Effect of molecular architecture on the self-diffusion of polymers in aqueous systems: A comparison of linear, star, and dendritic poly(ethylene glycol)s

Star polymers with a hydrophobic cholane core and four poly(ethylene glycol) (PEG) arms, CA(EG_n)₄, have been synthesized by anionic polymerization. Pulsed-gradient spin-echo NMR spectroscopy was used to study the diffusion behavior of the star polymers, ranging from 1000 to 10,000 g/mol, in aqueous solutions and gels of poly(vinyl alcohol) (PVA) at 23 °C. The star polymers have a lower self-diffusion coefficient than linear PEGs at equivalent hydrodynamic radius. In water alone, the star polymers and their linear homologues have a similar diffusion behavior in the dilute regime, as demonstrated by the similar concentration dependence of the self-diffusion coefficients. In the semidilute regime, the star polymers tend to aggregate due to their amphiphilic properties, resulting in lower self-diffusion coefficients than those of linear PEGs. ¹H NMR T₁ measurements at 10-70 °C revealed that the PEG arms of the star polymers are more mobile than the core, suggesting the star polymers in solution have a conformation similar to that of poly(propylene imine) dendrimers.     

Quantitative determination of pore-structure change and permeability estimation under hydrate phase transition by NMR

Quantitatively characterizing the seepage features is critical important for multi-fluid flow in gas hydrate accumulations; however, limited researches concern water permeability during hydrate phase transition. In this work, nuclear magnetic resonance (NMR) measurement is employed to observe the in situ formation and dissociation of tetrahydrofuran (THF) hydrate in porous media. Results indicate that the relative free water and bound water consumption during hydrate phase transition can affect the seepage features of sediments. In addition, we investigate the growth habits of THF hydrate in quartz glass sand and find the growth pattern of the hydrate transforms from suspension to cementation when its saturation exceeds approximately 35%. The Tokyo model shows that the hydrate are heterogeneous distribution of pore-filling and likely to evolve in larger pores; The findings clearly show that NMR is an efficient and direct technique for investigating the seepage characteristics during hydrate phase transition as well as pore fluid distribution in sediments.     

Synthesis and characterization of high molecular weight water-soluble polymers

The synthesis of high molecular weight acrylic water-soluble polymers in heterophase water-in-oil polymerizations is discussed. A mechanism has been elucidated which includes elementary reactions in the continuous (organic) and dispersed (aqueous) phases, as well as the interfacial layer. The latter allows for the identification of interfacially active species which can concurrently enhance stability and increase the linear molecular weight of the polymer. Suitable species are found to contain multiple radically active functional groups on either the hydrophilic or hydrophobic moieties. A one-point light-scattering method is also developed which improves the accuracy in molecular-weight estimation to /pi5%. compared with /pi10% for the conventional dilution procedure. This is demonstrated for high molecular weight polyacrylamides and is found to reduce the sample measurement time fourfold, to 20 min.     

质量分数为25%高渗乙草胺乳油的研制

在w(乙草胺)=25%乙草胺乳油中加入高渗剂氮酮,使其活性成分渗透力大大增强,在有效成分降低一半的情况下,其药效优于或相当于w(乙草胺)=50%乙草胺乳油。通过对国内3个厂家生产的氮酮进行筛选,确定其生产厂家及用量,并对w(乙草胺)=25%高渗乙草胺乳油参照GB/T19137-2003《农药低温稳定性测定方法》及GB/T19136-2003《农药热贮稳定性测定方法》进行了冷贮、热贮实验,实验合格后,进行了田间药效及毒理实验,最后确定w(乙草胺)=25%高渗乙草胺乳油的配方。     

Design and preparation of high permeability porous mullite support for membranes by in-situ reaction

The natural mineral kaolin combined with alumina additives Al(OH)₃,α-Al₂O₃ and AlF₃ was used to prepare porous mullite ceramic membrane supports using an in-situ reaction. The effects of composition and sintering temperature on the sintering behavior, pore structure, permeability and microstructure of the resulting porous mullite supports were extensively investigated. The experimental results showed that excess SiO₂ in kaolin can be consumed by adding alumina precursors, which resulted in a stiff skeleton of interlinked needle-like mullite crystals in-situ during the sintering. The needle-like mullite crystals touched each other and formed a short network, which acted as a porous skeletal network structure. This network resulted in a highly permeable porous structure. The resulting support is suitable for the preparation of asymmetric ceramic membranes. The densification and pore structure of the support can be effectively adjusted by control of the quantity of alumina precursors in the composition and the sintering temperature. Sintering the subject mullite compositions at 1500 °C for two hours resulted in support structures with an average porosity of 45.9%, an average pore size of 1.3 µm and a penetrating porosity of 35.9%.     

Temperature-responsive permeability of porous PNIPAAm-g-PE membranes

Grafting a temperature-responsive polymer, poly(N-isopropylacrylamide) (PNIPAAm), onto porous polyethylene (PE) membranes by UV irradiation was investigated. A wide range of graft yields (5–449%) was achieved by varying irradiation time (20–240 min) and monomer concentration (1.2–3.6 wt %). Characterization by XPS and SEM shows that the graft polymers are located both on the external surfaces as well as inside the pores of the membranes. Diffusional permeation experiments show that two distinct types of temperature responses were observed, depending on the graft yield; permeability increases with temperature in low graft yield membranes, while permeability decreases with temperature in high graft yield membranes. A mechanism explaining the dual valve functions of the graft membrane is proposed based on the location of the graft polymers on the membrane. It was also observed the permeability response exhibits a maximum with permeant molecular weight. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2133–2142, 1998     

Synthesis and characterization of high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Solid‐state carbon‐13 NMR study of material composites based on sugarcane bagasse and thermoplastics polymers

The composites formed by sugarcane bagasse and thermoplastic polymers, such as polypropylene (PP), polyethylene (PE), and ethylene‐co‐vinyl acetate (EVA), have been analysed by carbon‐13 high‐resolution solid‐state nuclear magnetic resonance (NMR), employing crosspolarization magic angle spinning (CPMAS); variable contact‐time experiment and proton spin‐lattice relaxation time in the rotating frame. NMR responses showed that these techniques can be used to observe the degree of compatibility and homogeneity of different polymers composites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2150–2154, 2001     

Novel NMR techniques for porous media research

Recent years have seen a significant progress in the study of porous media of natural and industrial sources. This paper provides a brief outline of the recent technical development of NMR in this area. These progresses are relevant for NMR applications in material characterization.     

Rigid and microporous polymers for gas separation membranes

Microporous polymers are a class of microporous materials with high free volume elements and large surface areas. Microporous polymers have received much attention for various applications in gas separation, gas storage, and for clean energy resources due to their easy processability for mass production, as well as microporosity for high performance. This review describes recent research trends of microporous polymers in various energy related applications, especially for gas separations and gas storages. The new classes of microporous polymers, so-called thermally rearranged (TR) polymers and polymers of intrinsic microporosity (PIMs), have been developed by enhancing polymer rigidity to improve microporosity with sufficient free volume sizes. Their rigidity improves separation performance and efficiency with extraordinary gas permeability. Moreover, their solubility in organic solvents allows them to have potential use in large-scale industrial applications.     

高渗透性聚酯长丝土工布YH-301油剂的研制

本文通过对高渗透性聚酯长丝土工布油剂的特性分析，介绍了以阳离子季铵盐为抗静电剂，与其它醚型非离子表面活性剂复配出YH—301油剂，以及该油剂的稳定性好、泡沫少，效果良好。     

Synthesis, characterization, and high gas permeability of poly(diarylacetylene)s having fluorenyl groups

Diarylacetylenes having fluorenyl groups and other substituents (trimethylsilyl, t-butyl, bromine, fluorine) (1a-1) were polymerized with TaCl₅-n-Bu₄Sn. Monomers 1a-l produced high molecular weight polymers 2a-l (M_w 5.1 × 10⁵-1.3 × 10⁶) in 12-59% yields. All of the polymers were soluble in common organic solvents, and gave tough free-standing membranes by the solution casting method. The onset temperatures of weight loss of polymers 2a-l in air were over 400 °C, indicating considerably high thermal stability. All the polymer membranes showed high gas permeability; e.g., the oxygen permeability coefficient (PO₂) of 2a was as large as 4800 barrers. Membrane 2d possessing two fluorine atoms at meta and para positions of the phenyl ring showed the highest oxygen permeability (PO₂ = 6600 barrers) among the present polymers.     

Sequential vapor sorption of additional penetrants in preswollen polymers

Uptake and removal of a second penetrant in polymer samples preexposed to another vapor dictate many industrially important processes. Both the kinetics and equilibrium sorption can be strongly affected by the presence of the first permeant in the polymeric matrices. A novel experimental setup was constructed to study penetrant uptake in sequence. Sorption of the second vapor took place while the partial vapor pressure of the first vapor was maintained, so that diffusion into the preswollen polymer approximated transport in a pseudobinary system. Polybutylene was chosen in this work to illustrate the capability of this versatile experimental system. Both the rate of diffusion and equilibrium sorption of the second vapor were found to depend on the prevailing composition of the preswollen polymer for all penetrant pairs studied.     

疏水缔合水溶性聚合物的合成与表征

综述了疏水缔合型水溶性聚合物合成与表征方法，介绍了在合成过程中提高油溶性单体和水溶性单体混溶性的方法，简述了疏水物质含量的核磁共振、紫外光谱、裂解气相色谱等测定方法。     

Selective multi-component diffusion measurement in zeolites by pulsed field gradient NMR

The potential of pulsed field gradient (PFG) NMR for selective diffusion measurement in multi-component liquids is far from being fulfilled in multi-component diffusion studies with zeolites. We present two recent developments in PFG NMR instrumentation, which will significantly improve the measuring conditions for multi-component diffusion in zeolites and other nanoporous materials. They include options for an enhancement of the sensitivity with respect to smaller displacements by a novel principle of field gradient pulse matching and with respect to selectivity between different components by combining PFG NMR with magic angle spinning (MAS) NMR with a microimaging gradient system. The potentials and limitations of the two options are demonstrated by the first results of selective PFG NMR self-diffusion measurements with zeolitic adsorbate–adsorbent systems containing as much as four different species of guest molecules.     

稠油高温相对渗透率实验数据处理方法及软件开发

稠油高温相对渗透率实验数据处理包括水热物性参数计算、实验数据光滑插值、模型求解,这些过程依靠手工计算繁琐,效率低。常规相对渗透率数据处理方法拟合函数单一,适应性差。为此采用了Borland C＋＋编制了稠油蒸汽驱油、湿氮气驱油和热水驱油三种实验条件下的相对渗透率数据处理计算软件,提供了多种数据拟合和处理方法,并且考虑了实验仪器死体积中原油产出非活塞驱、压力滞后、数据波动、数据异常等因素的影响。该软件可以提高高温相渗数据处理的效率和准确性,易于实现数据处理的规范化。     

Thermodynamic model for the permeability of light gases in glassy polymers

The permeability of light gases in a series of different glassy polymers is analyzed through a thermodynamic‐based approach for solubility and diffusivity. The nonequilibrium thermodynamic model for glassy polymers describes the solubility of the different penetrants; diffusivity is given as the product of a mobility factor and a thermodynamic factor. The latter is predicted by the nonequilibrium lattice fluid thermodynamic model, while the mobility coefficient is determined using the experimental permeability data. For rather soluble penetrants (e.g., CO₂), a plasticization factor is also accounted for, considering the mobility to depend exponentially on penetrant concentration, as often observed experimentally. The model is able to describe accurately the experimental behavior in a simple and effective way, considering only two adjustable parameters. The mobility coefficient is found to depend on the penetrant size (critical volume) and on the fractional free volume of the polymer matrix, following rather general and reasonable correlations. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2776–2788, 2015     

Diffusion of ammonia in silicalite studied by QENS and PFG NMR

Ammonia diffusivities in silicalite have been studied by quasi-elastic neutron scattering (QENS) and pulsed-field gradient (PFG) NMR for temperatures between 200 and 500 K and loadings from 1.5 up to 4.3 molecules per unit cell. The diffusion coefficients obtained by both techniques increase with increasing ammonia concentration. The QENS diffusivities refer to only a certain fraction of molecules, because during the time scale of the measurement the other part of molecules is essentially immobile, in interaction with silanol groups. During the much larger time scale of the PFG NMR experiment, ammonia molecules assume both states of mobility, leading to an average diffusivity which is smaller than the diffusivity of the mobile molecules recorded by QENS. The difference between the diffusivities derived from both techniques decreases when the proportion of immobile molecules is taken into account. The residence time of ammonia in interaction with silanol groups is about two orders of magnitude longer than with oxygen atoms.     

NMR spectroscopy as basis for characterization of Pluronic® F108 and its derivatives

The hydroxyl end groups of Pluronic®F108 {a triblock copolymer surfactant of poly(ethylene glycol) and poly(propylene glycol) [PEG‐PPG‐PEG]} were modified into primary amine, sulfonic acid, and quaternary ammonium equivalents for use in affinity chromatography. NMR was used for monitoring the efficacy of modifications on intermediaries and final products. The primary amine equivalents were prepared via conversion of the hydroxyl groups to a tosylate, its displacement with an azide, followed by reduction to the primary amine. The sulfonic acid equivalents were prepared via hydroxyl group tosylation, the displacement of tosylate with thiol, and its oxidation to sulfonic acid. The conversion to trimethyl ammonium was achieved via hydroxyl group tosylation, tosylate displacement by halide, and halide displacement with trimethylamine. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 109–117, 2000