Polycationic Salts V [1]. 15N NMR Spectra of Amines, Ammonium Salt Monomers, and Polymers of Styrene Based Trialkylammonium Salts

Summary.  ¹⁵N NMR spectroscopy was found to be essential for the detailed characterization of tertiary amines, vinylbenzylammonium salts, and polymers derived from these compounds. It proved important for the characterization of low 2-ionene oligomers and vinylbenzylammonium salts derived thereof as well. The polymers of these novel monomers were also characterized and identified. Received November 25, 1999. Accepted (revised) January 10, 2000     

Characterization and quantification of microstructures of a fluorinated terpolymer by both homonuclear and heteronuclear two‐dimensional NMR spectroscopy

Fluoropolymers are usually insoluble in organic solvents. Insolubility of fluoropolymers limits basic characterization such as microstructural investigations. In the family of fluoropolymers, terpolymer of tetrafluorethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF), named THV is one of the newest members. There are nine grades of THV available. Among the nine grades, THV‐221 G is an ideal model polymer for basic characterization purposes. THV‐221 G is soluble in solvents such as acetone and ethyl acetate. In the current report, both homonuclear and heteronuclear 2D NMR experiments were employed in solution on THV‐221 G. The homonuclear gradient correlation spectroscopy NMR measurement revealed that THV has two adjacent TFE units in addition to TFE‐HFP sequence orders. The fraction of the microstructures is quantified by the analysis of 1D solution ¹⁹F NMR spectrum. Further, the gradient heteronuclear single quantum coherence experiment helped with the clarification of chemical environments of the units TFE, HFP, and VDF. The 1D solution ¹³C NMR spectrum was helpful in clarifying sequence assignments of VDF. It is concluded that THV is a random polymer with a limited fraction of TFE‐TFE and TFE‐HFP sequence orders in addition to head‐to‐tail polymerization of VDF unit. Copyright © 2014 John Wiley & Sons, Ltd.     

29Si NMR研究TEOS/DDS双前驱体体系的水解动力学

原位引入有机组分对氧化硅体系改性是合成有机-无机杂化硅材料的重要方法. 利用原位的²⁹Si液体核磁, 研究了甲醇为溶剂、氨水催化条件下的四乙氧基硅烷(TEOS)和二甲基二乙氧基硅烷(DDS)原位共水解的动力学过程. 通过改变反应体系中氨和水的浓度, 拟合出单体及中间产物浓度随时间的变化曲线, 得到了TEOS和DDS各自的水解速率常数以及相应各反应物的反应级数. 与单前驱体水解一致的是, 在双前驱体系中TEOS和DDS自身的反应级数仍保持一级, 但是氨和水的反应级数都有不同程度的增大. 与单前驱体水解速率方程相比, 混合体系中TEOS的水解速率常数增大. 同时, DDS在双前驱体中比单前驱体中的水解速率常数有很大程度的减少. 水解动力学表明, TEOS和DDS在双前驱体体系中显示出更平行的水解速率. 利用固体²⁹Si MAS NMR, XPS及小角X射线散射(SAXS)手段对双前驱体体系研究得到的信息显示, 碱催化条件下原位的TEOS水解中间物与DDS中间产物的原位共缩聚程度很弱.     

Study of cellulose/ethylene diamine/salt systems

To better understand the complex interactions leading to dissolution of cellulose in ethylene diamine (EDA)/salt solvents, studies of interactions in sub systems of solution components and a model system based on cellobiose were conducted. Interaction between EDA and salt cation was investigated through comparison of solvation of K⁺, Na⁺ and Li⁺ in the EDA/H₂O binary solvent system. The least degree of solvation of K⁺ in EDA increased its availability for direct interaction with cellulose. Wide angle X-ray diffraction was utilized to study the interaction between EDA and cellulose. The effect of various solvents on cellulose crystalline polymorph was compared. The results indicated that cellulose was easily accessible to EDA and 1,3-diaminopropane, but was not affected by water or ethanolamine. The effect of salt concentration was investigated using cellobiose as a model compound through HSQC (Heteronuclear Single Quantum Coherence) NMR spectroscopy. Solid state CP/MAS (cross polarization/magic angle spinning) ¹³C NMR spectroscopy was employed to characterize changes in the conformation of the CH₂OH group of cellulose during dissolution. A mechanism scheme of cellulose dissolution in EDA/KSCN systems was proposed based on the information gathered.     

Oligomeric Alkoxysilanes with Cagelike Hybrids as Cores: Designed Precursors of Nanohybrid Materials

Well‐defined alkoxysilane oligomers containing a cagelike carbosiloxane core were synthesized and used as novel building blocks for the formation of siloxane‐based hybrid networks. These oligomers were synthesized from the cagelike trimer derived from bis(triethoxysilyl)methane by silylation with mono‐, di‐, and triethoxychlorosilanes ((EtO)_nMe_3?nSiCl, n=1, 2, and 3). Hybrid xerogels were prepared by hydrolysis and polycondensation of these oligomers under acidic conditions. The structures of the products varied depending on the number of alkoxy groups (n). When n=2 and 3, microporous xerogels (BET surface areas of 820 and 510 m² g^?1, respectively) were obtained, whereas a nonporous xerogel was obtained when n=1. ²⁹Si NMR spectroscopic analysis suggested that partial rearrangement of the siloxane networks, which accompanied the cleavage of the Si–O–Si linkages, occurred during the polycondensation processes. By using an amphiphilic triblock copolymer surfactant as a structure‐directing agent, hybrid thin films with a 2D hexagonal mesostructure were obtained when n=2 and 3. These results provide important insight into the rational synthesis of molecularly designed hybrid materials by sol–gel chemistry.     

Curing Kinetics and Thermal Stability of Diglycidyl Ether of Bisphenol‐A Using Mixtures of Heterocyclic Derivatives of Stannanes and 4,4′‐Diaminodiphenylsulfone

Curing kinetics of diglycidyl ether of bisphenol-A (DGEBA) in the presence of varying molar ratios of derivatives of stannanes to 4,4'-diaminodiphenylsulfone (DDS) was investigated by the dynamic differential scanning calorimetry. The derivatives were synthesized by reacting 1 mole of biguanide (B) with 1 mole of phenylethyltindihydride (PETH) or phenylmethyltindihydride (PMTH) or phenylbutyltindihydride (PBTH) and designated as BPETH or BPMTH or BPBTH respectively. These derivatives were characterized by elemental analysis and spectroscopic techniques such as IR, ¹H NMR, ¹³C NMR and ¹¹⁹Sn NMR. The mixtures of these derivatives to DDS at ratios of 0∶1, 0.25∶0.75, 0.5∶0.5, 0.75∶0.25 and 1∶0 were used to investigate the curing behaviour of DGEBA. The multiple heating rate method (5, 10, and 15 and 20 ℃•min^－1) was used to study the curing kinetics of epoxy resins. The thermal stability of the isothermally cured resins was also evaluated using dynamic thermogravimetry in a nitrogen atmosphere.     

Preparation of telechelic oligomers by controlled thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene)

It was found that telechelic isotactic oligo(1-butene) and telechelic oligo(propylene-ran-1-butene) could be isolated as nonvolatile oligomers from polymer residues resulting from the thermal degradation of isotactic poly(1-butene) and poly(propylene-ran-1-butene), respectively. Their structures were determined by ¹H and ¹³C NMR with attention being paid to their reactive end groups. The maximum average number of terminal vinylidene groups per molecule (f_TVD) was 1.8, indicating that about 80 mol% were α,ω-diene oligomers having two terminal vinylidene groups. This useful new telechelic oligomer had a lower polydispersity than the original polymer, in spite of its lower molecular weight and T_m. The composition of end groups of nonvolatile oligomers obtained by thermal degradation of poly(propylene-ran-1-butene) could be explained by the differences in bond dissociation energy and activation energy of elementary reactions during thermal degradation, based on the monomer composition of the original polymer.     

Effect of ethylene glycol on the end group structure of poly(3-hydroxybutyrate)

Ralstonia eutropha was cultivated in a culture medium supplemented with ethylene glycol (EG), which is known to act as a chain transfer agent in the production of poly(3-hydroxybutyrate) (PHB). The PHB extracted from the bacterial cells was analyzed by ¹H and ³¹P NMR spectroscopies and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The addition of EG exerted a remarkable influence on the mass of production and molecular weight of PHB, and then was found to result in chain transfer and termination reactions. MALDI-TOF MS of the partially hydrolyzed PHB revealed that either succinate or glutarate combined with the hydroxyl terminals of PHB as polymerization starters. From ³¹P NMR analysis, the carboxyl groups of the succinyls and glutaryls held in the terminals of the isolated PHB were found to be capped with EG, giving the telechelic polyester with hydroxy functionalities. Based on these results, we propose a plausible mechanism of enzymatic polymerization in the microbial PHB synthesis in the presence of EG.     

Synthesis of telechelic oligostyrenes by the ozonoloysis of poly(styrene-stat-butadiene): Protection of styrene units against ozone attack by the use of Di-N-alkyl amides as sacrificial ozone scavengers

Polystyrene and a poly(styrene-stat-butadiene) have been reacted with ozone in various solvents to establish the conditions necessary for the production, from the latter, of telechelic oligostyrenes having high and controllable end group functionalities. Polymeric ozonides produced by ozonolysis of poly(styrene-stat-butadiene)s, on workup with sodium borohydride or zinc/acetic acid, give dihydroxy- or dialdehyde-ended oligostyrenes, respectively. Workup with borane gives oligomers with a mixture of hydroxy and aldehyde end groups. Oxidative workup with selenium dioxide/hydrogen peroxide yields carboxylic acid-ended oligostyrenes. Workup with polymer-supported reducing or oxidizing agents was less successful. It is shown that side reactions associated with the synthesis of telechelic oligostyrenes by the ozonolysis route, i.e., attack at the α position and possibly also on the phenyl rings of the styrene units, can be minimized by the use of N-dialkyl amides, particularly dimethylacetamide, as sacrificial ozone scavengers. © 1996 John Wiley & Sons, Inc.     

The iterative synthesis of discrete dimethylsiloxane oligomers: A practical guide

Discrete dimethylsiloxane oligomers are interesting building blocks for the synthesis of high χ–low N block co-oligomers (BCOs) forming highly organized nanostructures. Here, a practical guide to the synthesis of molecularly defined oligodimethylsiloxanes (oDMS) from 7-mer to 40-mer via a linear growth strategy is described. The iteration of a hydroxylation reaction and the condensation of mono- or bifunctional hydroxysiloxanes with chloro-octamethyltetrasiloxane results in asymmetric and symmetric siloxanes, respectively. The synthesis contains critical washing and purification steps to remove minor amounts of low and high-molecular weight byproducts, which are detected using Fourier transform infrared spectrometry, gas chromatography–mass spectrometry, and size-exclusion chromatography. The oligomers are obtained on a multigram scale in yields of 94–50% and in high purity with only one molar mass detected. The formation of the chloride, hydroxide or hydride functional groups is adequately analyzed using ²⁹Si NMR spectroscopy. The hydride terminated siloxane oligomers are used in Karstedt catalyzed hydrosilylation reactions with alkene-functional substrates to obtain oDMS-based oligomers and BCOs. Byproduct formation as a result of isomerization and reduction are followed by ¹H NMR spectroscopy and minimized using dry conditions and low-catalyst loadings.     

Synthesis and Properties of Hyperbranched Polyimides Combined with Silica

Summary: The novel hyperbranched polyimide - silica hybrid materials containing theoretically 16 wt% of an inorganic phase were prepared via a sol-gel process. An amine terminated polyimide precursor (hyperbranched polyamic acid) was prepared from commercially available monomers 4,4′,4″-triaminotriphenylmethane and 4,4′-oxydiphthalic anhydride in molar ratio 1:1. Tetramethoxysilane and/or 3-glycidoxypropyltrimethoxysilane (also used as a coupling agent) were used as silica precursors. During thermal exposition the polyimide precursor was transformed to hyperbranched polyimide and hydrolyzed alkoxy groups reacted mutually to form silica. The final products were self-standing films, whose structure was characterized by using IR and ¹³C and ²⁹Si solid state NMR spectroscopy. The influence of the amount of silica and/or coupling agent on their structure and thermal properties was described.     

Additional evidence of possible structural effect of diol units in preformed oligoesters on solution copolycondensation with x,y‐dihydroxytoluenes and their isomers promoted by tosyl chloride/dimethylformamide/pyridine

A two‐stage copolycondensation of a mixture of equal parts of isophthalic acid and terephthalic acid was conducted using a tosyl chloride/dimethylformamide/pyridine condensing agent. In the initial stage x,y‐dihydroxytoluenes (x,y‐DHTs) or 2,4‐dihydroxyethylbenzene (2,4‐DHEB) was used and in the next stage isomeric DHTs or the DHEB was used. The results were examined in terms of how the reaction of the resulting oligomers with the next monomers proceeded, which was evaluated from distributions of the next monomers in the resultant copolymers as determined by ¹H NMR. A structurally selective reaction was observed. The preformed oligomers from symmetrically substituted 3,5‐DHT reacted randomly with similarly substituted 2,6‐DHT or asymmetric 2,4‐DHEB, but those from 2,4‐DHEB reacted selectively with both of 3,5‐ and 2,6‐DHT. In the reactions of the oligomers from 2,6‐DHT, they reacted randomly with 2,6‐DHT but selectively with 2,4‐DHEB. Such selective reactions were also observed in the reaction of p‐isomeric 2,5‐DHT with the oligomers prepared from 3,5‐ or 2,6‐DHT. When the monomers were copolymerized simultaneously instead of stepwise, they distributed randomly in the resultant copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5687–5694, 2004     

Synthesis and characterization of sulfonated copolyethersulfones

The present article deals with the synthesis and characterization of some sulfonated copolyethersulfones. The synthetic approach differs from the post sulfonation approach traditionally reported in the literature. The synthetic procedure is based on the use of sulfonated monomers which are then reacted with previously synthesized telechelic hydoxy‐ended poly (ether sulpnone)s. Combining the MALDI‐TOF MS and ¹H NMR analyses, with SEC‐Viscometry and TGA measurements, we demonstrate a powerful tool for characterizing the chemical composition, end chains, degree of sulfonation (DS) and molecular mass distribution (MMD) of disulfonated poly(arylene ether‐sulfone) copolymers. The characterization techniques allowed to determine the exact nature of the copolymers synthesized and to reveal some interesting features about the reaction. DMA data show that the glass transition temperature of sulfonated copolymers with similar DS increase as raise their MMD. Copolymers with a DS of 10–11 mol % reach a T_g of 244–246 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3010–3023, 2010     

Study of the spectroscopic characteristics of methyl (ligand) cobaloximes and their antibacterial activity

Spectroscopic characterization (IR, NMR and electronic spectra) of methyl (ligand) cobaloxime was done, where ligand = pyrazole, dimethyl pyrazole, alanine and alanine methyl ester. The frequency changes in the IR spectra and shifts in the NMR were explained on the basis of basicity of the ligand, steric hindrance, HSAB principle and dπ-pπ back-bonding from metal to ligand. Alanine and alanine methyl ester form more stable complexes than pyrazole and dimethyl pyrazole. Based on their IR and ¹H NMR spectra it is inferred that pyrazole and dimethylpyrazole bind to Co (III) via N-2 ring nitrogen, i.e. monodentate coordination.     

Densely crosslinked polycarbosiloxanes. I. Synthesis

Novel densely crosslinked polycarbosiloxanes were obtained by using functional branched prepolymers. Two types of soluble prepolymers were prepared from di- and trifunctional alkoxysilane monomers via cohydrolysis/condensation and for both final crosslinking occurred via hydrosilylation. The prepolymers having only vinyl functionalities (poly[phenylmethylvinyl]siloxanes, system A) were crosslinked by using a crosslinking agent with reactive silicon–hydrogen bonds. In the prepolymers having both silicon–vinyl and silicon–hydrogen functionalities (poly[phenylmethyl-vinylhydro]siloxanes, system B) crosslinking took place intermolecularly. For the characterization of the prepolymers ¹H-NMR, ²⁹Si–NMR, FT–IR spectroscopy, analytical SEC and VPO were employed. The prepolymers were fractionated with preparative SEC and the fractions analyzed with ¹H-NMR and analytical SEC. The crosslinking reaction was followed by FT–IR spectroscopy. The polymer networks were fully transparent homogeneous materials and are promising for future optical applications. © 1997 John Wiley & Sons, Inc.     

Synthesis of telechelic methacrylic siloxanes with cycloaliphatic substituents groups for UV-curable applications

Methacrylic functionalized siloxanes were prepared in a two-step process. In the first step, a series of telechelic glycidyl epoxy siloxanes were prepared, substituted with either methyl, cyclopentyl, or cyclohexyl groups. In the second step, the telechelic glycidyl epoxy groups were reacted with methacrylic acid. The reaction was monitored via acid value, and when the acid value was ?10, the reaction was terminated. Characterization of the methacrylic telechelic siloxane polymers were performed using ¹H NMR, ¹³C NMR and FT-IR. The methacrylated siloxanes were formulated with a free radical photo-initiator, UV-cured, and the rate of polymerization was monitored via photo-differential calorimetry. After curing, viscoelastic properties, and oxygen-permeability were evaluated. In addition, X-ray was used to evaluate the structure of the cured films. The rate of polymerization was dependent on substituent and increased with increasing substituent size. The oxygen permeability was dependent on crosslink density, and increased with increasing substituent size. The increase in permeability, and thus free volume was supported by X-ray studies which showed an increase in d-spacing with increasing alkyl size.     

Chemical and Optical Propertiesof New Highly Luminescent Alternating Oligo- m , p -phenylenevinylenes

 In this paper we report on the synthesis and characterization of a variety of poly-phenylenevinylene (PPV) derivatives containing para- and meta-linkages in the backbones. By the m-linkages the conjugation lengths of the oligo-m,p-phenylenevinylenes were limited, thus blueshifting the UV/Vis absorption and also the photoluminescence (PL) spectra. Alkoxy substituted oligo-m,p-phenylenevinylenes exhibited absorption and emission spectra at higher wavelengths than oligomers without oxygen directly attached to the backbone. Replacing p-phenylene by 4,4′-biphenylene moieties also led to a hypsochromic shift in the optical spectra. We chose the Heck coupling reaction to synthesize substituted oligomers consisting of alternating p-phenylenevinylene and m-phenylenevinylene units. They were characterized by ¹H NMR, ¹³C NMR, FT IR, UV/VIS, and GPC analysis.     

CP/MAS NMR investigations of silica gel surfaces modified with aminopropylsilane

Summary Aminopropyl chemically bonded phases for high performance liquid chromatography (HPLC) have been prepared using mono- and trifunctional methoxyor ethoxysilanes. Three types of silica gel with different surface characteristics were used as support for the chemically bonded phases (CBPs). Surface characteristics of the packings before and after chemical modification were determined by porosity parameters, elemental analysis and CP/MAS NMR spectroscopy.²⁹Si and¹³C CP/MAS NMR investigations gave informations about different interactions between aminosilyl ligands and/or these ligands and/or water molecules condensed in the pores of the silica gel surface. With decreasing pore diameter of the silica gel the proportion of protonated aminopropyl ligand increases.     

Characterization of signals in the solution 1H NMR spectrum of poly(isobutylene‐co‐p‐methylstyrene) and their utility

Poly(isobutylene‐co‐p‐methylstyrene) is an important precursor to Exxpro™ elastomers. A previous report detailed the characterization of both the proton and the carbon NMR spectra of the copolymer. 1 However, several resonances in the proton NMR spectrum of the copolymer were not assigned. Specifically, the proton methine resonance of the BSB triad sequence is now identified and used to calculate BSB triad contribution to the copolymer microstructure. This report describes the assignment of this resonance and other resonances associated with microstructural sequence distribution around p‐methylstyrene. The proton NMR signals of interest resonate at 2.8 ppm and 2.5 ppm in a typical spectrum for poly(isobutylene‐co‐p‐methylstyrene). The nature of these resonances were determined by preparation and characterization of specifically deuterated poly(isobutylene‐co‐p‐methylstyrene)s employing both one and two dimensional NMR techniques. The 2.8 ppm signal is assigned as the methine proton of a p‐methylstyrene incorporated between two isobutylene units (the BSB triad). The signal at 2.5 ppm is assigned to the meso‐BSS triad. Determination of these resonances allows for rapid evaluation of isolated p‐methylstyrene units (BSB triads) present in the copolymer using only ¹H NMR. The utility of this technique is demonstrated by comparing BSB triad values determined by ¹H and ¹³C NMR analysis. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1680–1686, 2000     

Practical application of 1H benchtop NMR spectroscopy for the characterization of a nonaqueous phase liquid from a contaminated environment

Nonaqueous phase liquids (NAPLs) located at the surface of the water table and/or below the water table are often a significant source for groundwater contamination near current or former commercial/industrial facilities. Due to the complex and long history of many industrial sites, these NAPLs often contain a complex mixture of contaminants and as such can be difficult to fully characterize using conventional analytical methods. Remediation and risk assessment activities at sites containing NAPLs may, subsequently, be hindered as the contamination profile may not be fully understood. This paper demonstrates the application of bench-scale ¹H nuclear magnetic resonance (NMR) spectroscopy as a practical tool to assist with the characterization of complex NAPLs. Here, a NAPL collected from a contaminated site situated near a former chemical manufacturing facility was analyzed using a combination of one-dimensional (1D) ¹H NMR spectroscopy and two-dimensional (2D) ¹H J-resolved spectroscopy (JRES). It is shown that 1D NMR experiments are useful in the rapid identification of the classes of compounds present, whereas 2D JRES NMR experiments are useful in identifying specific compounds. The use of benchtop NMR spectroscopy as a simple and cost effective tool to assist in the analysis of contaminated sites may help improve the practical characterization of many heavily contaminated sites and facilitate improved risk assessments and remedial strategies.