疏水基改性聚丙烯酰胺的合成及溶液性质

利用自由基胶束聚合法,由丙烯酰胺和甲基丙烯酸十八酯共聚合成了疏水缔合型水溶性聚合物.通过红外光谱表征了共聚物的结构,考察了共聚物浓度、盐浓度、剪切速率以及温度对共聚物溶液性能的影响.试验结果表明,聚合物质量分数大于临界缔合浓度(2%)时,溶液的粘度急剧增大;疏水缔合聚合物溶液的表观粘度随着溶液中NaCl质量分数的增加而增大.     

疏水缔合型丙烯酰胺类聚合物Ⅰ.疏水单体N-苯基甲酰胺-丙烯酰胺的合成与表征

通过异氰酸苯酯和丙烯酰胺(AM)的取代反应,制备了疏水缔合型单体N-苯基甲酰胺-丙烯酰胺(HMAM)。用红外光谱、核磁共振氢谱、质谱、元素分析和差示扫描量热仪对HMAM进行表征。结果表明,HMAM单体含有疏水和亲水基团,可用于制备新型水溶性疏水缔合型聚合物,该聚合物不溶于水和丙酮等强极性溶剂,但能溶于二甲亚砜和N,N-二甲基甲酰胺等中等极性的溶剂中。     

水溶性疏水缔合聚合物-膨润土纳米复合材料的研究

以有机改性膨润土、2-丙烯酰胺-2-甲基丙磺酸（AMPS）、 N,N-二甲基丙烯酰胺（DMAA）和季铵盐单体D-C₁₆Br为原料，通过原位聚合制备了一种新型水溶性疏水缔合聚合物-膨润土纳米复合材料。利用红外光谱、X-射线衍射仪对产物结构进行表征，并通过与纯共聚物AMPS/DMAA/D-C₁₆Br相比，研究了纳米黏土材料的引入对共聚物性能的影响。结果表明：在膨润土促进聚合物分子形成疏水缔合结构的作用下，具有复合插层结构的复合材料在热稳定性、耐温性、抗剪切性和黏弹性方面均优于纯聚合物，表明该纳米复合材料较纯共聚物具有良好的应用前景。     

含辣素衍生结构疏水缔合聚合物PAAH的合成、表征及溶液性质

以辣素功能结构单体N-（4-羟基-3-甲氧基-苄基）-丙烯酰胺（HMBA）为疏水单体,与丙烯酰胺（AM）和2-丙烯酰胺基-2-甲基丙磺酸钠（NaAMPS）通过自由基胶束共聚,制得三元疏水缔合聚合物P（AM-NaAMPS-HMBA）（简称PAAH）. 采用紫外-可见光谱、核磁共振氢谱、热重分析及扫描电子显微镜对共聚物的结构及形貌进行表征,利用原子力显微镜对聚合物水溶液的微观形貌进行观察,并对其溶解性、疏水缔合性、耐温性及抑菌性能进行了研究. 结果表明,所得共聚物中疏水单体含量与投料比基本一致;PAAH具有良好的速溶性,当聚合物浓度超过一定值后,溶液黏度急剧增加,且随着疏水单体含量增加,疏水缔合性能增强;原子力显微镜观察证实了聚合物水溶液中网络结构的存在. 与未改性的P（AM-NaAMPS）（简称PAA）共聚物相比,引入具有生物活性且带有刚性苯环结构的HMBA单体可使PAAH共聚物热稳定性增强,耐温性能提高,并赋予其优良的抑菌性能.     

一种核-壳缔合聚合物的高效驱油特性研究

油田产出水直接配注聚合物是聚合物驱的发展趋势和必然,基于提升聚合物在产出水中的综合驱油性能的多级结构和超分子效应的思路,以聚酰胺-胺改性并功能化的纳米二氧化硅为核,甲基-N,N-二辛基丙烯酰胺为疏水单体制备水溶性核-壳形缔合聚合物SHPAM;IR、~1H NMR、SEM和TEM表征SHPAM的结构。SHPAM的核-壳结构及疏水基团的缔合效应协同增强高矿化度产出水配制聚合物溶液的增黏性、抗剪切性及长期稳定性能,SHPAM的零剪切黏度是梳形聚合物(KYPAM)的60倍。SHPAM比KYPAM少500 mg·L~(-1),SHPAM有更强的流度控制性能,对岩心渗透率有良好的兼容性;水驱至含水率98%,0.30 PV的SHPAM驱(浓度1500 mg·L~(-1))提高原油采收率达25%。结果表明产出水配注SHPAM表现高效的驱油效率。     

功能高分子材料综合实验设计:荧光稀土液晶高分子防伪膜的制备

设计了一个综合性实验,将荧光稀土液晶高分子防伪膜的制备和现代分析测试技术应用于高分子专业的教学实验中,以提高学生的综合实践能力。实验包括荧光稀土液晶高分子的制备、表征、防伪性能评价3大部分。采用FTIR、荧光光谱仪、POM、XRD、TG表征荧光稀土液晶高分子的结构与性能;制备荧光稀土液晶高分子防伪膜对其防伪性能进行评价,给整个实验增添趣味性与实用性。通过开设该实验,可让学生了解功能高分子的前沿知识及现代分析测试技术的基本原理和用途,掌握专业的实验操作与数据处理方法,提高学生的综合实践能力和专业素质。学生实验证明该综合实验适用于本科实验教学。     

疏水缔合聚丙烯酰胺与双子表面活性剂的相互作用

制备了一种脂肪酸酯双磺酸盐型双子表面活性剂, 利用粘度法、界面张力法和原子力显微镜研究了疏水缔合聚丙烯酰胺与双子表面活性剂在溶液中的相互作用. 实验结果表明: 疏水缔合聚丙烯酰胺在溶液中能够通过自组装形成疏水微区并发展成网络结构, 疏水微区与表面活性剂在溶液中能形成混合胶束; 当一定量的表面活性剂加入时, 对疏水缔合聚丙烯酰胺的自组装起促进作用, 而过多双子表面活性剂的加入又会对聚合物分子的自组装起抑制作用, 从而显著影响疏水缔合聚丙烯酰胺的溶液性质, 随着表面活性剂浓度的增加, 聚合物溶液粘度先增加、再降低; 同时, 疏水缔合聚丙烯酰胺对双子表面活性剂的界面性能也有较大影响, 聚合物的加入使双子表面活性剂降低油/水界面张力的能力下降, 油/水界面张力达到平衡所需时间延长.     

功能聚合物表面的制备及其化学修饰

介绍了一个综合化学实验--功能聚合物表面的制备和化学修饰,及其教学思路。通过相分离法制备功能聚合物表面,探究不同溶剂组分对聚合物表面功能的影响,同时通过点击化学的方法对亲水表面进行修饰制备疏水表面,用静滴法测量表面接触角大小,并借助扫描电子显微镜对修饰前后的功能聚合物进行表征。结果显示,随着溶剂配方中1-癸醇的减少和环己醇的增加,亲水表面的接触角增大,疏水表面接触角减小,修饰过后的亲水表面表现出良好的疏水性能。该综合实验整合了大学化学基础知识、化学学术前沿以及实验基本技能,有利于培养学生的创新思维,提高综合能力。     

疏水缔合聚合物在石英砂表面的吸附——疏水基含量和微嵌段长度对吸附的影响

研究了不同分子结构的疏水缔合聚合物和部分水解聚丙烯酰胺在45、55和65 ℃下的静态吸附特征。 实验结果表明,疏水缔合聚合物的疏水基含量和微嵌段长度可以改变聚合物在石英砂表面的最大吸附量,而其中疏水基含量是主要影响因素,等温吸附曲线出现2个平台区。 随着温度的升高, 部分水解聚丙烯酰胺吸附量增大,而缔合聚合物则表现出相反的规律;缔合聚合物通过改变疏水基含量和微嵌段长度来影响其吸附性能。     

电化学沉积制备聚苯胺纳米阵列及性能研究的综合化学实验

为将导电聚合物超级电容器电极材料引入到本科教学实验中，设计了综合探究性高分子材料制备实验——电化学沉积制备聚苯胺纳米阵列及性能研究。首先采用电化学法构筑导电高分子聚苯胺纳米阵列；然后运用紫外光谱、拉曼光谱、扫描电子显微镜和电化学工作站等，分别对聚苯胺阵列的化学结构、形貌和电化学性能进行表征。从材料的合成角度来看，该实验可以使学生了解和掌握电化学合成导电聚合物的机理与方法；从材料的结构和性能表征方面来看，可以使学生学习和操作科研类的大型仪器设备，对学生的动手操作能力具有实质性的锻炼。此外，该综合性实验很好地将化学制备与材料的应用相结合，方法简单，耗时短，重复性好，可作为高分子类专业本科生综合探究性实验开设。     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

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.     

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.     

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.     

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.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

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.