CO2‐Switchable Oil/Water Emulsion for Pipeline Transport of Heavy Oil

By mixing an aqueous solution of tertiary amine, N,N‐dimethylethanolamine (DMEA), with naphthenic acid (RCOOH) derived from heavy oil, a CO₂ switchable zwitterionic surfactant (RCOO^?DMEAH⁺) aqueous system was constructed. The CO₂ switchability of this zwitterionic surfactant was confirmed by visual inspection, pH measurements, and conductivity tests, i.e., the RCOO^?DMEAH⁺ decomposed into RCOOH, DMEAH⁺ and HCO₃^? after bubbling CO₂ through but switched back to its original state by subsequent bubbling N₂ through at 80 °C to remove the CO₂. The interfacial tension tests of heavy oil in DMEA aqueous solutions indicated that the solution containing 0.5 wt% of DMEA and 0.2 wt% of NaCl resulted in the lowest interfacial tension. The O/W emulsion formed when aqueous solutions of DMEA were used to emulsify heavy oil exhibited the best performance when the oil/water volume ratio, DMEA concentration, and NaCl concentration were 65:35, 0.5 and 0.2 wt%, respectively. The feasibility of pipeline transport of the O/W heavy oil emulsion was evaluated. The results illustrated that the demulsification of the O/W emulsion after transport could be easily realized by bubbling CO₂ through. Although demulsification efficiency still needs to be improved, the recycling of the aqueous phase after demulsification by removal of CO₂ looks promising.     

Synthesis and Performance Evaluation of CO2/N2 Switchable Tertiary Amine Gemini Surfactant

A type of switchable tertiary amine Gemini surfactant, N,N′‐di(N,N‐dimethyl propylamine)‐N,N′‐didodecyl ethylenediamine, was synthesized by two substitution reactions with 3‐chloro‐1‐(N,N‐dimethyl) propylamine, bromododecane and ethylene diamine as main raw materials. The structure of the product was characterized by FTIR and ¹H‐NMR. We also investigated the surface tension when CO₂ was bubbled in different concentrations of surfactant solution and the influence of different CO₂ volumes on surface tension under a constant surfactant concentration. Finally the surface tension curve and the related parameters were acquired by surface tension measurements. The experimental results showed that the structure of the synthesized compounds were in conformity with the expected structure of the surfactant, and displayed a better surface activity after bubbling CO₂. The critical micelle concentration (CMC) surface tension at CMC (γ_cmc) pC₂₀ (negative logarithm of the surfactant's molar concentration C₂₀, required to reduce the surface tension by 20 mN/m) surface excess (Γ_max) at air/solution interface and the minimum area per surfactant molecule at the air/solution interface (A_min) were determined. Results indicate that the target product had good surface activity after bubbling CO₂.     

Carbon dioxide switchable polymer surfactant copolymerized with 2‐(dimethylamino)ethyl methacrylate and butyl methacrylate as a heavy‐oil emulsifier

A CO₂‐switchable polymer surfactant was synthesized with 2‐(dimethylamino)ethyl methacrylate and butyl methacrylate. The conductivity, ζ potential, and particle size change illustrated the switchability of the surfactant, and this change could be repeated. Its surface tension decreased sharply when the sample was bubbled with CO₂; this indicated the enhancement of the surface activity. In the heavy‐oil emulsion with a surfactant concentration of 8 g/L, the viscosity almost reached the highest stability. When CO₂ overflowed the emulsion, it became unstable when the temperature beyond 40°C. The emulsion had a nice resistance to inorganic salt, which was maintained stably even when the concentration of NaCl was as high as 90,000 ppm. The emulsion could later be broken by the removal of CO₂. Its hydration rate was over 22 times faster than that in the presence of CO₂. The amount of residual oil in water was only about 53.84 ppm; this showed a good demulsification ability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41307.     

Carbon Dioxide Absorption into Stirred Emulsions of n‐Alkanes

Volumetric mass transfer coefficients k_La for CO₂ absorption into n‐alkane/water emulsions were determined at oil volume fractions of 0–100 % in a stirred tank at a stirring speed of 1000 min^?1. The oil was n‐heptane, n‐hexadecane, or n‐dodecane. The decrease of k_La with increasing volume fraction of dispersed oil can be uniformly correlated to the emulsion viscosity with the power of ?0.72. Only the addition of n‐heptane caused a strong increase of the mass transfer coefficient. Upon addition of the surfactant sodium dodecyl sulfate to n‐heptane emulsions, k_La decreased as for the other oils. The increase can therefore be attributed to the spreading of n‐heptane on the bubble surface enabling gas‐oil contact, whereas spreading is inhibited by the ionic surfactant.     

Synthesis of switchable amphipathic molecules triggered by CO2 through carbonyl‐amine condensation

Five long‐chain alkyl amidines were synthesized by condensation of N,N‐dimethylacetamide with octylamine, decylamine, dodecylamine, tetradecylamine, and hexadecylamine, respectively. Synthesis conditions including solvent, pH, temperature, and ratio of reactants were studied. The series of long‐chain alkyl amidine compounds reacted with dry ice to produce amidinium bicarbonates cationic amphipathic molecules. The critical micelle concentration (cmc) and surface tension at cmc (γ_cmc) measured by drop volume method show that these amphipathic molecules have excellent surface activity. The changes of cationic content measured by two‐phase titration and conductivity before and after bubbling CO₂, show different properties between amidines and amidinium bicarbonates cationic amphipathic molecules. The switchable function of the amidinium bicarbonate cationic amphipathic molecule in emulsification and demulsification was studied. Practical applications : Our innovative work is synthesizing switchable amphipathic molecules, N′‐alkyl‐N,N‐dimethylacetamidines, by carbonyl‐amine condensation. Compared with a former way of synthesis, our work shows great potential advantages in industrial application. Our synthesis route is simpler with higher yield and is carried out at ambient temperature. Moreover, the products are environmentally friendly. Compared with traditional amphipathic molecules, our products, N′‐alkyl‐N,N‐dimethylacetamidines, show good switchable properties, which can be switched on and off, trigged by CO₂.This means these products can be reused for several times, which is significant for environmental protection.     

CO2‐responsive polymer surfactant formed by noncovalent binding between dimethyl‐dodecylamine and alginate

A new kind of polymer surfactant, noncovalent binding between N,N‐dimethyl‐dodecylamine and alginate (C₁₂A‐Alg), was successfully prepared by mixing N,N‐dimethyl‐dodecylamine (C₁₂A) and sodium alginate (NaAlg) in the appropriate mole ratio and bubbling CO₂. C₁₂A was successfully grafted onto the alginate molecule by electrostatic interaction. The structure of C₁₂A‐Alg was confirmed by Fourier transform infrared and NMR spectroscopies. The polymer surfactant C₁₂A‐Alg has superior performance in foamability and emulsification. This foaming/defoaming and emulsification/demulsification behavior can be triggered by bubbling CO₂/N₂, demonstrating that the polymer surfactant C₁₂A‐Alg is switchable. © 2018 Society of Chemical Industry     

Solubilization and release of fragrance agents in the aqueous solution of CO2 switchable surfactants

This study describes the enhancement in the solubility and controlled-release of fragrance agents (menthol, four n-alkanols, and three aromatic esters) using three CO₂ switchable surfactants (N-alkylimidazolium bicarbonates). The surfactants significantly improved the solubility of fragrance agents in water. N-Dodecylimidazolium bicarbonate was the most effective surfactant to solubilize menthol. A stability test indicated that the surfactant could stably disperse menthol in water. Moreover, the surfactants improved the solubility of n-alkanols to different levels, however, the solubility of the aromatic esters equally. The release of menthol from the surfactant solution under N₂ at different durations of bubbling time, temperatures, and flow velocities were studied.     

In situ surfactant generation as a means of miniemulsification?

In situ emulsification, where the surfactant is synthesized spontaneously at the oil/water interface, has been put forth as a simpler method for the preparation of miniemulsions‐like systems. Miniemulsions are relatively stable oil‐(e.g., monomer)‐in‐water emulsions having droplet sizes anywhere in the range of 50–500 nm, and are typically created with high shear and stabilized by the combination a surfactant and a costabilizer. Using the in situ method of preparation, emulsion stability and droplet and particle sizes were monitored and compared with conventional emulsions and miniemulsions. Styrene emulsions prepared by the in situ method do not demonstrate the stability of a comparable miniemulsion. Upon polymerization, the final particle size generated from the in situ emulsion did not differ significantly from the comparable conventional emulsion polymerization; the reaction mechanism for in situ emulsions is more like conventional emulsion polymerization rather than miniemulsion polymerization. Similar results were found when the in situ method was applied to controlled free radical polymerizations (CFRP), which have been advanced as a potential application of the method. Molecular weight control was found to be achieved via diffusion of the CFRP agents through the aqueous phase owing to limited water solubilities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Stability improvement of CO2 foam for enhanced oil‐recovery applications using polyelectrolytes and polyelectrolyte complex nanoparticles

CO₂ foam for enhanced oil‐recovery applications has been traditionally used in order to address mobility‐control problems that occur during CO₂ flooding. However, the supercritical CO₂ foam generated by surfactant has a few shortcomings, such as loss of surfactant to the formation due to adsorption and lack of a stable front in the presence of crude oil. These problems arise because surfactants dynamically leave and enter the foam interface. We discuss the addition of polyelectrolytes and polyelectrolyte complex nanoparticles (PECNP) to the surfactant solution to stabilize the interface using electrostatic forces to generate stronger and longer‐lasting foams. An optimized ratio and pH of the polyelectrolytes was used to generate the nanoparticles. Thereafter we studied the interaction of the polyelectrolyte–surfactant CO₂ foam and the polyelectrolyte complex nanoparticle–surfactant CO₂ foam with crude oil in a high‐pressure, high‐temperature static view cell. The nanoparticle–surfactant CO₂ foam system was found to be more durable in the presence of crude oil. Understanding the rheology of the foam becomes crucial in determining the effect of shear on the viscosity of the foam. A high‐pressure, high‐temperature rheometer setup was used to shear the CO₂ foam for the three different systems, and the viscosity was measured with time. It was found that the viscosity of the CO₂ foams generated by these new systems of polyelectrolytes was slightly better than the surfactant‐generated CO₂ foams. Core‐flood experiments were conducted in the absence and presence of crude oil to understand the foam mobility and the oil recovered. The core‐flood experiments in the presence of crude oil show promising results for the CO₂ foams generated by nanoparticle–surfactant and polyelectrolyte–surfactant systems. This paper also reviews the extent of damage, if any, that could be caused by the injection of nanoparticles. It was observed that the PECNP–surfactant system produced 58.33% of the residual oil, while the surfactant system itself produced 47.6% of the residual oil in place. Most importantly, the PECNP system produced 9.1% of the oil left after the core was flooded with the surfactant foam system. This proves that the PECNP system was able to extract more oil from the core when the surfactant foam system was already injected. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44491.     

Stabilization of CO2‐in‐water emulsions with high internal phase volume using PVAc‐b‐PVP and PVP‐b‐PVAc‐b‐PVP as emulsifying agents

Two newly‐designed hydrocarbon surfactants, that is, poly(vinyl acetate)‐block‐poly(1‐vinyl‐2‐pyrrolidone) (PVAc‐b‐PVP) and PVP‐b‐PVAc‐b‐PVP, were synthesized using reversible addition–fragmentation chain transfer polymerization and used to form CO₂/water (C/W) emulsions with high internal phase volume and good stability against flocculation and coalescence up to 60 h. Their structures were precisely determined by nuclear magnetic resonance, gel permeation chromatography, thermal gravimetric analysis, and differential scanning calorimetry. Besides low temperature and high CO₂ pressure, the surfactant structures were the key factors affecting the formation and stability of high internal phase C/W emulsions, including the polymerization degrees of CO₂‐philic block (PVAc) and hydrophilic block (PVP), as well as the number of hydrophilic tail. The surface tension of the surfactant aqueous solution and the apparent viscosity of the C/W emulsions were also measured to characterize the surfactants efficiency and effectiveness. The surfactants with double hydrophilic tails showed stronger emulsifying ability than those with single hydrophilic tail. The great enhancement of the emulsions stability was due to decrease of the interface tension as well as increase of the steric hindrance in the water lamellae, preventing a frequent collision of CO₂ droplets and their fast coalescence. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46351.     

CO2‐switchable polymeric vesicle‐network structure transition induced by a hairpin‐line molecular configuration conversion

A triblock copolymer, containing a polyethylene glycol (PEG) block and two symmetrical poly(2‐(dimethylamino)ethyl methacrylate) (PDM) blocks, was synthesized by using PEG‐based macroinitiator with copper‐mediated living radical polymerization. The conductivity tests showed that the copolymer exhibited switchable responsiveness to CO₂, i.e., a relatively high conductivity of solution can be switched on and off by bubbling and removing of CO₂. According to the nuclear magnetic resonance results, the CO₂‐switchable conductivity variation could be attributed to protonation and deprotonation of tertiary amine groups in PDM blocks. Moreover, at a proper weight concentration 0.5%, the copolymer aqueous solution displayed a CO₂‐switchable viscosity variation. Scanning electron microscopy, cryogenic transmission electron microscopy, and dynamic light scattering characterization jointly demonstrated that the viscosity variation was the result of a CO₂‐switchable vesicle‐network aggregate structure transition. This structure transition can actually be attributed to a hairpin‐line molecular configuration conversion in terms of the reasonable mechanism discussion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44417.     

Synthesis and Properties of a Series of CO2 Switchable Surfactants with Imidazoline Group

Switchable surfactants are environment-friendly compounds, which can be separated from the system or lose surface activity after completing their function during one stage of a process. In order to study switchable properties of a kind of CO₂ switchable surfactant with an imidazoline group, four 2-alkyl-1-hydroxyethylimidazolines were synthesized by condensation of N-(2-hydroxyethyl)ethanediamine with dodecanoic, tetradecanoic, hexadecanoic, and octadecanoic acids. Then, the series of long-chain alkyl imidazoline compounds were reacted with dry ice to produce imidazolinium bicarbonates cationic surfactants. The critical micelle concentration (CMC) and surface tension at CMC (??_cmc) measured by the Wilhelmy plate technique show that these surfactants have excellent surface activity. The changes of conductivity before and after bubbling CO₂ show the conversion between imidazolines and imidazolinium bicarbonates cationic surfactants. Conductivity cycles indicated that these surfactants could be switched by CO₂ reversibly and repeating this three times. However, their switchable function on the emulsification-demulsification of water-alkane was dissatisfactory due to the emulsibility of amide which was hydrolyzed from 2-alkyl-1-hydroxyethylimidazoline. Therefore, the application of these switchable surfactants needed to be studied further.     

Simple chemical polymerization method for the deposition of a conducting polyaniline on the surface of acrylonitrile–butadiene–styrene. II. Treatment in organic free solvent

We developed a simple method for the deposition of a uniform layer of polyaniline (PANI) on the surface of acrylonitrile–butadiene–styrene (ABS). The method consisted of two steps: the soaking of ABS samples in a water‐based aniline solution stabilized by surfactants followed by the oxidative polymerization of the adsorbed and absorbed monomer. The three types of surfactants (molecular N,N‐dimethyl‐octalamine‐N‐oxide, anionic sodium dodecyl sulfate, and cationic hexadecyl trimethyl ammonium bromide) were used to prepare and stabilize the aniline emulsions in water. After treatment, the ABS surface was completely covered by PANI (as seen with scanning electron microscopy). The surface conductivity after PANI coating reached values between 10^?3 and 10^?4 S/□ in the best developed conditions. The chemical nature of the surfactant affected the particular setting of the aniline/surfactant emulsion preparation (time of ultrasonification = 15–30 min), its optimal concentration (2–10 wt % aniline and 0.1–0.2M surfactant), and other parameters of treatment, such as time (10 s to 20 min) and temperature (20–60°C) of soaking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1752–1758, 2004     

Reversibly pH-Switchable Anionic-Surfactant-Based Emulsions

To develop a convenient and reversible strategy for phase separation and re-emulsification of surfactant-based emulsions, we established a method for pH switching of emulsions formed from a pH-switchable anionic surfactant, potassium dodecyl seleninate (C₁₂SeO₂K). Upon acidification, C₁₂SeO₂K was protonated to give a precipitate of dodecyl seleninic acid (C₁₂SeO₂H); upon basification, C₁₂SeO₂H was neutralized restore C₁₂SeO₂K. The pH-switchable window of the emulsion thus obtained was a pH range of 7 to 8. Reversible changes in both interfacial tension by ~10.2 mN m^?1, as well as the mechanical, steric, and/or electrical barriers formed by C₁₂SeO₂K at the interface of the oil–aqueous solution account for the fully reversible phase separation and re-emulsification of the C₁₂SeO₂K-based emulsions. A stable emulsion (i.e. the time needed to separate 1 mL of H₂O from 6 mL of emulsion at 25 °C is larger than 1 h) could be cycled at least 25 times when the pH was varied between 7 and 8.     

Viscoelastic Surfactants with High Salt Tolerance,Fast‐Dissolving Property,and Ultralow Interfacial Tension for Chemical Flooding in Offshore Oilfields

Injected chemical flooding systems with high salinity tolerance and fast‐dissolving performance are specially required for enhancing oil recovery in offshore oilfields. In this work, a new type of viscoelastic‐surfactant (VES) solution, which meets these criteria, was prepared by simply mixing the zwitterionic surfactant N‐hexadecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (HDPS) or N‐octyldecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propane sulfonate (ODPS) with anionic surfactants such as sodium dodecyl sulfate (SDS). Various properties of the surfactant system, including viscoelasticity, dissolution properties, reduction of oil/water interfacial tension (IFT), and oil‐displacement efficiency of the mixed surfactant system, have been studied systematically. A rheology study proves that at high salinity, 0.73 wt.% HDPS/SDS‐ and 0.39 wt.% ODPS/SDS‐mixed surfactant systems formed worm‐like micelles with viscosity reaching 42.3 and 23.8 mPa s at a shear rate of 6 s^?1, respectively. Additionally, the HDPS/SDS and ODPS/SDS surfactant mixtures also exhibit a fast‐dissolving property (dissolution time <25 min) in brine. More importantly, those surfactant mixtures can significantly reduce the IFT of oil–water interfaces. As an example, the minimum of dynamic‐IFT (IFT_min) could reach 1.17 × 10^?2 mN m^?1 between the Bohai Oilfield crude oil and 0.39 wt.% ODPS/SDS solution. Another interesting finding is that polyelectrolytes such as sodium of polyepoxysuccinic acid can be used as a regulator for adjusting IFT_min to an ultralow level (<10^?2 mN m^?1). Taking advantage of the mobility control and reducing the oil/water IFT of those surfactant mixtures, the VES flooding demonstrates excellent oil‐displacement efficiency, which is close to that of polymer/surfactant flooding or polymer/surfactant/alkali flooding. Our work provides a new type of VES flooding system with excellent performances for chemical flooding in offshore oilfields.     

Reversibly Redox‐Switchable Anionic Surfactant Contains Two Selenium Atoms

To better control the interfacial activities of selenium‐containing surfactants, a redox‐switchable anionic surfactant containing 2 selenium atoms, namely sodium 3‐((3‐(benzylselanyl)propyl)selanyl)propyl sulfate (SBSe₂S), has been designed and synthesized. Upon oxidation by H₂O₂, the 2 divalent selenide groups in the hydrophobic tail of SBSe₂S are converted into the corresponding selenoxides. The initial hydrophobic tail of SBSe₂S gets separated into 3 segments by 2 hydrophilic selenoxide groups, destroying the bola‐type structure. The interfacial activities of SBSe₂S in aqueous solution could thereby be switched off to a greater degree than in the case of its counterparts containing only a single selenium atom. After reduction with Na₂SO₃, the 2 selenoxide groups in SBSe₂S‐Ox are restored to the initial selenide. Consequently, the interfacial activities of SBSe₂S could be reversibly switched by alternate addition of H₂O₂ and Na₂SO₃, without obvious deterioration over 5 cycles.     

Preparation of highly concentrated inverse emulsions of acrylamide‐based anionic copolymers as efficient water rheological modifiers

Highly concentrated inverse anionic polymeric emulsions (with a solid content of up to 63 wt %) were prepared using a two‐step methodology: (i) First, acrylamide, acrylic acid, and its ammonium salts crosslinked copolymers were obtained by inverse emulsion polymerization, (ii) The water/volatile oil mixture was then separated from the heterogeneous system by vacuum distillation. To maintain sufficient stability during the reaction and distillation processes, a ternary surfactant mixture was used. A surface response methodology was employed to obtain the optimal values of the factors involved in both process and product specifications, and to maximize the high performance of these inverse anionic polymer emulsions. This yielded a product containing up to 63.2 wt % solids capable of achieving Brookfield viscosities as high as 40.3 Pa·s, using an aliquote of these concentrated inverse polymer emulsions (1.8 wt % in deionized water). Rheological characterization (oscillatory and rotational measurements) was carried out to evaluate the behavior of the diluted inverse anionic polymer emulsion in water thickening. The methodology developed can be used to formulate a wide range of viscoelastic (G″/G′) water‐based products from anionic water soluble polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43502.     

Preparation of acrylamide‐based poly‐HIPEs with enhanced mechanical strength using PVDBM‐b‐PEG‐emulsified CO2‐in‐water emulsions

Poly(vinyl acetate‐alt‐dibutyl maleate)‐block‐poly(ethylene glycol) (PVDBM‐b‐PEG) copolymers were synthesized via reversible addition–fragmentation chain transfer radical polymerization and used as emulsifiers to form stable CO₂‐in‐water high internal phase emulsions (C/W HIPEs). Then, highly interconnected cellular polyacrylamide (PAM) and poly(acrylamide‐co‐N‐hydroxymethyl acrylamide) [P(AM‐co‐HMAM)] poly‐HIPEs with enhanced mechanical strength were prepared based on the stable C/W HIPEs. The porous structures of the PAM poly‐HIPEs, as well as morphology and compressive modulus, could be influenced by the surfactant concentration and the length of the CO₂‐philic tails of the surfactants. PAM poly‐HIPEs with the smallest average pore diameter (11.12 ± 0.62 μm) and the highest compressive modulus (22.65 ± 0.10 MPa) could be obtained by using the short CO₂‐philic chains of the PVDBM‐b‐PEG surfactant at a high concentration (1.0 wt %). Moreover, with the copolymerization of N‐hydroxymethyl acrylamide (HMAM) comonomers with acrylamide, the compressive modulus of the obtained P(AM‐co‐HMAM) poly‐HIPEs was three times higher than that of PAM poly‐HIPEs. Both PAM and P(AM‐co‐HMAM) poly‐HIPEs were employed as scaffolds to guide H9c2 cardiac muscle cellular growth. Fluorescence images showed that a smaller average pore size and a narrower pore‐size distribution were helpful for cell growth and proliferation on these materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46346.     

Synthesis and Assessment of a CO2‐Switchable Foaming Agent Used in Drilling Fluids for Underbalanced Drilling

In underbalanced drilling, a switchable foam fluid is essential to reduce the drilling cost. A switchable foaming agent was synthesized by carbonyl–amine condensation and characterized by Fourier transform infrared and ¹H nuclear magnetic resonance (NMR) spectroscopy. Thermogravimetric analysis and differential scanning calorimetry showed that the tolerable temperature limit of the surfactant was 128 °C. The effectiveness of CO₂/N₂ switching was confirmed by analysis of the electrical conductivity and surface tension. Utilizing the foaming agent, 3 different foam systems (unstable, stable, and hard) were designed for drilling after formula optimization. Experimentally, the self‐circulation indicated that the foaming fluids still maintained great foaming performance even after multiple cycles. The experiment also indicated that the suspension of the foam systems was 50–90 times that of water and had a significant resistance to salts (NaCl, CaCl₂). Besides, the foam systems found that the suitable foaming temperature was 40–100 °C and that the hard foam system could maintain the foaming performance up to 120 °C. In the oil resistance experiment, the foaming ability of the foam systems decreased obviously above a kerosene content of 5% (w/v), whereas a certain foaming performance still could be ensured below 10% kerosene.     

Microstructure and glass‐transition temperature of novel star N‐SIBR

In this study, a polymeric N‐functionalized mutilithium (N‐M‐Li) compound was prepared from commercial divinylbenzene (DVB) and lithiohexamethyleneimine (LHMI), and star‐shaped copoly(styrene–butadiene–isoprene) was obtained by anionic polymerization using preformed N‐M‐Li as initiator, tetramethylethlenediamine (TMEDA) as polar modifier, and cyclohexane as solvent. The microstructure and the glass–transition temperature (Tg) of copolymers were characterized by ¹H NMR and differential scanning calorimetry (DSC), respectively. It showed that the non‐1,4‐structure content and the Tg of copolymers increased with the increase of TMEDA dosage or the decrease of polymerization temperature; however, the effects of the initiator concentration and DVB dosage on them were not obvious. We also obtained the relationships between the non‐1,4‐structure content of copolymers and the Tg of copolymers respectively, and between the ln(T/Li) (TMEDA/N‐M‐Li, mole ratio) and the non‐1,4‐structure content of copolymers, as follows: Tg (°C) = 0.6258C_{non 1,4}?55.93 and C_{non 1,4} = 20.79 ln K+59.11, where K is T/Li value. Therefore on the basis of experimental results, we realize polymer design according to our practical requirements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5848–5853, 2006