尼龙66与甲基丙烯酸甲酯接枝共聚合的研究——DMA/硫酸铜引发体系

烯类单体与聚酰胺(尼龙)纤维接枝共聚合已有报道.Varma等人研究了Ce4+引发丙烯腈、丙烯酰胺分别与尼龙纤维的接枝共聚反应。Lenka发表了用P2O48-引发甲基丙烯酸甲酯(MMA)与尼龙6纤维接枝共聚合的研究结果.Nayak等人报道了用乙酰丙酮锰为引发剂使MMA与尼龙6接枝共聚合.本文以二甲基苯胺(DMA)/硫酸铜为引发体系,用MMA接枝尼龙66纤维丝,研究了Cu2+浓度等因素对该接枝共聚反应的影响.     

亚麻等麻类纤维与乙烯基类单体接枝共聚反应的研究进展

近年来,乙烯基类单体与亚麻、大麻、苧麻等麻类纤维的接枝共聚反应已得到关注。本文着重总结接枝的引发方法,包括:1.辐射引发接枝;2.光引发接枝;3.Ce(Ⅳ)离子引发接枝;4.锰盐引发接枝;5.V(Ⅴ)离子引发接枝;6.Fenton's 试剂(Fe~(2+)-H_2O_2)引发接枝;7.过硫酸盐氧化还原引发体系接枝。上述各类引发体系及接枝纤维的结构与性能表征均在本文中作了述评。     

纤维素与苯乙烯-丙烯腈共聚用单体的接枝共聚

研究了以高锰酸钾为引发剂,苯乙烯-丙烯腈共聚用单体与纤维素的接枝共聚。讨论了影响接枝共聚反应的一些参数,反应规律和接枝共聚物的结构及性质。实验表明,在以水为介质的反应体系中,接枝共聚反应可顺利进行。     

Mn^3＋引发淀粉与丙烯腈接枝共聚物的研究

用过渡金属离子或其配合物引发淀粉的接枝共聚是一个饶有兴趣的课题。Ce~(4 )离子引发淀粉与烯类单体的接枝共聚已有广泛报道。Mehrotra等用稳定的[Mn(H_2P_2O_7)_3]~(3-)引发淀粉与烯类单体的接枝共聚取得了满意的结果。本文报道用电镜,x-射线衍射和热重分析等方法对这一接枝共聚物的形态、结构和热稳定性的研究结果。     

罗布麻纤维与丙烯酸酯类接枝共聚物结构和性能的研究

本文以氧化还原体系引发丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸丁酯(BA)与罗布麻纤维的接枝共聚反应,用IR、SEM和X-射线衍射等手段表征了接枝纤维的结构。与纯罗布麻纤维相比较,接枝纤维具有较高的断裂伸长率和较低的杨氏模量,柔顺性增加;耐酸、碱能力随接枝率的增加而提高,但吸湿率不降。     

铬酸引发丙烯酸正丁酯与淀粉接枝共聚反应

作为淀粉改性方法之一 ,不饱和酸及其酯与淀粉接枝共聚反应是一个较新的研究领域 ,其中以 Ce4 +离子作为引发剂的较多[1,2 ] ,也有用Mn3+-H2 SO4 体系 [3]和 Mn[( H2 P2 O7) 3]3-引发体系的[4 ] 。铬酸是一种具有强氧化性的强酸 ,虽然它单独存在时并不引发乙烯类单体的聚合 ,有报道[5] 铬酸可以引发丙烯腈与苎麻纤维素接枝共聚 ,淀粉和纤维素同属于碳水化合物。本文对铬酸引发丙烯酸正丁酯与淀粉接枝共聚反应进行了研究 ,考察了反应条件对接枝反应的影响。1　实验部分1 .1　原料可溶性淀粉 (北京奥特生物技术责任有限公司 ) ,丙烯酸正丁…     

[Mn(H_2P_2O_7)_3]~(3-)引发淀粉与丙烯腈接枝聚合反应的动力学研究

以[Mn(H_2P_2O_7)_3]~(3-)为引发剂,研究了丙烯腈与玉米淀粉的接枝共聚反应。由实验结果求出了反应速率与引发剂浓度、单体浓度、淀粉浓度和反应温度的关系,推导并验证了接枝反应动力学模型,探讨了反应机理,求得了接枝反应活化能。     

含羧基和吡啶基两性离子交换纤维的制备研究

采用γ射线预辐照PP纤维引发 4VP和AA(或AANa)或 4VP和MAA(或MAANa)接枝共聚 ,制得不同接枝率和不同链段结构的弱酸弱碱两性离子交换纤维。采用 4VP/AANa共接枝时 ,在不同单体投料比范围内获得高于 4 2 0 %的总接枝率。研究了纤维的预辐照剂量、单体浓度、摩尔盐含量、交联剂含量以及接枝温度和时间等条件对接枝共聚反应的影响。适宜的接枝共聚反应条件为 :预辐照剂量为 8× 10 4Gy ,单体浓度 10 % ,摩尔盐加入量约 0 .0 5 % ,交联剂用量 2 % ,接枝温度 65℃ ,时间 4h。发现两性纤维呈现双螺旋结构形态。对比自制的弱酸、弱碱离子交换纤维 ,所制备的两性纤维对酸性、中性、碱性氨基酸的吸附量比较大 ,对不同氨基酸具有不同的吸附分离能力     

PEB/MMA-AN悬浮接枝共聚反应机理

研究了乙烯-1-丁烯共聚物(PEB)弹性体与甲基丙烯酸甲酯(MMA)-丙烯腈(AN)悬浮接枝共聚反应行为及接枝共聚产物对SAN树脂增韧作用随反应时间的变化规律, 用凝胶渗透色谱法和傅里叶变换红外光谱法对接枝共聚产物进行了表征, 分析了接枝共聚反应机理, 推算了接枝链分子量. 结果表明, 体系首先发生链增长自由基向PEB转移终止形成非接枝共聚物(MAN_L)和PEB大分子自由基引发单体共聚形成接枝链(g-MAN)的反应, 接枝反应结束后体系发生明显的非接枝共聚形成非接枝共聚物(MAN_H)的反应; MAN_L的分子量低于g-MAN的分子量, 而g-MAN的分子量明显低于MAN_H的分子量; 在接枝共聚过程中发生已接枝和未接枝PEB断链并随机再接生成多嵌段共聚物的副反应; 在反应初期, 接枝链的AN单元含量接近于非接枝共聚物的AN单元含量, 在反应中后期前者远低于后者.     

甘蔗髓与丙烯腈的接枝共聚

本文研究了以Fe~(2+)—H_2O_2为引发剂引发甘蔗髓与丙烯腈的接枝共聚反应。研究了亚铁含量,H_2O_2浓度,单体量,反应液比、温度和时间对接枝反应的影响;探讨了接枝共聚物碱水解条件,如碱浓度和用量、水解温度和时间、接枝增量等因素对水解产物吸水性能的影响。结果表明,在一定的条件下可获得较高接枝增量的接枝共聚物,降低反应液比或增加单体量均可明显提高接枝增量,接枝增量对水解产物吸水性能的影响不大。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

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.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

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.