Preparation of phosphorus-modified PITQ-13 catalysts and their performance in 1-butene catalytic cracking

A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their catalytic performance in 1-butene catalytic cracking was evaluated in a fixed fluidized bed reactor. The results showed that the crystallinity, surface area and pore volume of P-modified PITQ-13 catalysts decreased with the increasing amounts of P. The number of weak acid sites increased, whereas that of strong acidity decreased. The selectivity to propylene in 1-butene cracking reactions increased because of the decrease in strong acidity. The yield of propylene achieved 41.6% over PITQ-13-2 catalyst with a P content of 1.0 wt%, which was 5.1% greater than that achieved over HITQ-13 catalyst.

1-Butene isomerization and metathesis over Mo/mordenite-alumina: Factors influencing product distribution and induction period

Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.

Production of propene from 1-butene metathesis reaction on tungsten based heterogeneous catalysts

A new propene production route from 1-butene metathesis has been developed on heterogeneous 10WO3/Al2O3-HY catalysts with different HY contents. It is found that the catalysts play bi-functionally first for the isomerization of 1-butene to 2-butene and then for the cross-metathesis between 1-butene and 2-butene to propene and 2-pentene. The combination of HY zeolite and Al2O3 is prerequisite for the production of propene. The propene yield keeps increasing with the HY content in the range of 10-70 wt%, where 10WO3/Al2O3-70HY exhibits the highest propene yield. The MS-H2-TPR and MS-O2-TPO characterizations indicate that the increase of HY content in the catalysts weakens the interaction between W species and supports, whereas enhance the probability of coking on the metal species and acid sites.

MCM-36 zeolites tailored with acidic ionic liquid to regulate adsorption properties of isobutane and 1-butene

Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.

1-丁烯/丙烯共聚物的合成及结晶行为

使用最新开发的负载型Ziegler-Natta催化剂合成1-丁烯/丙烯共聚物,催化剂活性可达9 kg/(g·h)以上。采用13C NMR,IR,XRD,DSC等方法对所得共聚物的组成、链结构和结晶行为进行表征。实验结果表明,1-丁烯/丙烯共聚物中连续排列的丙烯单元结构含量少,IR谱图和XRD谱图中未出现聚丙烯晶体对应的特征峰,表明丙烯很好地参与了共聚反应;^(13)C NMR谱图分析计算结果表明,共聚物中丙烯含量为3.3%~18.9%(x)。在实验条件范围内,共聚单体丙烯的引入可加速共聚物由晶型Ⅱ向晶型Ⅰ转变,当丙烯含量不低于7.8%(x)时,晶型Ⅱ在48 h内基本转变为晶型Ⅰ(占比不低于96.2%);当丙烯含量不低于12.6%(x)时,晶型Ⅱ在24 h内基本转变为晶型Ⅰ(占比不低于96.1%)。

The influence of different monodentate P-ligand mixtures on Rh-catalyzed 1-butene hydroformylation

Four monodentate P-ligands and their mixtures（six groups of double-ligand systems,four groups of triple-ligand systems and one group of tetra-ligand system）were used with Rh（acac）（CO）2（acac=acetylacetonate）or Rh（acac）CO（PPh3）as the catalyst in the hydroformylation reaction of 1-butene.It was found that different Rh catalysts showed little difference in the catalysis performance.The general order of catalysis performance is doubleligand system 〉 single-ligand system〉triple-ligand system 〉 tetra-ligand system.Some synergistic effect in the double-ligand system was detected which needs a further investigation.

Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22 zeolite

The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid （i.e., IL） with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22 （i.e., MCM-22-IL） was characterized by FT1R, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to l-butene （I/O） were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene （I/O） was significantly im- proved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length oflLs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.

Strong influences of polymerization temperature on ethylene/1-hexene copolymerization catalyzed by (2-PhInd)_2ZrCl_2/methyl aluminoxane

Ethylene/1-hexene was copolymerized by an unbridged zirconocene, (2-PhInd)2ZrCl2/MAO (methyl aluminoxane) at 0 °C and 50 °C respectively. High copolymerization activity and 1-hexene incorporation were observed at 0 °C, with the co- polymer formed having random sequence distribution and narrow molecular weight distribution. Ethylene polymerization at 50 °C showed high activity, but copolymerization at 50 °C showed much lower activity, which decreased sharply with increasing 1-hexene concentration in the monomer feed. Copolymer formed at 50 °C showed blocky sequence distribution and broad mo- lecular weight distribution. A mechanism model based on ligand rotation hindered by the propagation chain has been proposed to qualitatively explain the observed phenomena.

COPOLYMERIZATION OF 1-OCTENE WITH STYRENE BY RARE EARTH COORDINATION CATALYSTS

The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10^(-3) L^2/mol^2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR.

COPOLYMERIZATION OF ETHYLENE WITH 1-OCTENE USING Et(Ind)_2ZrCl_2/MAO CATALYST

Copolymerization of ethylene/1-octene was carried out in toluene withvarious concentrations of comonomer in the feed using Et(Ind)_2ZrCl_2/MAO (methyl alu-minoxane) as catalyst. It was found that with the increase of 1-octene concentration in thefeed the content of 1-octene in the copolymer increases, while the density, melting point,crystallinity and intrinsic viscosity of copolymer decrease. A copolymer with very lowdensity, containing 11.5 mol% of 1-octene (VLLDPE) can be produced with this catalystsystem. The effect of temperature and zirconium aluminum mole ratio of the catalyst onthe copolymerization was also investigated. The results of ^(13)C NMR determination of thecopolymer showed that the 1-octene units in the copolymer are principally isolated.

Application of Et_3NHCl-AlCl_3 Ionic Liquid as an Initiator in Cationic Copolymerization of 1, 3-Pentadiene with Styrene

The random copolymer poly （1, 3-pentadiene-co-styrene） formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride （Et3NHCl-AlCl3） room temperature ionic liquid as initiating agent in toluene was analyzed using IR spectra in conjunction with gel permeation chromatography （GPC）. The room temperature ionic liquid was found to have high initiatic activity for copolymerization.

乙烯与1-己烯共聚合及其共聚物研究

在1 L聚合釜中进行乙烯与1-己烯共聚合,研究了乙烯与1-己烯共聚合的动力学、竞聚率及所制共聚物的结构与性能,并模拟了串联和并联工艺。结果表明:1-己烯的共聚合能力较好,且具有较好的氢调敏感性,共聚合过程平稳,共聚物颗粒形态较好;乙烯-1-己烯共聚物与参比试样物性基本相当,熔融焓、结晶焓和1-己烯含量略高。

ROLE AND IMPORTANCE OF RADIUS OF GYRATION OF CHAINS IN THE MELT IN THE CRYSTALIZATION OF POLY(1-BUTENE)

Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystalline layered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared to the crystal thickness (d(c)), the volume occupied by the chain in the melts i.e., the radius of gyration (R-g), plays a very important role in polymer crystallization. When d(c) less than or equal to R-g, crystallization does not necessitate a chain disentangling. The entanglements are just shifted into the amorphous regions. However, as d(c)>R-g, i.e., as the crystal thickness gets larger than the radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change of crystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(I-butene). A change in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystallization temperatures increase. Even more, such a change is molecular weight dependent, and shifts to lower temperature as molecular weight decreases. There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A change of crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization has been discussed based on the radius of gyration of chain in the melt (R-g), and very good agreement is obtained.

丙烯/1-丁烯共聚合的工业化实践

一般的无规共聚聚丙烯通过共单体的引入破坏聚丙烯分子链的规整性,降低球晶尺寸实现聚合物的透明化,同时提高产品抗冲击性能。然而,当选用乙烯为共单体时,较低的刚性以及较高含量的正己烷抽提物使其无法满足卫生要求较高的食品和医疗用品领域。当选用1-丁烯作为共聚单体时,可有效克服乙烯作为共聚单体时的不足。通过对聚丙烯装置进行技术改造以及生产工艺控制和优化,开发出丙烯/1-丁烯共聚技术及其聚丙烯新产品,应用于食品包装、医疗卫生等领域。

Crystallization and Crystalline Structure of Syndiotactic Polypropylene and Syndiotactic-Poly(1-Butene) Blend

The crystallization and crystalline structure of syndiotactic-polypropylene (sPP) and syndiotactic-poly(1-butene) (sPB) blend containing 10 (Bl-10), 25 (Bl-25), 50 (Bl-50), 75 (Bl-75), and 90 (Bl-90) wt% of sPB, have been investigated by means of differential scanning calorimetry (DSC), FT-IR, and wide-angle X-ray diffraction (WAXD) analyses. The melt-crystallization behavior of the blend samples was studied by DSC on the cooling process at constant rates. Bl-50, Bl-75, and Bl-90 showed lower crystallization temperatures than the neat sPP. sPP in Bl-75 showed the lowest crystallization rate among the blend samples. Bl-90 showed a two-phase molten state, and sPP in Bl-90 crystallized via two-stepprocess. Time evolution of FT-IR spectroscopy at room temperature detected conformational transformation of the sPP polymer chain in the blend samples of Bl-50 and Bl-75. The absorption peaks intensity in the FT-IR spectra derived from the helical conformations in the crystalline phase decreased, and the planar zigzag conformations in the amorphous and mesophase phases decreased over the crystallization time. The time evolution of the WAXD profile of Bl-90 indicated that sPP in the blend accelerated the crystallization of sPB. The crystallized Bl-10, Bl-25, and Bl-50 samples showed diffraction peaks in WAXD profiles and melting endothermic peak in DSC profiles derived from only the sPP crystal. The crystallinity and melting temperature of sPP in the crystallized Bl-10, Bl-25, and Bl-50 samples were almost independent of the sPB content. Both the crystalline structure of sPP and sPB were detected in Bl-75 and Bl-90. Bl-75 showed the lowest crystallinity and melting temperature of sPP among the blend samples.

Copolymer 1保护高眼压大鼠视神经的免疫学机制

目的探讨Copolymer 1(Cop 1)对实验性高眼压性青光眼视神经保护作用的相关免疫学机制。方法对27只大鼠采用烧灼巩膜上静脉制作双眼高眼压模型,在眼压升高的第3周,取12只模型大鼠于后脚皮内注射100μg Cop 1和等体积的完全弗氏佐剂(CFA)混合乳化液(实验组);另取12只模型大鼠作为对照组,后脚皮内注射等体积PBS和CFA的混合乳化液;其余3只模型大鼠作为空白对照组,不做任何处理。1周后取出大鼠脾淋巴细胞,采用流式细胞仪检测T细胞亚群的变化;ELISA法检测T细胞分泌细胞因子的变化;[3H]thymidine标记检测淋巴细胞的增殖。结果实验组大鼠的CD4+CD25+Treg/CD4+比值显著高于对照组和空白对照组(P<0.05)。实验组IL-10分泌量和分泌浓度均显著高于对照组和空白对照组,差异有统计学意义(P<0.05),但三组间INF-γ分泌量和分泌浓度比较差异均无统计学差异(P>0.05)。三组间体外刺激淋巴细胞指数比较差异无统计学意义(P>0.05)。结论 Cop 1能诱导CD4+CD25-向CD4+CD25+Treg转化,促进Th1转化为Th2,并增加IL-10的分泌。

Copolymer1保护视神经的作用及作用机制

Copolymer1(Cop1)是美国FDA批准的一种用于治疗多发性硬化的多聚肽类药物。许多实验用Cop1免疫动物,发现Cop1对钳伤和高眼压造成的视神经损伤有保护作用。我们对Cop1作用的免疫学机制的研究进展进行综述。

HELIX SENSE-SELECTIVE COPOLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE WITH CHIRAL ANIONIC INITIATORS

Optically active copolymers of pairs of three monomers, triphenyl (methyl methacrylate)and one or two pyridyl substituted methyl methacrylate homologues, were obtained by helix-sense-selective copolymerization using complexes of organolithium with chiral ligand as anionicinitiators in toluene at low temperature. The copolymers obtained with (-)-sparteine (Sp) and(S,S)-(+)-and (R, R)-(-)-2, 3-dimethoxy-1, 4-bis (dimethylamino) butanes((+)-and (-)-DDB) complexes of organolithium showed low optical activity, but PMP complex with N, N-diphenylethyleneamine monolithium amide (PMP-DPEDA-Li) was effective in synthesizingcopolymers of high optical rotation ([α]_D^(25) about+320～1370°)which were comparable to thoseof relative homopolymers with one-handed helical structure.

Syntheses of Cellulose-Type Polysaccharide by Means of Ring-Opening Copolymerization of Anhydroriboses ABRP and AIRP

Two kinds of 1,4-anhydroribose derivatives,1,4-anhydro-2,3-O-benzylidene-T-D-ribopyranose(ABRP)and 1,4-anhydro-2,3-O-isopropylidene-T-D-ribopyranose(AIRP)were prepared fromD-ribose.The ringopening copolymerizations of ABRP and AIRP in various feed ratios were carried out with SbCl_5 and BF_3OEt_2 as catalyst at low temperatures.The copolymer structure was characterized by means of ^(1)H,^(13)C NMR spectroscopy and specific rotation.When SbCl_(5)was used as catalyst,the copolymer obtained had completely 1,4-β-pyranosidic structure,i.e.,cellulosetype structure.However,when BF_(3)OEt_2 was used as catalyst,the copolymer had a mixed structure of furanosidic and pyranosidic units.

ESTIMATION OF REACTIVITY RATIOS OF METHYL ACRYLATE WITH N-ARYLMETHACRYL-AMIDE COPOLYMERS BY ~1H NMR METHOD

The copolymerizations of methyl acrylate （MA） with different N- arylmethacrylamide （N-ArMA） were carried out in benzene solution by free radical initiation. The compositions of the copolymers were deter mined by;H NMR method. The monomer reactivity ratios were calculated by the Fineman-Ross （F-R） method. The reactivity ratios and the activity of various N-ArMA with MA were investigated.