Effect of Pre-coated Vs. Added Coupling Agents on the Vulcanization of Silica-filled Polyisoprene

Solid-state ¹³C NMR was utilized in analysis of the crosslink structure in silica-filled polyisoprene. Samples containing either a pre-coated coupling agent, a coupling agent added in the mixing process, or polyethylene glycol (PEG) were vulcanized and the type and density of crosslinking determined. The precoated coupling agent sample gave lower %swelling, lower extraction amounts, and a lower T ₂ relaxation than the mixed coupling agent, indicating increased crosslinking or increased filler –rubber interaction. The precoated also showed less cis –trans isomerization than the mixed, which may be due to its more uniform coating effect on the silica. The PEG sample yielded a ¹³C spectrum similar to an unfilled sample indicating decreased silica adsorption of vulcanization agents. Neither coupling agent significantly decreased the total sulfurization nor the percent monosulfidic crosslinks from that of a silica-filled sample without coupling agent.     

1H NMR Imaging Study of Molecular Mobility in Silica-Filled, TBBS-Sulfur Vulcanized Cis-Polyisoprene

The interactions of silica in zinc-activated, sulfur-vulcanized cis-1.4 polyisoprene were characterized at the 75% cure state using ¹H NMR imaging spectroscopy. Variables examined included silica loading, mixing conditions, and presence of additives, including a coupling agent and polyethylene glycol. Rheometer curves indicated a decrease in cure rate and cure state as silica was increased. ¹H NMR imaging showed an increase in the T₂ relaxation times, and a decrease in the proton spin density N(H) as the filler load increases. Mixing conditions did not affect the cure rate, cure state, or the average T₂ relaxation time; however, the distribution of relaxation times broadened with poor mixing. The presence of a coupling agent increased the cure rate and cure state, as well as decreased the T₂ relaxation times as compared with samples with the same silica level, but without coupling agent. Polyethylene glycol (PEG) had slightly higher average T₂ relaxation times, and a slightly broader distribution as compared with the sample without PEG added.     

Use of isotopic labeling for mechanistic studies of the methanol-to-hydrocarbons reaction. Methylation of toluene with methanol over H-ZSM-5, H-mordenite and H-beta

Methylation of toluene (in one case benzene) with methanol has been investigated over four different zeolites: Small and large crystal ZSM-5, dealuminated mordenite and zeolite beta. The feed ratio methanol/arene was varied over a wide range, mostly >1, using nitrogen or helium as carrier gas. A rather high space velocity was employed (WHSV (methanol + arene): 5–35 h⁻¹). The reaction temperature was 350°C or 375°C. A parallel set of experiments was performed using ¹³C methanol (99% ¹³C). The products were analyzed by on-line gas chromatography using a GC–MS system allowing determination of isotopic composition of the more important products, i.e., ethene, propene and the arenes when ¹³C methanol was employed, otherwise a FID was used. The goal was to obtain mechanistic information, and no attempt has been made to optimize for any particular reaction product.

The experiments showed that ethene and propene were isotopically mixed, containing 50–75% ¹³C. The 25–50% ¹²C atoms coming from the reactant arene. Over all catalysts the arene was, when fed alone, essentially inert with 0.5% or less conversion, giving neither ethene nor propene in measurable quantities. The isotopic distribution in ethene was indistinguishable from a random distribution. Propene, although being close to, displayed some deviation from randomness. The ¹²C/¹³C isotopic ratio in propene was equal to that in ethene, and they both varied with the methanol/arene ratio in the feed, but much less so than the variation in feed composition.

The results support a pool mechanism where the catalytic activity for converting methanol to hydrocarbons is connected with the presence of adsorbates in the zeolite cavities which add methanol and split off product molecules, notably ethene and propene. Formation of ethene by reaction between C₁ species is at best a minor reaction. While formation of propene may take place by a homologation/cracking mechanism, this route was of minor importance here.

Polymethylbenzenes which were formed in many cases displayed a pronounced isotopic scrambling, containing up to six ¹³C atoms in the benzene ring. Molecules with fewer ¹³C atoms than the number of added methyl groups were also identified.     

Spectroscopic analysis of carbon dioxide and nitrogen mixed gas hydrates in silica gel for CO2 separation

In this study solid-state NMR spectroscopy was used to identify structure and guest distribution of the mixed N₂ + CO₂ hydrates. These results show that it is possible to recover CO₂ from flue gas by forming a mixed hydrate that removes CO₂ preferentially from CO₂/N₂ gas mixture. Hydrate phase equilibria for the ternary CO₂–N₂–water system in silica gel pores were measured, which show that the three-phase H–L_w–V equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO₂ in the vapor phase decreased. ¹³C cross-polarization (CP) NMR spectra of the mixed hydrates at gas compositions of more than 10 mol% CO₂ with the balance N₂ identified that the crystal structure of mixed hydrates as structure I, and that the CO₂ molecules occupy mainly the abundant 5¹²6² cages. This makes it possible to achieve concentrations of more than 96 mol% CO₂ gas in the product after three cycles of hydrate formation and dissociation.     

The Effect of Ethylene Diamine Dilaurate and Silane Coupling Agent on Cure Characteristics,Mechanical, and Thermal Properties of Silica-Filled Natural Rubber Composites

The influence of a new coupling agent, ethylene diamine dilaurate (EDD) and a commercial silane coupling agent, (Si-69) on the cure characteristics, mechanical and morphological properties of silica-filled natural rubber (NR) composites was studied. The results show that scorch time and cure time decreased with an increase in both coupling agents' content, but maximum and minimum torques exhibit the opposite trend. The mechanical properties such as tensile strength and tensile modulus, M100 and M300, increased with increasing both coupling agents' content but at a similar coupling agent content, silica-filled natural rubber composites with Si-69 exhibit better tensile strength (more than 2 phr) and tensile modulus than does EDD. Elongation at break (Eb) of silica-filled natural rubber increased with increasing EDD content but Si-69 exhibits the opposite trend. Scanning electron microscopy (SEM) study of tensile fracture surfaces shows the better tensile strength of silica-filled natural rubber composites with Si-69 and EDD over control composites (without EDD or Si-69). Thermogravimetric analysis (TGA) results indicate that silica-filled NR composites with EDD have higher thermal stability than Si-69. Fourier transform infrared spectra (FTIR) provided an evidence of interaction between EDD and Si-69 with silica in NR composites.     

Control of ordered structure and morphology of cubic mesoporous silica SBA-1 via direct synthesis of thiol-functionalization

Well-ordered cubic mesoporous silicas SBA-1 functionalized with thiol groups have been synthesized via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strongly acidic conditions. Various synthesis parameters such as HCl concentration, synthesis temperature, and time for hydrothermal treatment were systematically investigated as a function of MPTMS contents. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), solid-state ¹³C and ²⁹Si NMR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and nitrogen sorption measurements. Direct evidence of the presence of chemically attached thiol moieties was provided by solid-state ²⁹Si and ¹³C NMR spectroscopy. A high degree of structural ordering was still retained when MPTMS loading was incorporated up to 20 mol% in the synthesis mixture. Increasing the synthesis temperature and the time for the hydrothermal treatment not only increased the degree of framework cross-linking, but also did not lead to the undesirable phase transformation as often observed in the conventional synthesis of pure silica SBA-1. SEM results reveal that the morphology of thiol-functionalized SBA-1 depends on the HCl concentration used in the synthesis. The sample prepared with a low acid concentration exhibits a highly isotropic morphology with more facets than that of pure silica SBA-1, whereas it changes to a spherical shape as the acid concentration is increased. The maximum content of the attached thiol group (–SH) in the mesoporous framework is 2.39 mmol/g. The thiol-functionalized SBA-1 mesoporous materials are efficient Hg²⁺ adsorbents.     

Covalent bonding of wood through chemical activation

The reaction of softwood thermomechanically pulped fibres with succinic anhydride (SA) and its subsequent reaction with hexamethylene diamine (HMDA) were examined, the latter employing the coupling agents dicyclohexylcarbodiimide, or diisopropylcarbodiimide. FTIR and ¹³C NMR studies showed amide linkages were produced between SA modified fibres and the diamine. Wood veneers were covalently bonded using this technology. It was found that during hot pressing bonding occurs between SA treated veneers and HMDA without the need for a coupling agent.     

Organo-modified mesoporous silicas for organic pollutant removal in water: Solid-state NMR study of the organic/silica interactions

The adsorption properties of various organo-modified mesoporous silicas towards a methoxy-modified chlorophenol in water have been studied. Phenyl, propyl, hexyl and hexadecyl groups were selected to study the possible interactions that the pollutant could preferentially develop with the surface sites. The best performing sample appears to be the hexyl-modified porous silica and one of the least performing the un-modified mesoporous silica. The physical state of the adsorbed chlorophenol in these two confined environments as well as the pollutant/surface interactions were characterized by a combination of solid-state NMR techniques. The ¹H and ¹³C NMR responses show a high mobility of the molecules in both the modified and un-modified silica, suggesting the absence of strong interactions between the pollutant and the surface, despite the large difference in the chemical nature of the silica surface sites.     

蒙药材止泻木子生物碱的分离与纯化

以夹竹桃科植物止泻木子的干燥种子为原材料,采用乙醇提取法对其生物碱类物质进行粗提取,通过硅胶柱层析和重结晶技术对生物碱粗提物进行分离和纯化。利用核磁共振波谱和质谱法对其一种生物碱单体进行化学结构和分子量鉴定。实验结果表明,用70%乙醇在60℃条件下静止浸取3次,每次提取6 h,得到止泻木子总生物碱提取物,其得率达到0.244%。经过硅胶柱分离和重结晶纯化,可获得3种生物碱单体。对HPLC检测纯度达到94.89%的2号生物碱单体进行核磁共振波谱和质谱检测,得知该生物碱单体是一个分子量为356.59的锥丝碱（conessine）。该结果有利于了解以止泻木子为主要成分的蒙药药剂作用机理。     

Synthesis and proton conductivity of sulfonic acid functionalized zeolite BEA nanocrystals

The objective of this study is to prepare sulfonic acid functionalized zeolite BEA nanocrystals, and determine the bulk proton conductivity of this new material. Phenethyl functionalized zeolite BEA nanocrystals are synthesized using a mixture of fumed silica and phenethyltrimethoxysilane as silica sources. Contact of the phenethyl zeolite BEA nanocrystals with concentrated sulfuric acid removes the organic structure-directing agent (SDA) and simultaneously sulfonates the phenethyl moieties. Detailed characterizations of the zeolite BEA nanocrystals are performed using dynamic light scattering (DLS), Fourier transform Raman spectroscopy (FT-Raman), ²⁹Si cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (²⁹Si CPMAS NMR), ¹³C CPMAS NMR, ¹H MAS NMR, thermogravimetric (TGA) analyses, transmission electron microscopy (TEM) and powder X-ray diffraction (XRD). Sulfonic acid functionalized zeolite BEA nanocrystals have proton conductivities in the range of 1.2 × 10⁻³–1.2 × 10⁻² S/cm compared to 1.5 × 10⁻⁴ S/cm for unfunctionalizated zeolite BEA.     

Optimum conditions for high resolution C n.m.r. of coal- and oil-derived products

Factors affecting the spin-lattice relaxation times T₁ of ¹³C resonances at 62.9 MHz were investigated for simple mixtures of tetralin, ethylbenzene, pentane and phenol and the prominent resonances of an anthracene oil and a coal-derived hydrogenation oil. Parameters varied were solvent temperature and nature—Cr(acac)₃, Cr(dpm)₃, Cr(hfac)₃, Fe(acac)₃, Fe(dpm)₃—and concentration of a paramagnetic relaxation agent (PARR). Effects of PARRs on relaxation rates are strongly dependent on neighbouring acidic or basic centres, but are much more uniform for Cr(hfac)₃ than for Cr(acac)₃. The presence of basic or acidic compounds does not significantly affect the relaxation of ¹³C of the neutral components. Optimum experimental conditions are characterized by nearly uniform T₁ values of all resonances to be detected. While 2D spectra allow disentanglement of overlapping lines, choosing optimum conditions for the neutral constituents may lead to a loss of signals from the acidic or basic compounds.     

季铵型改性壳聚糖的制备及其在兔毛织物抗菌整理中的应用

以三乙胺和环氧氯丙烷为原料,合成醚化剂3-氯-2-羟丙基三乙基氯化铵。以甲壳素为原料通过醚化反应合成了季铵型甲壳素（CCT）,再经脱乙酰得到季铵型阳离子改性壳聚糖（CCTS）。采用红外光谱（FTIR）、核磁碳谱（¹³C NMR）对其化学结构进行了表征,运用黏度法和分光光度法测定了黏均分子量和溶解性等理化性能。采用最小抑菌法对CCTS的抗菌活性进行了测定,得到其对大肠杆菌的最低有效抑菌浓度（MIC）为0.2g/L,优于天然壳聚糖的MIC值。以柠檬酸为交联剂、次磷酸钠为催化剂,用CCTS对兔毛织物进行抑菌整理,考察织物经整理的抑菌效果和耐洗性。经5次洗涤后结果表明,CCTS对大肠杆菌的抑菌率达99.9%以上,抑菌率高于CCT和天然壳聚糖,是一种针对动物毛织物良好的天然高分子长效抑菌整理剂。     

Al, N, C and H NMR spectra and negative-ion electrospray mass spectra of the 2:1 aluminium(III) complexes of azo dyes derived from anthranilic acid

The ²⁷Al, ¹⁵N, ¹³C and ¹H NMR spectra in DMSO and mass spectra of 2:1 aluminium(III) complexes (1b–4b) derived from anthranilic acid azo coupling products with 4-tert.butylphenol (1a), 2-naphthol (2a) acetoacetanilide (3a) 3-methyl-1-phenylpyrazol-5-one (4a) were measured and analysed. It was found that the aluminium atom was six-coordinated, being bound to two oxygens and the nitrogen originating from anthranilic acid.     

Estimation of silica flocculation in SBR/BR compounds reinforced with different silica contents from their rheocurves

The rheocurves of silica-filled styrene–butadiene/polybutadiene rubber (SBR/BR) compounds containing 3-octadecyltriethoxy silane (OTES) and bis-[triethoxysilylpropyl]tetrasulfide (TESPT) were investigated to examine the effects of silica content and silanes on silica flocculation during mixing and cure. SBR/BR compounds without curatives were also prepared to infer the effect of cure on silica flocculation. The maximum torque of the compounds could be deconvoluted to individual source torques such as silica flocculation during mixing and cure, crosslinking of rubber, and coupling between rubber and silica by assuming the independence of silica flocculation from cure and coupling. Torque due to silica flocculation increased with the silica content of the SBR/BR compounds, but its effect was significantly reduced by the addition of OTES or TESPT. TESPT suppressed silica flocculation and facilitated coupling, thus yielding enhanced tensile properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48559.     

C nuclear magnetic resonance spectral analysis of stereosequences in ethylene-propylene copolymer

A number of split peaks dependent on both comonomer sequences and stereosequences were observed in the ¹³C nuclear magnetic resonance (n.m.r.) spectrum of ethylene-propylene (E-P) copolymer. The ¹³C chemical shifts of methylene carbon in stereoisomers of the respective hexad comonomer sequences were predicted by a chemical-shift calculation using the gamma effect on ¹³C chemical shifts and Mark's rotational isomeric state model for E-P copolymer. Assignments of the split peaks that arise from different hexad stereosequences were given by comparison between the observed and calculated chemical shifts. Reference was made to the hexad assignments of comonomer-sequence-dependent peak splittings determined in our previous calculation of ¹³C n.m.r. chemical shifts of stereoregular E-P copolymers. The tacticities were estimated for successive (not separated by ethylene units) propylene units in the hexad sequences.     

CHAINGROWTH IN FISCHER-TROPSCH CATALYSIS, AS OBSERVED WITH TRANSIENT-KINETIC METHODS

An abrupt change in the reaction ambient from ¹²CO/H₂ to ¹³CO/H₂ leads to a gradual ingrowth of ¹³C in hydrocarbon chains. From the rate of ¹³C ingrowth we calculate C—C bonds to form on a time scale varying from ≤1 s (ruthenium) to ≥10s (cobalt).     

宁东红石湾煤大分子模型构建及量子化学计算

使用工业分析、元素分析、固体核磁（¹³C NMR）、X射线光电子能谱（XPS）、傅里叶变换红外光谱（FT-IR）对宁东红石湾（HSW）煤样进行表征,获得煤样中元素赋存的种类、价态、化学键环境等物质微观结构的关键参数。结果表明HSW煤结构以芳香族为主,占75.96%,桥接芳碳与周碳比为0.315,可知其结构中以萘为主,苯和蒽为辅。氧原子主要以醚氧基（C-O）、羰基（C=O）和羧基（-COO）的形式存在,其中C-O占53.57%。氮原子以吡啶和吡咯的形式存在。苯环的连接方式以三、四取代为主,分别占47.77%、32.97%,脂肪族中环烷烃或脂肪烃-CH₃占优势。确定HSW煤的分子式为C₂₂₁H₁₄₈O₂₈N₂,分子量为3142.32。在此基础上结合计算机辅助实现了二维和三维大分子模型构筑。应用量子化学计算对HSW煤大分子模型进行了优化及核磁共振、红外光谱模拟,验证了所建模型的合理性。最终实现了HSW煤的微观分子结构的实验与量子化学描述。     

Hydrocarbon structural group analysis of Athabasca asphaltene and its g.p.c. fractions by C n.m.r.

Asphaltene from the Athabasca oil sand bitumen separated according to molecular weight by gel permeation chromatography was examined by high resolution solution-state ¹³C and ¹H and solid state ¹³C n.m.r. Integration of the inverse gated decoupled solution state and CP/MAS ¹³C n.m.r. spectra gave the aromaticity of each fraction as well as the relative number of carbon atoms responsible for well resolved signals in the aliphatic portion of the spectra. A two-pulse spin-echo ¹³C n.m.r. sequence in the solution state, and dipolar dephasing in the solid state, permitted the assignment of each aliphatic carbon signal to a methyl, methylene, or methine carbon; no quaternary aliphatic carbons were observed. These signals show that the aromatic core of the asphaltene is surrounded by alkyl chains with a mean length of 7.7 for the lowest molecular weight fraction (MW 1200), increasing to 12 for the highest MW fraction (MW 16900). Aromaticity of the fractions obtained from solution spectra ranged from 34 to 48%, the highest aromaticity being associated with the lowest molecular weight asphaltenes. In the solid state, the aromaticity ranged from 31 to 42 %. The degree of branching ranged from 0.5 per chain for the low MW asphaltene to 1.0 for the high MW fraction. The highest naphthenic carbon content was found in the high MW fractions; the 1200 MW fraction appeared to be nearly devoid of such carbon, this fraction having a much higher aromaticity than the second-lowest MW fraction.     

Two-dimensional H- and C-NMR spectra of some azo dyes containing amino or acetamido groups

The ¹H- and ¹³C-NMR spectra of 12 azo dyes containing amino or acetamido groups have been measured. Two-dimensional H,H-COSY, NOESY, H,C-COSY and COLOC spectra and one-dimensional selective INEPT spectra have been used in the assignment of ¹H and ¹³C chemical shifts. Hydrogen bonding has also been studied in these compounds.     

The retarding action of sugars on cement hydration

Sugars retard the hydration of Portland cement. The effectiveness of different sugars is compared from studies of solution analysis, calorimetry, calcium binding ability and alkaline stability. The best retarders, sucrose and raffinose, have a remarkable ability to solubilize cement constituents and in particular give rise to dramatic increases in the amount of silica in solution. However, ¹³C and ²⁹Si N.M.R. do not reveal the existence of sucrose-silicate complexes. The retarding action of sugars is explained in terms of adsorption onto and poisoning of hydrate surfaces.