Apparent Kinetics of 1-Decene Polymerization Catalyzed Using the Ionic Liquid[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]

Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.

STUDY ON 1-HEXENE POLYMERIZATION BASED ON ZIEGLER-NATTA CATALYSTS WITH DOPED SUPPORT

A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.

原子转移自由基聚合修饰植物乳杆菌及其对黄曲霉毒素B_(1)吸附脱除作用

为了研究植物乳杆菌材料对黄曲霉毒素去除新方法,为黄曲霉毒素B_(1)的高效生物去除提供了新思路。本文采用基于聚多巴胺的原子转移自由基聚合方法(Polydopamine-based Atom Transfer Radical Polymerization,p-ATRP)和细胞自催化的无铜添加原子转移自由基聚合方法(Cell-catalyzed Copper-free Atom Transfer Radical Polymerization,c-ATRP)对植物乳杆菌活细胞表面进行修饰,引导原子转移自由基聚合(Atom Transfer Radical Polymerization,ATRP)体系自组装聚合反应形成聚合物材料,对修饰后的植物乳杆菌进行表征,并比较修饰前后植物乳杆菌对黄曲霉毒素B_(1)吸附脱附能力。结果表明,未修饰的植物乳杆菌,细胞表面圆润光滑,经过p-ATRP修饰后的植物乳杆菌,细胞表面变得极为粗糙,经过c-ATRP修饰后的植物乳杆菌,细胞表面出现褶皱;未修饰的植物乳杆菌的Zeta点位为-8.43 mV,经过Dopamine和PNIPAAm修饰后的植物乳杆菌点位分别为1.791和13.767 mV;植物乳杆菌在0.1~100μg/mL黄曲霉毒素B_(1)吸附率为75.3%,p-ATRP和c-ATRP修饰的植物乳杆菌比未修饰的植物乳杆菌吸附能力分别提高了7.8%和6.4%。在相同黄曲霉毒素B_(1)浓度下,植物乳杆菌脱附率为6.1%,p-ATRP和c-ATRP修饰的植物乳杆菌脱附能力分别提高了14.4%和42%。经过修饰后的植物乳杆菌显著提升了植物乳杆菌对黄曲霉毒素的吸附和脱附能力。

铁矿物协同Shewanella oneidensis MR-1介导的钒(V(Ⅴ))还原及其作用机制

矿物协同微生物可以将高毒性的V(Ⅴ)还原为毒性及流动性较低的V(Ⅳ),从而达到治理钒污染的目的.以希瓦氏菌Shewanella oneidensis MR-1为试验菌株,采用黄铁矿、菱铁矿、马基诺矿3种铁矿物作为受试矿物,考察铁矿物协同微生物对V(Ⅴ)的还原特性,探讨影响V(Ⅴ)还原的因素,并研究马基诺矿协同S.oneidensis MR-1还原V(Ⅴ)对胞内酶活性、胞外聚合物(EPS)及电子传递的影响,解析铁矿物协同微生物介导的V(Ⅴ)还原机制.结果表明,3种铁矿物均能促进S.oneidensis MR-1对V(Ⅴ)的还原,其中马基诺矿的效果最佳,V(Ⅴ)还原率由对照组的80.84%提高到95.54%.马基诺矿协同S.oneidensis MR-1还原V(Ⅴ)的还原率与初始V(Ⅴ)浓度及pH值成反比,与矿物添加量及接菌量成正比.添加马基诺矿后,胞内的硝酸盐还原酶(NAR)、亚硝酸盐还原酶(NIR)、还原型烟酰胺腺嘌呤二核苷酸(NADH)及ATP水平均有不同程度的提高,EPS中蛋白质、多糖和核酸的含量增加,电子传递能力增强,从而促进V(Ⅴ)生物还原.扫描电镜-能量散射X射线谱(SEM-EDS)和X射线光电子能谱(XPS)显示,马基诺矿促进S.oneidensis MR-1将V(Ⅴ)还原为不溶性V(Ⅳ),形成沉淀聚集在菌体周围.

OBD-1(黑色)可逆热致变色微胶囊制备及其在防伪领域的应用

当今社会,假冒伪劣产品泛滥,给社会经济带来严重的负面影响。旨在研发一种灵敏度高、温变区间小、耐酸耐碱的OBD-1(黑色)可逆热致变色微胶囊,并将其应用在温变防伪涂料。选取黑色发色剂OBD-1、双酚A、十六醇为芯材料,脲醛树脂为壁材料,通过原位聚合法制备微胶囊。利用显微镜观察微胶囊的外部形貌,通过激光粒径测定仪对微胶囊粒径及粒径分布范围进行了测定,考察了微胶囊制备时的不同的制备条件对微胶囊粒径大小和样品性能的影响,并得到最佳制备比例。

STUDY ON THE MECHANISM OF 1-OCTENE ZIEGLER-NATTA POLYMERIZATION BASED ON THE NUMBER OF ACTIVE CENTERS

The number of active centers (C_p)-t and k_p-t profiles of Solvay type TiCl_3 - AlR_3 (R=C_2H_5, i-C_4H_9) or Stauffer AA TiCl_3-Al (C_2H_5)_3 catalyzed 1-octene polymerization were determined by using an acetyl chloride quenching method as well as kinetic data. The results show that in the studied systems k_p decreases when C_p increases, indicating the presence of two or more types of different active centers. The C_(p^(-t)) plots of the Solvay TiCl_3-AlR_3 systems show the presence of both stable active centers and unstable centers which decay in the polymerization process. The phenomena are explained based on a model of active center plurality. The increases of C_p in the induction periods are also discussed.

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,^(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ^(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.

CATIONIC POLYMERIZATION OF 1,3—PENTADIENE INITIATED BY ORGANIC AZIDE/Et_2AlCl

The cationic polymerization of 1, 3-pentadiene was initiated by the organic azide/Et_2 AlClinitiating system in CH_2Cl_2 and n-hexane. The polymerizations were also carried out in parallelwith organic chloride/Et_2AlCl and Et_2 AlCl alone for comparison. The Et_2 AlCl- induced polymer-ization gives a low yield while the polymerization initiated by organic chloride/Et_2 AlCl producesmainly insoluble product. In contrast, the polymerization with azide/Et,AlCl has a high conver-sion and the resulting polymer having a high molecular weight is totally soluble. The SEC spectraof the polymers have clearly shown the differences between these initiating systems.

STUDY ON POLYMERIZATION MECHANISM OF 3, 9,-DIALLYL-3, 9, -DIBENZYL-1, 5, 7, 11-TETRAOXASPIRO [5, 5] UNDECANE

A new monomer, 3,9-diallyl-3, 9-dibenzyl-1, 5,7,11 - tetraoxa- spiro [5,5] undecane (6) was prepared by the reaction of 2- allyl- 2' - benzyl- propanediol - 1.3 with dibutyltin oxide, and then treated with CS_2. Monomer 4 could be initiated by cationic initiators to give a viscous polymer (white powder in the case of polymerization at 0℃). Upon the NMR and IR spectra of the obtained polymer, the components and their relative amount were estimated. The polymerization mechanism was discussed.

SINGLE LANTHANUM TRIS(N-PHENYLETHYL-3,5-DI-t-BUTYLSALICYLALDIMINATO)S INITIATOR FOR RING-OPENING POLYMERIZATION OF 1,4-DIOXAN-2-ONE IN BULK

A rare earth Schiff base complex:lanthanum tris(N-phenylethyl-3,5-di-t-butylsalicylaldiminato)s [La(OPEBS)_3] was successfully applied as single component initiator for the ring-opening polymerization of 1,4-dioxan-2-one (PDO) in bulk.The influence of reaction conditions,such as polymerization temperature,the molar ratio of the monomer to initiator (M/I) on the monomer conversion and molecular weight of the polymer has been investigated.Poly(1,4-dioxan-2-one) with a viscosity-average molecular weight (My) o...

VINYL POLYMERIZATION OF NORBORNENE CATALYZED BY [2-(2-BENZIMIDAZOLYL)-6-((1-ARYLIMINOETHYL)PYRIDYL)]NICKEL CHLORIDE/MAO SYSTEM

The catalytic system of[2-(2-benzimidazolyl)-6-((1-aryliminoethyl)pyridyl)]nickel chloride/MAO(methylalu- minoxane)was found to be good active for vinyl polymerization of norbornene and provided polymers with relative narrow molecular distributions.Various reaction parameters,such as the ratios of nickel precursor to MAO or monomer norbornene, and the nature of the ligands in complexes were carefully investigated to realize their effects on the catalytic activities, polymer molecular weight and molecular we...

SYNTHESIS AND CATIONIC RING-OPENING POLYMERIZATION OF 1, 4-ANHYDRO-2, 3-DI-O-(P-AZIDOBENZYL)-α-D-RIBOPYRANOSE

New highly stereoregular 2, 3 -di- O-(p-azidobenzyl )-(1 →5 ) - α-D -ribofuranan was synthesized byselective ring-opening polymerization of 1, 4-anhydro-2, 3 - di-O -(p-azidobenzyl )-α-D -ribopyranose(ADABR) using phosphorus pentafluoride or tin tetrachloride as catalyst at low temperature indichloromethane. The monomer was obtained by the reaction of p - bromomethyl -phenyleneazide with 1, 4 -anhydro-α-D-ribose in DMF. The structure of poly(ADANR) was identified by specific rotation and ^(13)C-NMR spectroscopy. Acid chloride-AgCl_4 complex catalyst such as CH_2=C(CH_3)C^+OClO_4^- used in thepolymerization resulted in polymers with mixed structures, i.e. (1→5)-α-D-ribofuranosidic and (1→4)-β-D-ribopyranosidic units. However, with C_6H_5C^+OClO_4^- as catalyst, pure (1→5)-α-D-ribofuranan was obtained.The effects of catalyst, polymerization temperature and time on polymer stereoregularity were examined, andthe mechanism of the ring-opening polymerization was discussed.

STUDY ON THE CATIONIC POLYMERIZATION OF 1, 3-PENTADIENE INITIATED BY AlCl_3/ALKYL HALIDE SYSTEMS

The cationic polymerizations of 1, 3-pentadiene were initiated by AlCl_3 in n-hexaneat 30℃ in the presence of alkyl halides, i.e., tert-butyl chloride, tert-butyl bromide andisobutyl chloride. The effects of these halides on the polymer yield, molecular weight,crosslinking reaction, cyclization and polymer microstructure, have been investigated. Twomain side reactions, crosslinking and cyclization, were suppressed and reduced by theaddition of the halides. The proportion of 1, 4 units of polymer chains was increasedby the presence of the halides, which reduced the polymer yield and the molecular weightof polymers.

3-甲基-1-戊烯-4-炔-3-醇合成工艺的改进

以液氨和金属钙为原料通过氨基化制得氨基钙,经炔化得到乙炔钙,乙炔钙再与甲基乙烯酮反应制得乙炔醇钙盐,经水解、挥发氨、水蒸气蒸馏、萃取、回收溶剂、粗馏、精馏制得3-甲基-1-戊烯-4-炔-3-醇。考察金属试剂、催化剂硝酸高铁投入量、阻聚剂和萃取剂对合成及产物的影响。结果表明,选用金属钙作为金属试剂,催化剂硝酸高铁投入量为金属钙质量的0.8%,改性复合阻聚剂和CH2Cl2萃取剂较为合适。该工艺合成路线得到的3-甲基-1-戊烯-4-炔-3-醇纯度达98%以上,物质的量收率71.0%。

浅谈单气1区块优快钻井液技术

单气1区块位于济阳坳陷滨县凸起,由于地层造浆严重,浅层定向过程中常常发生阻卡事故,严重滞缓钻井进程。在优选聚合醇润滑防塌钻井液体系的基础上,现场针对不同井段采用相应的钻井液处理技术,确保单气1-斜1井和单气1-斜5井顺利完钻,井身质量好,机械钻速快,达到了优质高效钻井的目的。

Synthesis and optical properties of an alternating copolymer composed of MEHPV and 1,3,4-oxadiazole

A poly （ p-phenylenevinylene ） （ PPV ） alternating copolymer, poly [ （ 2, 5-diphenylene-1, 3, 4-oxadiazole ）-4-4＇ - vinylene-alt-2-methoxy-5-（ 2-ethylhexyloxy ）-1, 4-phenylenevinylene] （oxa-MEHPV）, is synthesized by Heck coupling reaction and characterized with UV-vis, Fourier transform infrared （ FT-IR ）, ^1H-NMR and photoluminescence （ PL ） spectroscopy, oxa-MEHPV possesses an outstanding thermal stability and shows excellent solubility in common organic solvents such as dichloromethane, chloroform, toluene, and tetrahydrofuran（THF）. The introduction of the electron-deficient 1, 3, 4-oxadiazole units into the MEH-PPV backbone also increases the electron affinities of the conjugated segment, which leads to the blue-shift of the maximum absorption wavelength and makes the polymer have a high optical band-gap energy, good electron-transporting stability and high PL quantum yield.

Synthesis,crystal structure and adsorption properties of a novel Fe(Ⅲ) porous coordination polymer containing 1,4-naphthalenedicarboxylate ligand

A novel porous coordination polymer,iron naphthalenedicarboxylate Fe（OH）（1,4-NDC）·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid（1,4-H2NDC） at 150℃.The compound crystallizes in a tetragonal space group P42/nmc：a=2.1447（4） nm,c=0.68849（14） nm,V=3.1669（11） nm3,Z=8,R=0.0845,wR=0.1829.The crystal structure exhibits a three-dimensional framework which is composed of infinite chains of corner-sharing octahedral Fe（OH）2O4 with 1,4-NDC ligands forming two types of channels with square-shaped cross-sections.The large channels present a cross-section of 0.76 nm×0.76 nm,while the small channels are about 0.30 nm×0.30 nm.No structural transformation occurs after removing the guest water molecules,while a robust structure generates with permanent porosity.The adsorption measurements show that the anhydrous sample of the compound can adsorb CO2 into its pores.The adsorption isotherms for methanol,acetone,tetrahydrofuran and benzene are also measured.

利用分子标记辅助选择聚合水稻抗病基因Pigm-1和Xa23

【目的】创制抗稻瘟病和白叶枯病水稻新材料。【方法】以携带抗稻瘟病基因Pigm-1的双抗77009和抗白叶枯病基因Xa23的IRBB23为父本,以象牙香占为母本,利用杂交和复交方法,借助于分子标记辅助选择技术,在分离世代对目标基因进行检测,结合田间多代选育和抗性鉴定,选育多抗、综合性状优良的5个稳定株系,分析其农艺性状;然后利用三系不育系靓香A分别与象牙香占及5个稳定株系进行杂交配组,对杂交组合的农艺性状和品质性状进行分析,并对5个稳定株系进行恢复基因检测。【结果】获得R21-1、R21-2、R21-3、R21-4和R21-5 5个均含有Xa23和Pigm-1双基因稳定聚合系,这5个改良系对稻瘟病和白叶枯病均具有较好的抗性。不育系靓香A与5个稳定株系的杂交组合中,只有组合靓香A/R21-1表现结实正常,而其余组合均表现半不育;与亲本R21-1相比,组合靓香A/R21-1的有效穗数、每穗颖花数均表现优异亲本R21-1的特性,整精米率表现显著提高,米质可以达到二级部颁优质米标准。【结论】创制了5个稳定的Xa23和Pigm-1双基因聚合系,其中改良系R21-1含有恢复基因Rf3,可用于水稻多基因聚合育种。

Experiment and Modeling of Pure and Binary Adsorption of n-Butane and Butene-1 on ZSM-5 Zeolites with Different Si/Al Ratios

Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.

A New Luminescent Cd(Ⅱ) Coordination Polymer Constructed by Mixed 1,4-Naphthalenedicarboxylate and N-donor Chelating Ligand

In this work, we synthesized a new two-dimensional Cd（Ⅱ） coordination polymer, [Cd（1,4-NDC）（L）]（1）, by using mixed 1,4-naphthalenedicarboxylic acid（1,4-H2NDC） and typical chelating N-donor ligands 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-f][1,10]phenanthroline ligand（L）. Compound 1 crystallizes in monoclinic, space group P21/n with a = 12.936（5）, b = 15.245（5）, c = 13.499（5） ？, β = 105.456（5）o, V = 2565.9（16） A^3, Z = 4, C（31）H（16）CdClFN4O4, Mr = 675.33, Dc = 1.748 g/cm^3, F（000） = 1344, μ（MoKa） = 1.011 mm^-1, R = 0.0350 and wR = 0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd（Ⅱ） atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N–H···O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.