氢化丁苯共聚物结构的核磁共振波谱表征Ⅱ.微观结构的定量计算

在氢化丁苯共聚物¹³C-NMR谱脂肪碳部分谱带归属的基础上,根据各谱带的主要来源,推导出六个二单元浓度的计算公式。计算出二单元、一单元的相对含量,各结构单元的数均序列长度、嵌段含量和其它结构参数。加氢前后的¹H-和¹³C-NMR谱的组成计算结果基本一致。初步探讨了作为粘度指数改进剂的氢化丁苯共聚物微观结构与性能的关系,为合成提供了依据。     

α-溴代丙烯酰胺衍生物与丙氨酸反应产物的结构鉴定

本文测定了α-溴代丙烯酰胺与丙氨酸反应产物的¹H,¹³C-NMR谱,采用NMR的各种技术对其谱线进行归属,鉴定出该产物的化学结构,是氮丙啶化合物的一对等量的非对映异构体的混合物,并讨论了¹H,¹³C-NMR谱与立体化学的关联。本文测定的氮丙啶化合物的非对映异构体的¹³CNMR谱未见报道。     

氢化丁苯共聚物结构的核磁共振波谱表征Ⅰ.13C谱带的归属

本文分别用JEOL FX-90Q和Bruker AM-300波谱仪测定了氢化聚丁二烯和氢化丁苯共聚物的¹H,¹³C-NMR谱,得到了分辨率较高的谱图和新的结构信息。借助DEPT技术确定了各谱带的CH或CH₂类型。利用Grant-Paul和Lindeman-Adams介绍的化学位移经验计算公式,考虑苯基对α、β和γ碳原子的影响,计算了各种三单元序列中有关碳原子的化学位移。对脂肪碳部分的28组谱带重新进行了归属。化学位移计算值与实测值基本相符,并得到了不同组成的模型聚合物¹³C-NMR谱的各谱带强度变化规律的验证。     

用13C NMP研究环氧乙烷(EO)-环氧丙烷(PO)共聚物链结构

本文用¹³C-NMR研究EO-PO无规共聚物的序列结构,通过实验结果证明了Whipple等提出的以EO为中心的三单元组序列归属是合理的,得到一组取代参数,并在此基础上发现了EO'PO嵌段共聚物嵌段键合处特征峰,论述了无规共聚物和嵌段共聚物¹³C NMR谱的差异。     

赤霉低酸及其衍生物的13C-NMR研究

用JMOD和DEPT技术,并结合氘标记和进行一些化学反应,确定了赤霉低酸及其一些衍生物的¹³C-NMR谱中的所有¹³C峰归属。     

星型支化SBS嵌段共聚物的NMR研究

本文研究了由四氯化硅和氯硅烷等偶联聚合的多种星型支化SBS及其氢化试样的¹H和¹³C-NMR谱,确定了它们的三种不同支化度的星型支化结构。并研究了四官能度星型支化SBS试样的¹³C序列结构。     

无规丁苯共聚物的核磁共振波谱——二单元序列结构的定量计算

在前文谱带指认的基础上,用¹³C-NMR谱的脂肪碳部分计算了无规丁苯共聚物中十六种二单元的组成.由它们推出的四种结构单元的组成与从氢谱得到的结果相符.在本聚合体系下,二单元的序列长度和四种结构单元的平均持续比表明,苯乙烯单元(S)易形成短嵌段聚合物,1,2-丁二烯单元(v)显示出易与其它三种单体单元结合的趋势,反式1,4-丁二烯单元(t)和顺式1,4-丁二烯单元(c)除形成本身的嵌段聚合物以外,也易形成交替式结构.结果表明,¹³C-NMR是研究丁苯共聚物微观结构的有力工具.     

紫外光引发阳离子聚丙烯酰胺的红外光谱研究

以丙烯酰胺(AM)、 丙烯酰氧基乙基三甲基氯化铵(DAC)、 丙烯酸丁酯(BA)为单体,采用紫外光引发聚合制备阳离子聚丙烯酰胺P(AM-DAC-BA)。 采用紫外光谱和红外光谱研究其结构特征;分析AM,DAC,BA,P(AM-DAC-BA)的红外光谱中的典型红外振动频率的归属。 通过与单体红外光谱比较得出：由于聚合产物的对称性增加,聚合产物红外光谱更加简单。 P(AM-DAC-BA)的特性粘度随着光强、 BA含量、 光引发剂浓度、 光照时间的增加而增加。 选取AM,DAC,BA中的—CONH₂,—COOCH₂(CO), —COOCH₂—(C—O—C),—CH₂—N+(CH₃)₃基团吸收峰为特征吸收峰,随着光强、 BA含量的增加,特征峰面积增加;随着光引发剂浓度增加特征峰面积却呈现减少趋势;随着光照时间增加,峰面积是先减小后增加。 但不同P(AM-DAC-BA)在红外光谱上对应的特征吸收峰的峰型类似,特征峰位置基本一致。     

碳苷化合物的13C-NMR定量研究

本文报道了通过计算碳苷α,β端基异构体糖环上相同碳原子在¹³C-NMR全去偶谱和NNE谱中峰强度或峰面积之比进行定量研究的方法.结果表明,如果碳苷化合物具有合适的溶解度,可以得到很准确的结果,相对误差小于1%.     

8,2'-O-环化-9β-D-腺嘌呤阿拉伯糖苷的NMR及结构研究

8,2'-O-环化-9β-D-腺呤阿拉伯糖苷是阿糖腺苷合成过程中的一个关键性中间体,该化合物的NMR数据只有¹H-NMR谱的糖环1'位质子化学位移和偶合常数的报道,¹³C-NMR谱未曾报道。本文用2D-NMR、NOE-DIF等技术,对它的¹H、¹³C-NMR谱进行归属,进一步明确了它的结构。     

Poly(acrylamide‐co‐acrylic acid)/Poly(vinyl pyrrolidone) Polymer Blends Prepared by Dispersion Polymerization

The structure and properties of a three‐component system, a poly(acrylamide‐co‐acrylic acid)/poly(vinyl pyrrolidone) [P(AM‐co‐AA)/PVP] polymer blend prepared by dispersion polymerization, were studied. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the resulting P(AM‐co‐AA) microspheres with diameters between 200–300 nm were well‐dispersed in the PVP matrix. Fourier transform infrared spectra (FTIR) showed that intermolecular hydrogen bonding interaction occurred between the dispersed phase and the continuous phase. The mechanical properties of P(AM‐co‐AA)/PVP polymer blends were also determined. With different mass ratios of acrylamide to acrylic acid, it was found that the blends had better mechanical properties with increased AA content.     

Aggregation Behavior of Copolymer Containing Sulfobetaine Structure in Aqueous Solution

Copolymers containing sulfobetaine (P(AM/DMAPS)) were synthesized by aqueous copolymerization of acrylamide with 3-[N-(2-methacroyloylethyl)-N,N- dimethylammonio]-propane sulfonate. Aggregation and disaggregation of P(AM/ DMAPS) copolymer in aqueous solution as a function of copolymer concentration, added salts, and temperature were studied by dynamic laser light scattering. P(AM/DMAPS) copolymers exist as a mixture of individual chains and interchain aggregation in deionized water. At low copolymer concentrations (below 1.0 g L^?1), the intrachain aggregation is dominant. With increasing copolymer concentration, the interchain aggregation is enhanced. The addition of a small amount of salts (C_NaCl < 0.1 mol L^?1; C_MgCl2/CaCl2 < 0.05 mol L^?1) leads to the disaggregation of the intra- and interchain aggregation. Further addition of salts results in the enhancement of interchain aggregation. The influence of various cations (Na⁺, Ca²⁺, Mg²⁺) on the aggregation behavior increases in the order Na⁺ < Ca²⁺ < Mg²⁺. The increase of temperature from 25°C to 60°C facilitates the breakup of intrachain aggregation and the enhancement of interchain aggregation.     

Monomolecular film and absorption behavior of polymers having carboxyl groups

π-A isotherms of monolayers of various copolymers containing carboxyl groups derived from acrylic acid (AA) were measured. The conformation of polymer adsorbed on the water surface and interaction forces between polymer and water surface (considered to be a model for the surface of inorganic powders) owing to AA groups is discussed based on the π-A isotherms.

Polyacrylic esters having a small amount of AA groups formed the expanded type of monolayer. AA groups cause an increase in the interaction force between the polymer and water surface. Polymethyl methacrylate having a small amount of AA groups formed condensed-type monolayers, while with a large amount of AA groups it showed two types of monolayer collapse. Though polystyrene could not spread as a mono-layer, poly (styrene-acrylic acid) [p(St-AA)] copolymer formed a monolayer when the AA content was over 4 mol %. The adsorbance of P(St-AA) on water, calculated from π-A isotherm, is the same as that obtained on α-Fe₂O₃ independently. This means the conformation of the polymer on the solid surface and the interaction force can be discussed by using the π-A isotherm.     

高分子共聚物组成的13C-NMR测定

用DEPT编辑谱方法确定了丙烯酸丁酯-醋酸乙烯酯-丙烯酸共聚物的¹³C-NMR谱线归属,采用门控去偶,增加延迟时间,减小脉冲翻转角的方法,用¹³C-NMR定量地测定了其主要组成。     

Core–corona PSt/P(BA–AA) composite particles by two-stage emulsion polymerization

Raspberry-shaped composite particles with polystyrene (PSt) as core and poly(n-butyl acrylate-co-acrylic acid) (P(BA–AA)) as corona were synthesized via emulsion polymerization. The random copolymer, P(BA–AA), was pre-prepared and used as a polymeric surfactant, its emulsifying properties adjusted by changing the mass ratio of BA and AA. The morphology of the resulting core–corona composite particles, P(St/P(BA–AA)), could be regulated and controlled by varying the concentrations of P(BA–AA) or the mass ratio of BA:AA in P(BA–AA). The experimental results indicate that 3.0–6.0 wt% of P(BA–AA) is required to obtain stable composite emulsions, and P(BA–AA) with a mass ratio of BA:AA = 1:2 is able to generate distinct core–corona structures. A mechanism of composite particle formation is proposed based on the high affinity between the PSt core and the hydrophobic segments of P(BA–A). The regular morphology of the colloidal film is expected to facilitate potential application of core–corona particles in the field of light scattering. Furthermore, the diversity of core–corona particles can be expanded by replacing P(BA–AA) corona particles with other amphiphilic particles.     

PA和PPP三嵌段共聚物的带电态研究

采用半经验的Austin Model 1(AM1)方法,计算了-(PA)₄-(PPP)_m-(PA)₄-共聚物的带电状态,该系列共聚物具有典型的阱垒阱结构特征.与中性态相比,带电态下其分子结构表现为C—C键长发生显著的改变.在不同的掺杂浓度及不同的势垒宽度下,电荷在势阱中的分布是不同的. 关键词： 共聚物 有机量子阱 带电态 键长     

β-环糊精与环氧氯丙烷共聚物的13C-NMR研究

¹³C NMR测定了一个系列的环氧氧丙烷与β-环糊精的共聚物,进行了谱峰归属和DEPT谱验证,实验测得2,3-丙二醇基在β-环糊精C(2)-O-位、C(3)-O-位和C(6)-O-位取代的¹³C NMR化学位移α-取代效应参数,描述了该共聚物分子链的组成和链化学结构特征.     

新型Silole与窄带隙单体的交替共聚物的合成、荧光光谱及光伏性能

采用Pd催化偶联的方法合成了1,1-二乙炔基-2,3,4,5-四苯基Silole,并分别与2,1,3-苯并噻二唑(BT)和4,7-二(2-噻基)-2,1,3-苯并噻二唑(DBT)组成两种交替共聚物PS-BT和PS-DBT,并研究了两种共聚物的紫外吸收光谱、光致发光及光伏电池性能。PS-DBT具有更宽的可见光吸收范围和更强的吸收。两种共聚物溶液的光致发光光谱的最大发射波长均随着溶液浓度的增大逐步红移。光伏电池器件结构为ITO/PE-DOT/copolymers:PCBM(1:4)/Ba/Al。PS-BT和PS-DBT的开路电压分别为0.50,0.40V,填充因子(FF)分别为24%和33%,在模拟太阳光(AM1.5)照射下的能量转化效率(ECE)分别为0.009%和0.032%。     

CSC-P(AM-AA)重金属捕集絮凝剂的光谱表征及其对重金属去除研究

采用光聚合技术成功制备了羧甲基壳聚糖(CSC)、丙烯酰胺(AM)、丙烯酸(AA)的三元接枝共聚物,即壳聚糖基重金属捕集絮凝剂CSC-P(AM-AA)。为了证明接枝共聚产物的成功制备和表征其结构特征,采用红外光谱(IR)、X射线衍射(XRD)、差热-热重分析(TG-DSC)、扫描电镜(SEM)对其进行表征,结果表明成功制备出羧甲基壳聚糖的接枝共聚物CSC-P(AM-AA),且具有较好的溶解性;由于羧甲基壳聚糖的接枝改性使得CSC-P(AM-AA)具有与P(AM-AA)显著不同的结构特征。同时絮凝实验证明其具有较好的重金属螯合捕集效果,在pH为8、投加量为8 mg·L-1、转速为150 r·min-1时,CSC-P(AM-AA)对Cu2+的最佳去除率为87.0%。