高聚物的动态红外光谱研究

动态红外光谱法是研究高聚物在外加力场作用下变形或松弛现象的极为有用的手段。本文介绍了动态红外光谱法的实验技术以及若干近期的研究结果。     

矿物药金礞石的红外光谱分析

采用傅立叶红外光谱法分析了金礞石试样,对所得图谱进行解析,发现试样的红外光谱具备层状硅酸盐矿物的吸收特征.其吸收带主要分为4个区域:3 700～3 000 cm-1区间的OH伸缩振动吸收,1 620 cm-1左右处的H2O弯曲振动吸收,1 000 cm-1左右处的Si-O伸缩振动吸收和550～400 cm-1区间的Si...     

不同软段聚氨酯的红外光谱定量分析

以异佛尔酮二异氰酸酯(IPDI)为硬段,聚环氧丙烷醚二醇(PPG)和聚己内酯二醇(PCLD)、聚碳酸酯二醇(PCD)、聚四氢呋喃醚二醇(PTMG)为软段,通过改变软段组分及相对含量,合成了系列水性聚氨酯乳液。采用傅立叶自解卷积方法,对合成试样红外光谱的重叠谱带进行分峰处理,结果有效增强了红外谱图的表观分辨率,不仅可以辨认低含量组分的特征吸收,而且当软段含量为4%时仍可检出。采用积分面积法和峰高法进行定量计算并作线性回归分析,发现积分面积法的相关系数r大于0.95。积分面积法优于峰高法。氢键作用对定量结果有一定影响。核磁共振氢谱验证数据与定量分析结果一致。     

酚醛树脂固化过程的红外光谱分析

利用红外光谱(IR)及其变温样品池、定量分析程序对酚醛树脂固化过程中的结构变化进行了研究,它对于酚醛树脂固化过程的质量控制具有重要意义。     

海藻糖与脂质膜体系的红外光谱分析

冻干保护剂海藻糖对磷脂脂双层有保护作用，它可以降低磷脂主相变温度，抑制膜脂侧相分离和膜融合。本实验以蛋黄卵磷脂(EPC)为模型，通过相变发生时磷脂吸热量的变化，以及磷脂脂肪酸链CH2基团的对称伸展振动频率的变化，研究海藻糖对蛋黄卵磷脂(EPC)脂质膜相变时影响，并通过FTIR红外光谱分析得到进一步验证。     

聚酰胺酸结构及其亚胺化的红外光谱分析

利用变温透射红外光谱方法,通过跟踪聚酰胺酸（PAA）的亚胺化过程,对由均苯四酸二酐和4,4′-二氨基二苯醚合成的聚酰胺酸及经过加热亚胺化后生成的聚酰亚胺(PI)的红外吸收光谱进行分析,对聚酰胺酸和聚酰亚胺的红外谱峰进行合理的归属,发现聚酰胺酸在亚胺化过程中有-COO-和-NH+2存在,-COO-中羰基的对称与反对称伸缩振动分别位于1607和1406 cm-1,NH+2的伸缩振动则有3200、3133、2938、2880、2820和2610 cm-1等多个精细谱带。 并根据对-COO-和-NH+2谱峰的归属,提出聚酰胺酸生成聚酰亚胺的机理为聚酰胺酸中COOH的H+转移到聚酰胺酸中的NH上,形成NH+2,然后脱水环化生成聚酰亚胺。     

草酸钙结石形态的红外光谱分析

草酸钙结石主要是以一水草酸钙(COM)、二水草酸钙(COD)的形式存在。在解决缺少COD标样的难题后,将制备的COD样品与COM标样混合,然后采用红外光谱法对混合物进行分析研究,采用谱带比值法,确定了COD和COM在660和610 cm-1处与780和520 cm-1处的吸收度比值(R)与质量分数(w)的关系式,其线性回归方程分别为:R=11.95×10-3wCOD 0.873 61,r=0.983 63;R=4.74×10-3wCOD 0.886 52,r=0.992 44。同时为了减少压片、测定等因素引起的误差,采用零点交叉一阶导数法,测定在1 320 cm-1处吸收度一阶导数与COD质量分数(w)的关系式,其线性回归方程I=5.5×10-5w 9.2×10-5,r=0.996 60。线性良好。     

双马来酰亚胺树脂固化过程的红外光谱分析

利用傅里叶变换红外光谱法研究双马来酰亚胺树脂固化过程中的结构变化,认为双马来酰亚胺树脂固化反应分两进行,第一步是低温下的“ENE”反应,第二步是高温下的Diels-Alder反应,树脂第一步固化反应达到一定程度后,要进一步提高固化反应程度,必须提高温度才能使第二步固化反应发生。     

磺化聚苯乙烯胶体晶的红外光谱分析

单分散乳胶体系可以通过自组装形成有序的胶体晶结构 ,在窄波段光过滤器[1] 、生物医学传感器[2 ] 、智能化学传感器[3] 等领域具有重要的应用价值 .最近 ,人们以此有序结构作为模板 ,制备了有序孔材料[4～ 7] .另外 ,此有序结构在仿生学如模拟蛋白石等有序结构等方面也具有重要意义[8] .但是 ,一般的单分散体系如聚苯乙烯体系所形成的有序结构都属于硬性材料 ,缺乏对外场的响应特性 .此外 ,微球表面没有功能性基团 ,很难与其它物质兼容 ,这使得其作为模板合成其它复合材料的潜力大大降低 .本实验室通过对聚合物胶体晶进行改性 ,使其成为功…     

聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）互穿聚合物网络的研究

研究了（蓖麻油－聚乙二醇）聚氨酯／聚（苯乙烯－甲基丙烯酸甲酯－甲基丙烯酸）（ＰＵ／Ｐ（Ｓｔ－ＭＭＡ－ＭＡＡ））互穿聚合物网络（ＩＰＮ）．动态力学性能及透射电镜结果均表明该体系相分离较严重；ＩＰＮ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合，而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。形成ＩＰＮ后，其力学性能得以改善。透射电镜结果表明，聚氨酯网的交联密度直接影响ＩＰＮ的相区尺寸。形成ＩＰＮ后热稳定性提高，易于降解断链的Ｓｔ－ＭＭＡ－ＭＡＡ单体起到了自由基消除剂的作用。     

热塑性聚氨酯弹性体中的氢键作用──动态力学分析

采用动态力学分析方法研究了一系列由聚四氢呋喃(M_n=2000)、4,4-二苯基甲烷二异氰酸酯以及N-甲基二乙醇胺、1,4-丁二醇和1,2-丙二胺三种不同的扩链剂合成的TPU中的氢键作用.发现这种氢键作用符合Arrhenius型的温度依赖性.从弹性模量-温度关系曲线上估算出氢键解离活化能和物理交联密度     

聚氨酯／聚（苯乙烯—甲基丙烯酸甲酯—甲基丙烯酸互穿聚合物网络的研究

研究了聚氨酯／聚互穿合笺网络，动态力学性能及透射电镜结果均表明该体系相分离较严重。ＩＮＰ具有两个玻璃化转变温度，它们有不同程度的内移，形成一定程度分子水平的混合。而ＩＰＮ（５０／５０）其分子混合水平较大，互穿缠结程度较高。     

Characterization of graded polyurethane elastomer by FTIR

Polyurethane elastomers with graded structure were prepared in the graded temperature field. The samples were characterized by FTIR technology. The results show that the degree of microphase separation in the samples decreases with the decrease of the curing temperature. As far as the molar ratio of NH2 and NCO is concerned, the sample exhibits better graded morphology when the ratio is 0.95. The transparence of the samples prepared also changes gradually, increasing along the direction, in which temperature decreases.     

Some observations on FTIR emission spectroscopy of black solid samples

Application of FTIR emission spectroscopy to the study of optically opaque polymer samples containing high levels of carbon black/carbon fibre filler is considered. The effects of reduced emission and self-absorption are discussed.ICI Films     

Helical Biphenyl Bisazo Polyurethane: Preparation,Characterization and Analysis of Polymeric Thermo-Optic Switch

The bisazo chromophore molecule (CAAPM) and helical biphenyl bisazo polyurethane (HBBPU) were synthesized. The structures of CAAPM and HBBPU were characterized by FT-IR and UV-vis spectroscopic techniques. The measurements of refractive index and thermo-optic coefficient (dn/dT) of HBBPU were demonstrated at different wavelengths and different temperatures by the ATR technique. By using CCD digital imaging devices, transmission loss of the internal waveguide was measured. The refractive index dispersions and Sellmeyer coefficients of HBBPU were obtained by the Sellmeyer equation. A Y-branched switch based on the thermo-optic effect was proposed and the performance of the switch was simulated. With a branching angle of 0.143° and the FD-BPM method, the result showed that the power consumption of the thermo-optic switch could be only 3.6 mW, and the response time of the switch could reach about 8 ms. This is a significant improvement in reducing power consumption compared with the normal Y-branched polymer thermo-optic switch.     

金属硫化物矿物的远红外光谱表征

利用NEXUS670型傅立叶变换红外光谱仪测定了7种金属硫化物矿物的远红外光谱,结果发现金属硫化物矿物因其晶体结构和内部M-S化学键的不同,具有明显不同的谱形和振动频率.结合矿物的晶体结构和化学组成对部分谱带的归属和振动模式进行了探讨.     

FTIR analysis of hydrogen bonding in amorphous linear aromatic polyurethanes. I. Influence of temperature

Fourier-transform infrared spectral studies of an amorphous linear aromatic polyurethane at various temperatures were performed. Hydrogen bonding was studied in the N? H stretching (3347 cm^?1) and the bending (1535 cm^?1) regions, using the band decomposition technique. The variations with temperature are used to calculate the ratio of the absorptivity coefficients for the H-bonded to the “free” N? H vibrations. This ratio is found to be independent of temperature. The enthalpy and the entropy of hydrogen bond dissociation are also obtained as 9.6 kJ mol^?1 and 44.8 J mol^?1 K^?1, respectively. Two C?C in-plane vibrational bands of the aromatic rings at 1614 and 1598 cm^?1 were studied at different temperatures. The integrated absorbance for both bands decreases clearly and regularly with increasing temperature, and both bands shift to lower wavenumbers. This strongly suggests a specific interaction for the aromatic rings, probably N? H … π hydrogen bonds, which will be discussed in detail in the second part of this series. © 1994 John Wiley & Sons, Inc.     

聚氧化乙烯基聚合物电解质中离子缔合与结晶状态的傅立叶变换红外光谱(FTIR)研究

通过FTIR光谱技术对P(EO)_nLiX [X＝N(SO₂CF₃)₂, SCN, ClO₄] (n＝4～60)聚合物电解质的离子缔合行为进行了研究, 结果表明在PEO-LiSCN体系中缔合现象较为严重. 在高浓度时LiSCN主要以离子对、离子簇以及二聚体形式存在, 自由离子含量较少. 而对于LiTFSI和LiClO₄体系, 则以自由离子形式为主. 随着锂盐的加入, 由于其阴离子的增塑作用使聚氧化乙烯(PEO)中的晶相成分逐渐向无定形相转化. 当锂盐含量增加到一定程度, 体系中会有不同晶相复合物的形成.     

Analysis of renal stones by FTIR spectroscopy

A study of the chemical composition of renal stones is important for understanding their etiology. And the therapy for the stone disease is usually based on the analysis of calculi, permitting a porper management of the disease and the prevention of its recurrence. FTIR spectroscopy has been used for urinary stones analysis. The routine, easy and rapid measurements give unambiguous information about the stone composition. Especially a precise wavelength scale of the Fourier method is helpful here. A relatively good spatial resolution is important as very often the stones are composed of core and various layers of different chemical composition. A quantitative determination of the proportion of various materials in calculi is also possible.