High Temperature Gel Research Articles

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One of the main challenges in developing a process of continuous steam injection is to control the injection profile. Said profile is strongly affected by steam channeling to “thief zones” and the gravitational effect of override, both are characterized by preventing contact of the steam with reservoir zones containing considerable amounts of hydrocarbons thus decreasing the vertical sweep efficiency. These phenomena are favored by some features of the formation such as large thickness and reservoir heterogeneities and may affect the technical and economic feasibility of the project if they are not controlled and / or monitored properly.Several methodologies have been designed to address this problem. Among them are injecting surfactants for the formation of in situ foam, which seeks to reduce the mobility of steam; using thermal gels, for plugging high permeability channels; injection of solvents, used to enhance oil mobility; and water-alternating-steam injection (WASP) for scavenging of both upper and lower zone of the formation. This article collects relevant aspects of the mentioned methods, and a comparison is made in base of the number of applications, incremental production and implementation cost.Keywords: Steamflooding, In Situ Foams, Solvents, High Temperature Gels, Water Alternating Steam.

Rheological properties and crystallization behaviors of long chain branched polyethylene prepared by melt branching reaction

Abstract Long chain branched polyethylene (LCBPE) without gel was prepared by melt branching reaction in a Haake torque rheometer in the presence of peroxide and different multi-functional acrylate monomers, and the optimal reaction time was determined according to the transient torque curves. The Fourier transform infrared (FTIR) results indicated that multi-functional monomers had been grafted onto HDPE backbone. Rheometer, 13C NMR, and high-temperature gel permeation chromatography (HT-GPC) coupled with triple detectors were used to characterize the microstructure of the LCBPE. The results showed the LCB content and the degree of branching increased with the increasing of functionality of the multi-functional monomers. Moreover, the LCBPE samples exhibited higher apparent zero shear rate activation energy and clear strain-hardening behavior compared with pure HDPE. Various rheological plots including viscosity, storage modulus, loss angle, and Cole-Cole plots were used to distinguish LCBPE from linear HDPE. A possible mechanism for melt branching reaction was also discussed in this paper. Differential scanning calorimetry (DSC) and polarized optical microscopy (POM) were used to study the influences of LCB on the crystallization behavior and crystal morphology of all samples. It was found that the melt temperature and crystal morphologies of LCBPE were evidently different from that of pure HDPE due to the introduction of LCB.

The mechanism of grafting of maleic anhydride onto isotactic polybutene-1 assisted by comonomers

Radical melt grafting reactions between isotactic polybutene-1 (iPB-1) and maleic anhydride (MAH) were performed with different comonomers including styrene (St), alpha methyl styrene (AMS), and 1-decene in a Torque Rheometer. The reaction mechanism of comonomer/MAH melt grafting on iPB-1 was investigated by Fourier transform infrared spectroscopy (FTIR), high temperature gel permeation chromatography (HT-GPC), melt flow rate (MFR), and gel content test. The results showed that MAH grafted onto iPB-1 after degradation of macromolecular chains without comonomers. In contrast, in the presence of comonomers, intermediates that could graft on iPB-1 main chains before its degradation were obtained, so the three comonomers were able to suppress the degradation thus increasing the grafting degree of MAH. The intermediates could be 1-decene-co-MAH or electron transfer complex (CTC) while St or AMS was added. Moreover, AMS and 1-decene increased the molecular weight and polydispersity of iPB-1 because macroradicals tended to have coupling termination.

Solvent gradient fractionation and chain microstructure of complex branched polyethylene resin

A complex branched polyethylene resin with excellent processing and film-forming properties is fractionated through solvent gradient fractionation (SGF) technique. Here, the good solvent is 1,2,4-trimethylbenzene (TMB) and poor solvent is ethyl cellosolve (ECS). The fractions are further analyzed using high-temperature gel permeation chromatography (GPC) coupled with triple detectors (refractive index (RI)-light scattering (LS)-viscometer (VIS)), and 13C-nuclear magnetic resonance spectroscopy (13C-NMR). The molecular weight distribution of SGF fractions is very narrow, most of them are less than 1.1. The molecular weights of SGF fractions gradually increase as the content of good solvent increases in the mixture. The fractions with different molecular weights all have branching structure, the short chain branching is major in all fractions and along with certain content of long chain branching. Branching distribution across the molecular weight distribution is discussed in detail, and branching distribution within a SGF fraction is also researched.

Characterization of Low-Density Polyethylene in Dibutoxymethane by High-Temperature Gel Permeation Chromatography with Triple Detection

The study presents the possibility to replace the 1,2,4-trichlorobenzene (TCB) for the analysis by gel permeation chromatography (GPC) of low-density polyethylenes (LDPE) with dibutoxymethane (DBM, butylal), a halogen free and less toxic solvent. The molecular weight distributions and the viscosity plots were measured for commercial LDPE samples solubilized in TCB, and DBM, using a GPC system with triple detection (light scattering, differential refractive index and viscometer). Similar results were obtained in both solvents for the molecular weight and long chain branching distributions of the analyzed resins, thus confirming the possibility to replace TCB with DBM for the analysis by high-temperature GPC of all types of polyolefins.

Thermo‐oxidative degradation of additive free polyethylene. Part I. Analysis of chemical modifications at molecular and macromolecular scales

ABSTRACTThe effects of thermal oxidation on the molecular and macromolecular structures of additive free PE were investigated between 100 °C and 140 °C in air in order to tentatively establish non‐empirical structure/property relationships. In the first part, the changes in POOH concentration were assessed by three different analytical methods: iodometry, modulated differential scanning calorimetry, and Fourier transform infrared (FTIR) spectrophotometry after SO2treatment. All these methods provided very similar results until the end of the induction period, after which iodometry overestimated strongly POOH concentration because it titrates also other chemical species formed at high conversion ratios, namely double bonds. In parallel, the changes in carbonyl group concentration were determined by FTIR spectrophotometry after NH3treatment. As the accumulation kinetics of ketones, aldehydes, and carboxylic acids were closely interrelated, the question of their actual formation mechanisms in the current thermal oxidation mechanistic scheme was raised. An alternative reaction pathway was proposed for the bimolecular decomposition of POOH. In the second part, the corresponding changes in weight and number average molecular masses were monitored by high temperature gel permeation chromatography equipped with a triple detection technology. As both quantities decreased dramatically from the beginning of exposure and their ratioMw/Mntends toward the asymptotic value of 2 and it was concluded that a “pure” chain scission process operated. Finally, as the number of chain scissions perfectly correlates, the concentration sum of aldehydes and their oxidation products (i.e., carboxylic acids), it was also concluded that these carbonyl groups result exclusively from the β scission of alkoxy radicals. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43287.

A New High-Temperature Gel for Profile Control in Heavy Oil Reservoirs

Controlling the phenomenon of steam channeling is a major challenge in enhancing oil recovery of heavy oil reservoirs developed by steam injection, and the profile control with gel is an effective method to solve this problem. The use of conventional gel in water flooding reservoirs also has poor heat stability, so this paper proposes a new high-temperature gel (HTG) plugging agent on the basis of a laboratory experimental investigation. The HTG is prepared with nonionic filler and unsaturated amide monomer (AM) by graft polymerization and crosslinking, and the optimal gel formula, which has strong gelling strength and controllable gelation time, is obtained by the optimization of the concentration of main agent, AM/FT ratio, crosslinker, and initiator. To test the adaptability of the new HTG to heavy oil reservoirs and the performance of plugging steam channeling path and enhancing oil recovery, performance evaluation experiments and three-dimensional steam flooding and gel profile control experiments are conducted. The performance evaluation experiments indicate that the HTG has strong salt resistance and heat stability and still maintains strong gelling strength after 72 hrs at 200 °C. The singular sand-pack flooding experiments suggest that the HTG has good injectability, which can ensure the on-site construction safety. Moreover, the HTG has a high plugging pressure and washing out resistance to the high-temperature steam after gel forming and keeps the plugging ratio above 99.8% when the following steam injected volume reaches 10 PV after gel breakthrough. The three-dimensional steam flooding and gel profile control experiments results show that the HTG has good plugging performance in the steam channeling path and effectively controls its expanding. This forces the following steam, which is the steam injected after the gelling of HTG in the model, to flow through the steam unswept area, which improves the steam injection profile. During the gel profile control period, the cumulative oil production increases by 294.4 ml and the oil recovery is enhanced by 8.4%. Thus, this new HTG has a good effect in improving the steam injection profile and enhancing oil recovery and can be used to control the steam channeling in heavy oil reservoirs.

Novel polyethylene‐b‐polyurethane‐b‐polyethylene triblock copolymers: Facile synthesis and application

ABSTRACTA series of novel polyethylene‐b‐polyurethane‐b‐polyethylene (EUE) triblock copolymers is successfully prepared through a facile route combining the thiol‐ene chemistry, addition polymerization, and coupling reaction. The resulting EUE triblock copolymers are characterized by Nuclear magnetic resonance (1H NMR), Fourier transform‐infrared spectra (FT‐IR), High temperature gel permeation chromatography (HT‐GPC), Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), and Transmission electron microscopy (TEM). In addition, the EUE triblock copolymers have been evaluated as compatibilizers in the polymer blends of thermoplastic polyurethane elastomer (TPU) and high‐density polyethylene (HDPE). The SEM results show that the compatibility of immiscible blends is enhanced greatly after the addition of EUE triblock copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42967.

Preparation and Characterization of Polymeric Surfactants Based on Epoxidized Soybean Oil Grafted Hydroxyethyl Cellulose.

Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC) was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC acted as initiators and the polymeric ESO were covalently bonded to the HEC. Hydrolysis of ESO-grafted HEC (ESO-HEC) was performed with sodium hydroxide, and the hydrolyzed ESO-HEC (H-ESO-HEC) products were characterized via Fourier transform infrared (FT-IR) and (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopies, high-temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The results indicated that ring-opening polymerization of ESO occurred with the hydroxyl groups of HEC as initiators. The molecular weights of the H-ESO-HEC products were varied by adjusting the mass ratio of HEC and ESO. Through neutralizing the carboxylic acid of H-ESO-HEC with sodium hydroxide, novel polymeric surfactants (H-ESO-HEC-Na) were obtained, and the effects of polymeric surfactants on the surface tension of water were investigated as a function of concentration of H-ESO-HEC-Na. The H-ESO-HEC-Na was effective at lowering the surface tension of water to 26.33 mN/m, and the critical micelle concentration (CMC) value decreased from 1.053 to 0.157 g/L with increases in molecular weights of the polymeric surfactants. Rheological measurements indicated that the H-ESO-HEC-Na solutions changed from pseudoplastic property to Newtonian with increasing shear rate.

Analysis of Propylene‐1‐Butene Copolymer Composition by GPC with Online Detectors

SummaryThe use of High Temperature Gel Permeation Chromatography (HT‐GPC) with online infrared (IR) detector to analyze copolymer composition of propylene‐1‐butene (P‐B) copolymer is investigated in this study. This technique is based on the measurement of the methyl to methylene ratio by an online infrared detector. This measurement is made possible by the highly discriminating power of a modern multiple band filter‐based IR detector (IR5 MCT) to detect the P–B copolymer chemical structure. Also discussed is an alternative method, based on the application of the triple‐detector GPC (GPC with IR, viscometer and light scattering coupled detectors) approach and Mark–Houwink plot.

Comparison of chain structures between high-speed extrusion coating polyethylene resins by preparative temperature rising elution fractionation and cross-fractionation

Two polyethylene (PE) resins (samples A and B) are synthesized as high-speed extrusion coatings with similar minimum coating thickness and neck-in performance but different maximum coating speeds. Both samples are separated into seven fractions using preparative temperature rising elution fractionation. The microstructures of the original samples and their fractions are studied by high-temperature gel permeation chromatography, Fourier transform infrared spectroscopy, 13C nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and successive self-nucleation/annealing thermal fractionation. Compared with sample B, sample A has a broader MWD, more LCB contents, and less SCB contents. Moreover, sample A contains slightly more 30 °C and 50 °C fractions with lower molecular weights, and more fractions at 75 °C and 85 °C with higher molecular weight. The chain structure and its distribution in the two PE resins are studied in detail, and the relationship between the chain structure and resin properties is also discussed.

Characterization of Polypropylene in Dibutoxymethane by High-Temperature Gel Permeation Chromatography with Triple Detection

This study presents the possibility of replacing the 1,2,4-trichlorobenzene (TCB) recommended by ASTM D 6474 for the analysis by gel permeation chromatography (GPC) of polypropylenes with dibutoxymethane (DBM, butylal), a halogen-free and less toxic solvent. The molecular weight distributions as well as the K and alpha parameters of the Mark-Houwink-Sakurada equation were measured for different types of commercial polypropylene samples solubilized in TCB and DBM, using a GPC system with triple detection (light scattering, differential refractive index, and viscometer). For the analyzed resins, covering typical applications of polypropylene, the GPC method in DBM provided results similar to those obtained in TCB.

Thermomechanical modeling and simulation of a silicone gel for power electronic devices

The aim of the study is to develop some nodal models describing thermomechanical link in power devices. It is focused on modeling, simulating and testing a component: the silicone gel used in power electronics modules. Due to the future availability of high temperature gel, this study is a first step to establish a multi-physic model. The study aims to establish fast and compact electro-thermomechanical model than can be connected to circuit models, representing other packaging components. In the first stage, a finite element model of a commercial gel is defined and some simulation results are presented. In the second stage, an equivalent “electrical” compact model is also suggested and compared to measurements and 3D simulation results. The results presented concern temperature dispatching in both, simulations and measurements, and averaged stresses as well as displacement within the silicone. Future works will describe the thermomechanical link in nodal models, as well as real environment surrounding the silicone gel. Indeed, the silicone thermal expansion impact will be monitored.

Preparation of linear low-density polyethylene from ethylene by tandem catalysis of titanium(IV) and nickel(II) non-metallocene catalysts

Non-metallocene titanium(IV) complexes of 2-hydroxymethylphenol derivatives [O^O]TiCl2 2iPrOH (2–3), which can form a tandem catalytic system with a phenoxy-imine nickel complex (1), were firstly used as an in situ copolymerization catalyst to prepare linear low-density polyethylene (LLDPE) with ethylene as the sole monomer stock and Et2AlCl/Bu2Mg as the cocatalyst. During the reaction, 1/Et2AlCl oligomerized ethylene to linear α-olefins with high activity and selectivity, while 2–3/Et2AlCl+Bu2Mg copolymerized ethylene with the in situ generated α-olefins to LLDPE with high activity (up to 7.4×105g/molTihatm). The influence of the reaction conditions upon the catalytic activity and polymer structures and properties have been researched. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature 13C NMR spectroscopy and they were proven to be LLDPE with ethyl and butyl branches. The compositions of comonomers were tuned efficiently from 2% to 6% by different reaction conditions such as reaction temperature, Ni/Ti molar ratio and Al/(Ni+Ti) molar ratio. The melting points, degree of crystallinity and molecular weights (2.7×105–1.5×106) also changed correspondingly with the reaction conditions.

Well-Defined Polyethylene-Based Random, Block, and Bilayered Molecular Cobrushes

Novel well-defined polyethylene-based random, block, and bilayered molecular cobrushes were synthesized through the macromonomer strategy. Two steps were involved in this approach: (i) synthesis of norbornyl-terminated macromonomers of polyethylene (PE), polycaprolactone (PCL), poly(ethylene oxide) (PEO), and polystyrene (PS), as well as polyethylene-b-polycaprolactone (PE-b-PCL), by esterification of the hydroxyl-terminated precursors (PE, PCL, PEO, PS, and PE-b-PCL) with 5-norbornene-2-carboxylic acid and (ii) ring-opening metathesis (co)polymerization of the resulting macromonomers to afford the PE-based molecular cobrushes. The PE-macromonomers were synthesized by polyhomologation of dimethylsulfoxonium methylide, while the others by anionic polymerization. Proton nuclear magnetic resonance spectroscopy (1H NMR) and high-temperature gel permeation chromatography (HT-GPC) were used to imprint the molecular characteristics of all macromonomers and molecular brushes and differential scanning calorimetry (DSC) for the thermal properties. The bilayered molecular cobrushes of P(PE-b-PCL) adopt a wormlike morphology on silica wafer as visualized by atomic force microscopy (AFM).

Calibration curve establishment and fractionation temperature selection of polyethylene for preparative temperature rising elution fractionation

A series of copolymers of ethylene with 1-hexene synthesized using a metallocene catalyst are selected and mixed. The blend is fractionated via preparative temperature rising elution fractionation (P-TREF). All fractions are characterized via high-temperature gel permeation chromatography (GPC), C-13 nuclear magnetic resonance spectroscopy (C-13-NMR), and differential scanning calorimetry (DSC). The changes in the DSC melting peak temperatures of the fractions from P-TREF as a function of elution temperature are almost linear, thereby providing a reference through which the elution temperature of TREF experiments could be selected. Moreover, the standard calibration curve (ethylene/1-hexene) of P-TREF is established, which relates to the degree of short-chain branching of the fractions. The standard calibration curve of P-TREF is beneficial to study on the complicated branching structure of polyethylene. A convenient method for selecting the fractionation temperature for TREF experiments is elaborated. The polyethylene sample is fractionated via successive self-nucleation and annealing (SSA) thermal fractionation. A multiple-melting endotherm is obtained through the final DSC heating scan for the sample after SSA thermal fractionation. A series of fractionation temperatures are then selected through the relationship between the DSC melting peak temperature and TREF elution temperature.

Methylcellulose, a Cellulose Derivative with Original Physical Properties and Extended Applications

This review covers the preparation, characterization, properties, and applications of methylcelluloses (MC). In particular, the influence of different chemical modifications of cellulose (under both heterogeneous and homogeneous conditions) is discussed in relation to the physical properties (solubility, gelation) of the methylcelluloses. The molecular weight (MW) obtained from the viscosity is presented together with the nuclear magnetic resonance (NMR) analysis required for the determination of the degree of methylation. The influence of the molecular weight on the main physical properties of methylcellulose in aqueous solution is analyzed. The interfacial properties are examined together with thermogelation. The surface tension and adsorption at interfaces are described: surface tension in aqueous solution is independent of molecular weight but the adsorption at the solid interface depends on the MW, the higher the MW the thicker the polymeric layer adsorbed. The two-step mechanism of gelation is confirmed and it is shown that the elastic moduli of high temperature gels are not dependent on the molecular weight but only on polymer concentration. Finally, the main applications of MC are listed showing the broad range of applications of these water soluble cellulose derivatives.

Characterization of Polyethylene in Dibutoxymethane by High-Temperature Gel Permeation Chromatography with Triple Detection

This study presents the possibility of replacing the 1,2,4-trichlorobenzene (TCB) recommended by ASTM D 6474 for the analysis by gel permeation chromatography (GPC) of linear polyethylenes with dibutoxymethane (DBM, butylal), a halogen-free and less toxic solvent. The molecular weight distributions as well as the K and alpha parameters of the Mark-Houwink-Sakurada relationship were measured for polyethylene solutions in TCB and DBM, using a GPC system with triple detection (light scattering, differential refractive index, and viscometer). For commercial metallocene polyethylene resins typically used for film and packaging applications, the GPC method in DBM provided results comparable to those obtained in TCB.

Microstructure characterization of a complex branched low-density polyethylene

A low-density polyethylene (LDPE) resin with excellent processing and film-forming properties is fractionated through temperature rising elution fractionation (TREF) technique. The chain structures of both the original resin and its fractions are further analyzed using high-temperature gel permeation chromatography (GPC) coupled with triple detectors (refractive index (RI)-light scattering (LS)-viscometer (VIS)), 13C-nuclear magnetic resonance spectroscopy (13C-NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and successive self-nucleation/annealing (SSA) thermal fractionation. The 13C-NMR results show that the original resin has both short chain branch (SCB) (2.82 mol%) and long chain branch (LCB) (0.52 mol%) structures. The FTIR results indicate that the methyl numbers (per 1000 C) of the fractions gradually decrease from 81 to 46 with increasing elution temperature from 25 °C to 75 °C. The TREF-GPC cross-fractionation results show that the main component is collected at around 68 °C. The molecular weight of the components in the high elution temperatures of 60 °C to 75 °C is from 2.0 × 103 g/mol to 2.0 × 106 g/mol, and the relative amount is more than 80%. In the low elution temperature region below 50 °C, the molecular weights of the components range from 1.0 × 103 g/mol to 1.6 × 104 g/mol, and the relative amount is less than 10%. In the DSC results, the melting peaks of the fractions gradually increase from 80.1 °C to 108.8 °C with elution temperature. In the SSA thermal fractionation, each resin fraction shows a broad range of endotherm with multiple melting peaks (more than eight peaks). The melting peaks shift toward high temperatures with the elution temperature. The characteristic chain microstructure for the resin is also discussed in detail.

Comparing linear and cyclic synthetic homopolypeptides: Synthesis and molecular characterization

ABSTRACTThe synthesis and molecular characterization of a linear and a cyclic homopolypeptide of protected l‐tyrosine are reported. In this work, the successful synthesis of polypeptides exhibiting the desired linear and cyclic structures through various characterization methods such as high temperature gel permeation chromatography, Fourier transform infrared spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy, mass spectrometry, dynamic light scattering, differential scanning calorimetry, and thermogravimetric analysis was verified. The results are very promising especially if such cyclic materials will be potentially used as carriers for drug delivery, either through conjugation with specific ligands or directly through the functional hydroxyl groups of the monomeric units of poly(l‐Tyr) after deprotection. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 393–404