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二烯丙基二甲基氯化铵—丙烯酰胺反相乳液聚合的动力学特征研究 总被引:17,自引:1,他引:17
采用油酸失水山梨醇酯(SPAN)-壬基酚聚氧化乙烯醚(OP)复合乳化剂与K2S2O8-Na2SO3氧化还原引发剂,进行二烯丙基二甲基氯化铵-丙烯酰胺反相乳液共聚合,测得单体的竞聚率为γDADMAC=0.14±0.11,γAM=5.05±0.66;在单体浓度为25─45%,引发剂浓度0.06—0.1%,乳化剂浓度为5—9%,聚合温度303K条件下,得到了共聚反应动力学方程:Rp=k[M]0.68[I]1.31[E]0.73,文中对上述结果做了解释. 相似文献
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氯乙烯/N-苯基马来酰亚胺悬浮共聚合速率的研究 总被引:3,自引:0,他引:3
考察了单体配比、温度、引发剂浓度诸因素对氯乙烯(VC)/N-苯基马来酰亚胺(PMI)悬浮共聚速率的影响.VC/PMI共聚有显著的交叉终止,致使共聚速率降低,测得交叉终止速率常数的函数=5.77,PMI均聚综合速率常数的倒数值δ2=53.65,共聚表观活化能Ea=127.9kJ/mol,增长活化能Ep=63.7kJ/mol,聚合速率对引发剂浓度的反应级数为0.786.并对VC/N-环己基马来酰亚胺(CHMI)和VC/PMI两个体系进行了比较 相似文献
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氯乙烯/N—苯基马来酰亚胺悬浮共聚合速率的研究 总被引:4,自引:3,他引:1
考察了单体配比、温度、引发剂浓度诸因素对氯乙烯(VC)/N-苯基马来酰亚胺(PMI)悬浮共聚速率的影响,VC/PMI共聚有显著的交叉终止,致命共聚速率降低,测得交叉终止速率常数的函数φ=5.77,PMI均聚综合速率常数的倒数值δ2=53.65,共聚表观活化能Ea=127.9kJ/mol,增长活化能EP=63.7kJ/mol,聚合速率对引发剂浓度的反应级数0.786,并对VC/N=环己基马来酰亚胺( 相似文献
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在亚乙基双( 茚基) 二胺化茂铪(rac C2H4(Ind)2Hf(NMe2)2 ,简称1 ,Ind = 茚基,Me= 甲基) 催化作用下,对乙烯(E) 与1 辛烯(O) 无规共聚合进行了研究.作为比较,利用异亚丙基( 环戊二烯基)(1 芴基) 二甲基锆茂催化体系((CH3)2C(Fluo)(Cp)ZrMe2 ,简称2 ,Fluo = 芴基,Cp = 环戊二烯基) 对乙烯/1 辛烯在相同共聚合条件下进行了共聚合.结果表明,在单体浓度比[O]/[E] 较小时共聚合速率随单体浓度比增加而增加,进一步增加单体浓度比则导致共聚合速率降低.催化体系1/Al(iBu)2H/[Ph3C][B(C6F5)4](3) 催化共聚活性比2/ MAO高得多.共聚物中辛烯含量随反应单体1 辛烯含量的增加而增加,两单体竞聚率乘积( rE×ro) 小于1 ,表明聚合物为无规共聚物.相同共聚单体浓度比下1/Al(iBu)2H/3 催化共聚物中辛烯含量比2/ MAO 共聚物中辛烯含量高,表明前者具有更强的共聚合能力.所得无规共聚物熔点温度、结晶度、本体粘度及密度随共聚物中辛烯含量的增加而显著降低.辛烯含量较高时共聚物呈现明显无结晶行为.差示扫描量热分析显示,同乙烯均聚? 相似文献
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用双官能团引发剂进行的基团转移嵌段共聚研究 总被引:2,自引:1,他引:2
本文用二种双官能团引发剂进行基团转移嵌段共聚研究,得到了一系列实测分子量和理论分子量相近、分子量分布较窄的A-B-A型嵌段共聚物。用GPC、~1H-NMR、DSC等手段对嵌段共聚物进行了表征,证明确是两相嵌段共聚丙烯酸酯。发现位阻较大的单体作为第二单体时不利于聚合。过高的催化剂用量使嵌段共聚的总转化率降低。使用极性较大的溶剂可缩短第一步聚合的诱导期,但不影响第二步聚合的诱导期,即极性较大的溶剂有利于催化剂的离解。单体浓度增大使共聚物的分子量减小,多分散性指数增大。可通过单体投料比改变共聚物的热形变温度。 相似文献
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单茂钛催化剂的丙烯无规聚合反应及其动力学研究 总被引:4,自引:1,他引:4
比较了不同钛化合物/甲基铝氧烷(MAO)催化体系的丙烯无规聚合,催化活性次序为CpTi(OR)3>CpTi(OPh)3>CpTiCl3>Cp2TiCl2>Ti(OBu)4>TiCl4>Ti(OBu)2Cl2,所得聚丙烯用沸庚烷抽提8h,溶解95%以上,可溶部分经13C NMR、WADX、FTIR等分析证明为无规聚丙烯(aPP),是没有结晶性的弹性体.GPC测出其分子量Mw=8.0~10.0×104,Mw/Mn≈2.0.探索了催化体系CpTi(O n Pr)3/MAO中钛的浓度、[Al]/[Ti]摩尔比,丙烯聚合压力,聚合温度和时间对丙烯聚合反应的影响.研究了该催化体系丙烯聚合反应动力学规律,表观聚合反应速率对催化剂浓度和单体压力(浓度)都呈一级反应关系,表观聚合速率常数KP=292×105mol/L·h(40℃).活化能ΔE=-7.88×103J·mol-1,碰撞因子A=1.41×10-4mol/L·h. 相似文献
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单茂钛催化剂用于苯乙烯-乙烯嵌段共聚物的合成与表征 总被引:1,自引:0,他引:1
乙烯(E)与苯乙烯(S)的嵌段共聚合用自制的两种催化剂———茂基三呋喃甲氧基钛[CpTi(OCH2O)3]和茂基三苄氧基钛[CpTi(OCH2Ph)3]进行了研究.考察了促进剂三甲基铝(TMA)及乙烯的预聚合时间对聚合结果的影响,发现不同的催化体系有不同的[TMA]最佳值以及随着乙烯预聚合时间的延长总的催化效率降低.对嵌段共聚合产物用丁酮、四氢呋喃和氯仿连续萃取分离,得到四氢呋喃中的可溶级分即嵌段共聚物PE b sPS,它占总嵌段共聚合产物的40wt%~60wt%.对嵌段共聚物用DSC、WAXD、FTIR和13C NMR等方法进行了表征. 相似文献
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2-亚甲基-丁二酯酐和甲基丙烯酸甲酯在四氢呋喃中以过氧化二苯甲酰作引发剂进行自由基共聚合。由作图法求得这两种单体在66℃的共聚竞聚率:r1=4.22,r2=0.64,表明它们趋于嵌均共聚。用粘度法和GPC测量了共聚物的分子量和分子量分布。 相似文献
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以五甲基茂基三苄氧基钛[Cp* Ti(OBz)3] 和甲基铝氧烷( MAO) 组成的催化体用本体法合成出苯乙烯 乙烯共聚物Poly(S co E) .考察了共聚温度,共聚时间,Al/Ti 摩尔比,主催化剂浓度[Ti] 等条件对共聚反应的影响.共聚产物经沸丁酮,沸四氢呋喃(THF) 连续抽提分离,发现共聚物主要存在于THF 可溶级分中.可溶级分经DSC,13C NMR,WAXD,DMA 等手段分析,证明苯乙烯 乙烯共聚物为具有单一玻璃化转变温度( Tg) 无熔融温度的无规共聚物,显示弹性体的粘弹性行为. 相似文献
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用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%. 相似文献
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Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields. 相似文献
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Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments. 相似文献
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The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula. 相似文献
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Rebecca J. Burton Mandy L. CrowtherNeal J. Fazakerley Shaun M. FilleryBarry M. Hayter Jason G. KettleCaroline A. McMillan Paula PerkinsPeter Robins Peter M. SmithEmma J. Williams Gail L. Wrigley 《Tetrahedron letters》2013
The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines. 相似文献
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KMnO4-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields. 相似文献
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N. A. Nedolya 《Chemistry of Heterocyclic Compounds》2008,44(10):1165-1219
The review contains a concise historical account and information on the most significant researches undertaken by the staff
at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry
of Heterocyclic Compounds.
Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008. 相似文献
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Regiospecific and direct imidation of the methyl C(sp3)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products. 相似文献
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A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL. 相似文献
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A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions. 相似文献