Zn对Pt/SAPO-11催化剂物化及异构性能影响

通过浸渍法制备了Pt/SAPO-11催化剂, 分步浸渍法制备了Zn-Pt/SAPO-11双金属催化剂. 通过X射线衍射、低温氮物理吸附、氨程序升温脱附和吡啶吸附红外等手段对所得样品进行了表征. 实验结果表明, 助剂Zn的引入导致了催化剂的比表面积和孔容降低, B酸量减少而L酸量增加, 总酸量有所增加. 在300～380 ℃范围内对正庚烷的临氢异构化反应考察发现, 引入金属助剂Zn可以明显改变正庚烷的转化率, 而对C₇异构体的选择性影响不明显. 当Zn质量分数为0.2%, Pt质量分数为0.2%时, Zn-Pt/SAPO-11催化剂的正庚烷转化率及C₇异构体收率达到最大值; Zn含量继续增加时, 正庚烷转化率及C₇异构体收率均随之下降. 实验结果表明, 双功能催化剂中金属功能与酸性功能的匹配对正庚烷临氢异构化反应非常重要.     

聚乙烯塑料在连续超临界水反应器中的油化研究

在连续超临界水（SCW）反应器中考察了反应温度、停留时间和反应压力对聚乙烯（PE）降解油化的影响。实验结果表明,在120s、25MPa下,从500℃提高到550℃,液体收率呈现先升后降的趋势,在530℃达到最大值（79%）;在520℃、25MPa下,随停留时间的延长,PE裂解程度加深,产物轻质化程度提高,导致液体收率降低,停留240s时,气体收率达到43%;反应压力对产物收率的影响较小,气、液产物中烯/烷比随反应压力的增加而增大。     

喷气燃料中抗氧剂2,6-二叔丁基对甲酚的高效液相分析

 采用高效液相法分析喷气燃料HDF 1中的抗氧化剂 2 ,6 二叔丁基对甲酚 (简称BHT)含量 ,研究了二元混合流动相中甲醇 乙酸缓冲液的比例对燃料主体和BHT分离效果的影响 ,选择了最佳分离条件 (甲醇所占体积分数为 85 % ,流速为 1mL/min) ,在此条件下 ,可测出质量分数为 1× 10 -5的BHT。用该喷气燃料配制了BHT质量分数在 2 0× 10 -6到 12 0× 10 -6之间的标准溶液 ,考察了BHT质量分数与峰面积之间的关系 ,结果表明线性关系良好。     

碱性条件下废轮胎真空热裂解研究

研究了废轮胎橡胶粉在450℃～600℃真空热解系统中热解的特性,以及温度和添加Na2CO3、NaOH对热解气液态产物的影响。实验表明,真空下废轮胎热解油收率在550℃时达到最大值,为48%左右。添加3%的NaOH能明显促进废轮胎橡胶热解,480 ℃时油产率达到最大值49.66%,随后随着温度的升高油产率呈现下降趋势。添加3%的Na2CO3对热解的促进作用不明显。热解气体产物主要有H2、CO、CH4、CO2、C2H4、C2H6以及少量其他化合物。NaOH的加入使气体产品中的H2相对体积分数明显增加,而CH4、CO、C2等的体积分数降低。通过GC和GC-MS分析热解石脑油发现,热解油品中含有11%以上的柠檬油精。     

聚醋酸乙烯酯和共聚物大分子引发剂引发异丁烯正离子接枝共聚合反应

以AIBN为引发剂,通过自由基聚合方法先合成一定分子量(Mn=1.9×104g mol)和分子量分布(MWD,Mw Mn<2.5)的聚醋酸乙烯酯(PVAc)和醋酸乙烯酯(VAc)与醋酸异丙烯酯(IPAc)的无规共聚物聚(PVIPA).再以PVAc或PVIPA作为大分子引发剂,与共引发剂TiCl4配合,引发异丁烯进行正离子接枝共聚反应,并分别考察大分子引发剂用量、TiCl4浓度以及添加剂2,6二叔丁基吡啶(DtBP)或2甲基吡啶(MPY)对异丁烯聚合转化率和PVIPA或PVAc引发效率的影响,并进一步表征接枝共聚物的微观结构与组成含量.实验结果表明,PVIPA和PVAc可引发异丁烯进行正离子接枝共聚反应,前者的引发效率高于后者.加入适量DtBP或MPY时,可不同程度地提高引发效率.DtBP对减少聚合体系中微量水的引发和提高PVAc引发效率的作用更为明显,引发效率可达90%以上,加入适量添加剂MPY时,PVIPA引发效率可达60%左右.适当增加大分子引发剂用量和TiCl4浓度,也可提高PVIPA的引发效率至接近70%.在合适的实验条件下,可以得到极性主链为PVIPA与非极性支链为聚异丁烯(35.2%mol)的接枝共聚物PVIPA g PIB,该接枝共聚物的Mn为3.7×104g mol,分布指数MWD为2.52,且PIB支链平均分子量约为5.4×103g mol.     

自由基引发剂强化稠油催化水热裂解降黏行为

本文考察了自由基引发剂对胜利油田单56区块稠油样品催化水热裂解反应过程的协同强化作用.在反应温度为220℃,添加0.2 wt%的引发剂——过氧化二叔丁基,使水热裂解后的降黏率由不加引发剂时的61.4%升高到72.7%.此外,在引发剂存在、150℃条件下,降黏率可达到69.0%,表明引发剂的加入可显著提高较低反应温度下的水热裂解效果.对反应前后油样进一步分析发现,反应样品中饱和分、芳香分、胶质和沥青质平均分子量均下降;饱和分、芳香分含量增加,而胶质、沥青质含量下降;胶质、沥青质中氢碳原子比增加,含硫量减少,含氮量变化不大;表明重质组分在水热裂解过程中发生了裂解反应、尤其是含硫官能团在水热裂解中发生了反应;反应样品沥青质及胶质芳香环系的缩合程度降低.实验结果表明,反应过程中稠油重质组分发生了裂解,而且胶质的裂解程度更大,轻质组分含量增加,导致稠油黏度降低、流动性提高,在一定程度上改善了稠油的品质;引发剂可以在较低温度下产生自由基,从而使水热裂解反应在较低反应温度下有效进行.     

衍生化法合成高纯度顺式对叔丁基环己醇

由对叔丁基苯酚催化加氢合成顺/反对叔丁基环己醇的混合物。用适量的叔丁基二甲基氯硅烷(TB-DMSCl)衍生化反应,得顺式对叔丁基环己醇的纯度可达99.5%以上。加氢反应条件实验表明,当浓盐酸加量为0.25 g、异丙醇为溶剂和温度70～80℃时反应效果最佳。根据衍生化数据对顺/反对叔丁基环己醇分离的反应机理进行了推测。     

裂解气相色谱-质谱法研究聚醚酰亚胺的热裂解行为

采用裂解气相色谱-质谱技术研究了聚醚酰亚胺(PEI)在550℃、650℃和750℃裂解温度下的热分解行为.随着裂解温度上升,裂解产物明显增加.在750℃时聚合物分子链断裂完全,共鉴别到25种碎片组分.PEI热分解的碎片中叔丁基苯酚、叔丁基甲基苯酚、苯酚、苯胺、氰苯、2-苯基-1H-异吲哚-1,3(2H)-二酮等5种裂解产物最重要,因此可以依据这几种化合物定性鉴别聚醚酰亚胺.依据热分解产物的数量以及结构推断降解机理为:裂解首先从醚键开始,其次是酰胺基团中的C-N键,然后再经过一系列消除反应、成环反应、重排反应等形成多种裂解碎片.     

含氧光敏引发体系的研究——V.硫醇添加剂的作用

采用二笨甲酮/三乙胺/硫醇体系作为引发剂,在含氧条件下进行了MMA光聚合反应的动力学研究。实验结果指出,芳香族和脂肪族的硫醇都能加速体系中的光氧化反应,使聚合反应诱导期缩短,芳香族硫醇对聚合反应的加速作(?)比脂肪族硫醇有效。例如,对-甲苯硫酚作添加剂时,使相对量子收率φO_2/φN_2增加到1.8。     

Ni对Pt/SAPO-11催化剂物化及异构性能影响

通过浸渍法制备了Pt/SAPO-11催化剂,分步浸渍法制备了Ni-Pt/SAPO-11双金属催化剂。通过X射线衍射、低温氮物理吸附、氨程序升温脱附和吡啶吸附红外等手段对所得样品进行了表征。结果表明,助剂Ni的引入导致了催化剂的比表面积和孔容降低,同时,催化剂的B酸量、L酸量及总酸量均有所下降。在340℃时对正庚烷的临氢异构化反应中,当Pt含量0.2wt%时,Pt/SAPO-11催化剂的正庚烷转化率为45%,C7异构体收率为43%;而当Pt含量0.2wt%,同时Ni含量为0.2wt%时,Ni-Pt/SAPO-11催化剂的正庚烷转化率提高至72%,C7异构体收率提高至60%。     

The rôle of chain ends in the thermal degradation of anionic polystyrene

Direct evidence is given of the initiating rôle played in the thermal degradation of anionic polystyrene by chain ends, either present originally or formed during the degradation. In the early stages of degradation, the most likely bond scission in polystyrenes with benzylic type units (CH₂(C₆H₅)) at both chain ends involves the formation of toluene and an unsaturated terminal unit (CH₂C(C₆H₅)CH₂). The depolymerisation of polystyrene to a mixture of monomer and dimeric, trimeric, etc., fragments is then initiated by further scission at such unsaturated chain ends, giving α-methyl styrene and a depolymerising macroradical.After the early stage of degradation, a further overwhelming contribution to the formation of unsaturated chain ends is derived from chain transfer which occurs during depolymerisation. The concentration of unsaturated chain ends increases throughout the degradation process, thus accelerating the formation of the volatile products of depolymerisation. According to this mechanism of initiation, a constant ratio is found between rates of weight loss and of α-methyl styrene evolution throughout the degradation, independently of the original molecular weight of the polymer.     

Radiation crosslinking of polymethylhydrogensiloxane containing methoxy groups

The bulk viscosity of polymethylhydrogensiloxane containing methoxy groups (PMHS-A) was measured before and after irradiation. The gel point was then determined from the variation of viscosity by irradiation by comparing it with methoxy-free polymethylhydrogensiloxane (PMHS-B) and polydimethylsiloxane blocked by methoxyldimethylsilyl (PDMS-C) or trimethylsilyl (PDMS-D). The following results were obtained: (1) The G value of crosslinking by irradiation is 167, 52, 25, and 3 for PMHS-A, PMHS-B, PDMS-C, and PDMS-D, respectively. (2) The scission of the SiO? CH₃ bond is easier than that of the Si? H, Si? CH₃, or SiCH₂? H bond. The SiO? CH₃ bond is PMHS-A is severed from SiO· and ·CH₃ to induce chain reactions at the initial stage by irradiation. (3) It was confirmed that the commercial PMHS is at present free of methoxy groups. To replace the hydrogen of Si? H in the commercial PMHS with methoxy groups heat treatment with methanol was performed by which the G value of crosslinking was increased.     

Main chain scission reaction of poly(methyl methacrylate) caused by two-photon ionization of dopant

The main chain scission reaction of poly(methyl methacrylate) (PMMA) doped with N,N,N,′,N′-tetramethyl-p-phenylenediamine (TMPD) was examined by ESR spectroscopy and GPC measurement, and the scission mechanism was analyzed. The two-photon ionization of TMPD with excimer laser excitation at 77 K produced an ester radical anion of PMMA (PMMA·m?), which becomes the main chain tertiary radical ? CH₂? C˙(CH₃)? CH₂? after the detachment of the ester side group by annealing of the sample at room temperature. The main chain scission radical ˙C(CH₃)(COOCH₃)? (PMMA˙) which was produced by the β-scission from? CH₂? ˙C(CH₃)? CH₂? showed the 13-line ESR spectrum instead of the ordinary 9-line, due to the fast quenching of the sample to 77 K. The change of the molecular weight distribution was measured by GPC after several irradiation-and-annealing operations. The simulation of the GPC curve confirmed that the scission re-action occurs at random in the PMMA chain in the solid and the main chain scission yield from the ester radical anion, [PMMA˙]/[PMMA·m?], is 0.30. © 1995 John Wiley & Sons, Inc.     

正癸烷与二甲苯在超临界压力下的热裂解

采用连续流动装置对正癸烷和二甲苯在超临界压力下的热裂解对比研究. 用气相色谱和色质联用仪对其气相产物和液相产物进行分析, 计算气相产物产率和裂解转化率, 并运用计算化学方法获得正癸烷和二甲苯不同化学键的键能, 从实验和理论上分析其裂解反应的难易程度和裂解规律. 实验结果表明, 在4 MPa和650、700、750 ℃条件下, 正癸烷比二甲苯更容易裂解, 正癸烷裂解产物以C₁-C₃小分子的烃类和氢气为主, 而二甲苯裂解产物主要为乙苯、甲苯和其它芳香类化合物; 键能计算结果表明, 正癸烷碳链骨架的C－C键能和C－H键能均较小, 裂解反应的诱发步骤应该是C－C键断裂, 而二甲苯苯环上C－C和C－H键能均较大, 裂解诱发步骤应该是侧链甲基脱氢反应. 因此正癸烷裂解反应以C－C键断裂和脱氢反应为主, 二甲苯裂解主要发生侧链甲基C－C键断裂和脱氢反应, 而芳环则比较稳定, 理论计算键能分析与裂解实验结果一致.     

Pyrolysis mass spectrometry and gas chromatography of plasma-polymerized benzene and xylene

Pyrolysis mass spectra and gas chromatograms of plasma-polymerized benzene (PPB) and p-xylene (PPX) have been studied. Both polymers gave mass spectra that indicated the presence of disubstitution in an aromatic ring and of product molecules, such as biphenyl and ethylbenzene, trapped in the polymer matrix. The PPB spectrum showed fragments originating from ? C₆H_{4? n} structures and the PPX spectrum fragments originated from ? CH₂C₆H₄CH_{2? n} structures. Both the pyrolysis mass spectrum and chromatogram contained peaks that distinguished PPX from commercial polystyrene samples. A chain mechanism which involves H abstraction reactions under plasma activation is proposed. The highly crosslinked structures of the polymers are attributed to the subsequent addition of free radicals to the double bonds of a fragmented chain formed as a result of the scission of the C? C aromatic bond(s).     

N,N-Bis[ethoxy(methyl)silylmethyl]methylamines MeN[CH2SiMem(OEt)3-m]2 (m = 0-2). Synthesis and Reactions with Phenol

Previously unknown N,N-bis[ethoxy(methyl)silylmethyl]amines MeN[CH₂SiMe_m(OEt)_3-m ]2 (m = 0-2) were synthesized. According to UV spectral data, only MeN[CH₂SiMe₂(OEt)]₂ form hydrogen bond with phenol in a heptane solution. The amines with m = 0 and 1 fail to forms hydrogen bond with phenol [under the same conditions, N-(triethoxysilylmethyl)dimethylamine Me₂NCH₂Si(OEt)₃ forms a strong hydrogen bond with phenol]. All the amines (m = 0-2) enter transetherification with phenol to give compounds of the general formula MeN[CH₂SiMe_m m(OPh) _n (OEt)3-m-n]₂ (m = 0-2, n = 1-3). Refluxing of N,N-bis[ethoxy(methyl) silylmethyl]amines with excess phenol results in cleavage of the Si-C bond by phenol, providing phenoxysilanes Me_mmSi(OPh)4-m (m = 0-2) and trimethylamine.     

Cationic β-Scission of C−H and C−C Bonds for Selective Dimerization and Subsequent Sulfur-Free RAFT Polymerization of α-Methylstyrene and Isobutylene

A series of exo-olefin compounds ((CH₃)₂C(PhY)−CH₂C(=CH₂)PhY) were prepared by selective cationic dimerization of α-methylstyrene (αMS) derivatives (CH₂=C(CH₃)PhY) with p-toluenesulfonic acid (TsOH) via β-C−H scission. They were subsequently used as reversible chain transfer agents for sulfur-free cationic RAFT polymerization of αMS via β-C−C scission in the presence of Lewis acid catalysts such as SnCl₄. In particular, exo-olefin compounds with electron-donating substituents, such as a 4-MeO group (Y) on the aromatic ring, worked as efficient cationic RAFT agents for αMS to produce poly(αMS) with controlled molecular weights and exo-olefin terminals. Other exo-olefin compounds (R−CH₂C(=CH₂)(4-MeOPh)) with various R groups were prepared by different methods to examine the effects of R groups on the cationic RAFT polymerization. A sulfur-free cationic RAFT polymerization also proceeded for isobutylene (IB) with the exo-olefin αMS dimer ((CH₃)₂C(Ph)−CH₂C(=CH₂)Ph). Furthermore, telechelic poly(IB) with exo-olefins at both terminals was obtained with a bifunctional RAFT agent containing two exo-olefins. Finally, block copolymers of αMS and methyl methacrylate (MMA) were prepared via mechanistic transformation from cationic to radical RAFT polymerization using exo-olefin terminals containing 4-MeOPh groups as common sulfur-free RAFT groups for both cationic and radical polymerizations.     

Very low-pressure pyrolysis. VII. The decomposition of methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine,and tetramethylhydrazine. Concerted deamination and dehydrogenation of methylhydrazine

The rate constants (k_uni) for the first-order disappearance of the title molecules have been determined under VLPP conditions. The k_uni are not the rate constants of ultimate interest since they reflect the fact that energy transfer competes with the chemical decomposition. Use of the Rice-Ramsperger-Kassel-(Marcus) [RRK(M)] theory allows the determination of the high-pressure rate constants (k_α), if the mode of decomposition is known. The heats of formation of the radicals NH₂, CH₃NH, and (CH₃)₂N are known. These values should be usable for prediction of the activation energy for N? N bond homolysis in the hydrazines. Measured rate constants for UDMH and TMH bear this out, but the rate constant for MMH does not. This and other evidence lead to the conclusion that MMH decomposes via molecular concerted elimination of NH₃ and H₂ not and by N? N bond scission. The following values are preferred from this work (θ = 2.303RT in kcal/mole). Mode of decomposition is N—N bond scission unless noted otherwise in parenthesis: .     

Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO,and the product distribution of the F + CH3CHO reaction

Using a pulse-radiolysis transient UV–VIS absorption system, rate constants for the reactions of F atoms with CH₃CHO (1) and CH₃CO radicals with O₂ (2) and NO (3) at 295 K and 1000 mbar total pressure of SF₆ was determined to be k₁=(1.4±0.2)×10⁻¹⁰, k₂=(4.4±0.7)×10⁻¹², and k₃=(2.4±0.7)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹. By monitoring the formation of CH₃C(O)O₂ radicals (λ>250nm) and NO₂ (λ=400.5nm) following radiolysis of SF₆/CH₃CHO/O₂ and SF₆/CH₃CHO/O₂/NO mixtures, respectively, it was deduced that reaction of F atoms with CH₃CHO gives (65±9)% CH₃CO and (35±9)% HC(O)CH₂ radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH₂O radicals via C C bond scission occurs at a rate of <4.7×10⁵ s⁻¹. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 913–921, 1998     

Tautomerism of monochalcogenosilanoic acids CH3Si(O)XH (X = S,Se, Te) in the gas phase and in the polar and aprotic solution: An ab initio computational investigation

Computational investigations by an ab initio molecular orbital method (HF and MP2) with the 6‐311+G(d,p) and 6‐311++G(2df, 2pd) basis sets on the tautomerism of three monochalcogenosilanoic acids CH₃Si(?O)XH (X = S, Se, and Te) in the gas phase and a polar and aprotic solution tetrahydrofuran (THF) was undertaken. Calculated results show that the silanol forms CH₃Si(?X)OH are much more stable than the silanone forms CH₃Si(?O)XH in the gas‐phase, which is different from the monochalcogenocarboxylic acids, where the keto forms CH₃C(?O)XH are dominant. This situation may be attributed to the fact that the Si? O and O? H single bonds in the silanol forms are stronger than the Si? X and X? H single bonds in the silanone forms, respectively, even though the Si?X (X = S, Se, and Te) double bonds are much weaker than the Si?O double bond. These results indicate that the stability of the monochalcogenosilanoic acid tautomers is not determined by the double bond energies, contrary to the earlier explanation based on the incorrect assumption that the Si?S double bond is stronger than the S?O double bond for the tautomeric equilibrium of RSi(?O)SH (R?H, F, Cl, CH₃, OH, NH₂) to shift towards the thione forms [RSi(?S)OH]. The binding with CH₃OCH₃ enhances the preference of the silanol form in the tautomeric equilibrium, and meanwhile significantly lowers the tautomeric barriers by more than 34 kJ/mol in THF solution. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008