl 2,2-dimethyl-3-oxobutanoate and the subsequent hydrolysis or amidation with 3-aminopyridine.Single-crystal Xray diffraction analysis revealed that C1 and C2 form helical assemblies in which the components are connected by the dimerization of terminal carboxyl groups,whereas the longer C3 showed infinite hydrogen-bonded chains mediated by 1,4-dioxane used as a crystallization solvent.Pyridine-terminated P1 exhibited a three-dimensional hydrogen-bonded network owing to multiple NH…N(pyridine)hydrogen bonds in the solid state.P2 generated a double-helix-like fiber structure in the crystalline state.Among the pyridine-terminated polyketones P1−P3,only P2 showed gelation behavior in chloroform(100 mM concentration)at 25℃.The scanning electron microscopy measurement of xerogel P2 revealed the formation of rod-like structures with a thickness of approximately 0.5−3.5μm.These results demonstrate that the precise control of the polyketone chain length can significantly alter hydrogen-bonded self-assembly in the solid state and in solution even with the same terminal structures.

链霉菌次级代谢产物化学成分研究

研究链霉菌Streptomyces peucetius NA07292的次级代谢产物。采用Sephadex LH-20凝胶柱色谱、正相硅胶柱、反相硅胶柱、高效液相制备色谱等手段进行分离纯化,根据质谱、一维和二维波谱数据、理化性质等确定化学成分。分离到1个化合物,鉴定为4-O-(β′-D-glucopyranuronosyl)-ε-rho-domycinone(1),诸多同类吸收的化合物待分离。显示,化合物1是芳香族聚酮类化合物,这一类化合物被证明具有多种生物活性,但目前尚未有报道研究过相关活性,因此值得深入研究。

冰片二烯的合成研究

以α-蒎烯为原料合成2,6-二氯莰烷,再以2,6-二氯莰烷为原料合成冰片二烯。α-蒎烯合成2,6-二氯莰烷反应,当α-蒎烯和NaHCO3的物质的量之比为1∶1时,控制温度-10℃,反应7 h后,2,6-二氯莰烷的得率最高。2,6-二氯莰烷合成冰片二烯的工艺条件为,以叔丁醇钾为消除反应试剂,2,6-二氯莰烷与叔丁醇钾的物质的量之比为1∶4,二甲基甲酰胺(DMF)为溶剂、反应温度120℃、反应时间3 h。采用FT-IR、GC-MS和1H NMR等方法对2,6-二氯莰烷和冰片二烯进行了结构鉴定。

一氧化碳与苯乙烯溶液聚合反应研究

邻氯苯酚作溶剂 ,乙酸钯 /对甲苯磺酸铜和 2 ,2′,-联吡啶组成的催化体系催化苯乙烯和一氧化碳的溶液共聚反应 ,合成出特种高分子材料聚酮——聚 (1-氧代 - 2 -苯基丙撑 ) .研究了铜盐种类、对甲苯磺酸铜用量、甲醇用量、溶剂用量、苯乙烯量及强酸种类等对该共聚反应的催化活性的影响 .结果表明 ,溶液聚合的产物聚酮为一氧化碳与苯乙烯的交替共聚物 ,溶液聚合反应的催化活性高于沉淀聚合 。

钯-铜-稀土催化一氧化碳和苯乙烯交替共聚反应

利用乙酸钯、乙酸钕和对甲苯磺酸铜组成的催化体系催化一氧化碳和苯乙烯共聚,合成聚1-氧代-2-苯基丙撑(STCO)．用红外光谱、元素分析和X射线光电子能谱对共聚物进行表征．结果表明,产物为一氧化碳和苯乙烯的交替共聚物．同时研究了催化体系的配比、2,2’-联吡啶和对甲苯磺酸铜的用量以及不同的稀土盐和单体对体系催化活性的影响．此外,对催化剂的复配进行了对比实验．实验结果表明,以钯为主催化剂,并加入适量稀土盐与对甲苯磺酸铜,同时优化催化体系各组分的配比,可以有效地提高催化活性,降低STCO的成本．

红曲霉菌的研究进展

该文重点阐述了3个问题红曲固态培养技术液态培养技术及利用基因工程技术改造红曲霉菌种提高功能性红曲中莫纳可林K及降低红曲产品中桔霉素含量提出了应在红曲行业引入GMP和HACCP的管理体系并就红曲米工厂的现状提出了一些建议

聚丙烯腈树脂负载催化剂在聚酮合成中的应用

采用丙烯腈与二乙烯基苯交联合成聚丙烯腈树脂微球,考察了聚合工艺条件对微球的粒径、硬度等的影响。以负载有乙酸钯的聚丙烯腈树脂微球组成的催化体系催化一氧化碳和苯乙烯共聚合成聚酮(STCO)。研究了催化体系中的2,2’-联吡啶和对苯醌用量及反应时间对共聚反应的影响。利用红外光谱(IR)和扫描电镜(SEM)对树脂负载催化剂及聚合产物进行了表征。结果表明,树脂负载催化剂对聚酮合成反应具有较好的催化性能:当树脂用量为1g,乙酸钯为22.4mg时,聚酮产量达6.2384g。另外树脂在重复使用5次后仍具有一定的催化活性。

一氧化碳和苯乙烯交替共聚物的合成与表征

利用乙酸钯和２，２′－联吡啶组成的催化剂体系催化一氧化碳和苯乙烯交替共聚合成出聚（１－氧代－２－苯基丙撑）（ＳＴＣＯ）。采用ＩＲ、ＮＭＲ、元素分析以及广角Ｘ光散射对该聚合物以表征。该共聚物晶体为单斜晶胞，晶胞参数为ａ＝１５．７×１０－１０ｍ，ｂ＝６．１７×１０－１０ｍ，ｃ＝７．４５×１０－１０ｍ，α＝９０．０°，β＝１０４．３°，γ＝９０．０°；晶胞体积为６９７．２×１０－３０ｍ３；空间点群为Ｐ２１／ｃ。此外，对该共聚物热降解进行了初步研究。