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。     

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.     

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。     

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%).     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.