Polymerization of epoxidized soybean oil with maleinized polybutadiene

Epoxidized soybean oil (ESO) triglycerides were reacted with maleinized polybutadiene (MMPBD) to give plant‐oil‐based thermoset polymers. MMPBD samples were of two different molecular weights [high‐molecular‐weight maleinized polybutadiene (MMPBD‐H), maleate content = 10%, number‐average molecular weight (M_n) = 9000, and low‐molecular‐weight maleinized polybutadiene (MMPBD‐L), maleate content = 15%, M_n = 5000]. To increase the crosslink density of the product, a free‐radical initiator, benzoyl peroxide, was added to this mixture to further crosslink MMPBD through its double bonds. The characterizations of the products were done by dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, and IR spectroscopy. The ESO–MMPBD polymers were crosslinked rigid infusible polymers. ESO–MMPBD‐H–1 : 1 and ESO–MMPBD‐L–1 : 1 showed glass‐transition temperature values at −23, 78 and −17, 64°C, respectively, whereas the storage moduli of the two polymers at 25°C were 13 and 16 MPa, respectively. The storage moduli of the polymers remained the same or decreased with the addition of a free‐radical initiator. The storage moduli also decreased with increasing ESO concentration above a 1 : 1 epoxy‐to‐anhydride molar ratio. The surface hardness increased dramatically, and the equilibrium swelling ratio decreased with the addition of free‐radical initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of oil absorption resins filled with polybutadiene

Polybutadiene (PB) is used to fill an oil absorption resin as a physical crosslinker to construct a kind of 3‐dimensional network with a high degree crosslinking and low crosslink density. A series of acrylic resin particles with various compositions are prepared by suspension polymerization, using benzoyl peroxide (BPO) as an initiator and ethylene glycol dimethacrylate (EGDMA) as a chemical crosslinker. The effects of the polymerization temperature, initiator concentration, monomer feed ratio, and chemical and physical crosslinker concentrations on the oil absorbency and gel fraction (degree of crosslinking) are studied. The recipe and operation conditions are optimized as follows: a mass ratio of 3:1 for styrene (St)/dodecyl methacrylate or St/butyl acrylate, 0.5 wt % BPO, and 80°C for 7–8 h. The effect of the physical crosslinker (PB) concentration is complex. The oil absorbency increases with increasing PB at lower EGDMA concentrations. However, under this same condition, particles cannot be formed if the PB concentration is higher than a certain value. By contrast, there is an optimum PB concentration when the EGDMA concentration is higher. The oil absorption speed is also investigated. The presence of PB can speed up absorption. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3309–3314, 2003     

填充油对充油顺丁橡胶性能的影响

研究了填充高芳烃油和环烷油对充油顺丁橡胶性能的影响。结果表明：填充高芳烃油比填充环烷油的橡胶的拉伸强度、伸长率、生胶门尼略高，定伸应力略低；充油顺丁橡胶的门尼粘度值随填充油量的增大而减小。     

Gelation performance of poly(ethylene imine) crosslinking polymer–layered silicate nanocomposite gel system for potential water‐shutoff use in high‐temperature reservoirs

Polymer gels have been widely used for water shutoff in mature oil fields. In this paper, polyacrylamide (PAM)–montmorillonite (MMT) nanocomposites (NC) were prepared through in situ intercalative polymerization. Fourier transform infrared spectroscopy and X‐ray diffraction were conducted to characterize the prepared PAM/MMT nanocomposites. The gelation performance of poly(ethylene imine) (PEI) crosslinking PAM/MMT nanocomposite gel system (NC/PEI gel system) was systematically investigated by bottle testing and viscosity measurement methods. The results showed that the gelation performance of the NC/PEI gel system was greatly affected by the total dissolved solids, PAM/MMT nanocomposite concentration, and PEI concentration. The NC/PEI gel system exhibited much better thermal stability and gelation performance than the PAM/PEI gel system at the same conditions. The gelation performance after flowing through porous media of the NC/PEI gel system before injection and that of the subsequently injected gel system was different. The gel strength decreased and the gelation time was delayed after the gel system before injection was flowed through porous media. However, the gel strength of the subsequently injected gel system did not decrease, and only the gelation time was delayed after flowing through porous media. This study suggests that the NC/PEI gel system can be used as a potential water‐shutoff agent in high‐temperature reservoirs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44243.     

Crosslinking of isocyanate functional acrylic latex with telechelic polybutadiene. III. Application of a diffusion model

The diffusion and reaction of amino-telechelic polybutadiene (PBD-NH₂) in poly(styrene/n-butyl acrylate/TMI®) (PSBT) was studied. A monodisperse poly(St/BA/TMI) seed latex was prepared by semicontinuous emulsion polymerization. Two core/shell latices were also prepared semicontinuously, using the seed latex as the core and poly(St/BA) as the shell. These monodisperse latices were mixed with equivalent amounts of the telechelic PBD-NH₂ artificial latex before casting into films. The consumption of the TMI in these films was monitored by FTIR as a function of time and the NH₂/TMI ratio. The results showed that without the PSB shell, the PSBT particles (80 nm radius) could be penetrated by the PBD-NH₂ completely. A 24 nm PSB shell was found to act effectively as a barrier to preventing the penetration of the PBD-NH₂ inside the particles. This was consistent with previous TEM results, indicating that the crosslinking between the isocyanate in the PSBT particles and the amine in the PBD-NH₂ particles provided the driving force for the chain diffusion. A diffusion model was established for the PSBT/PBD-NH₂ system. Assuming steady-state diffusion, the effective diffusion coefficients were calculated based on the experimental data. This lead to the estimation of the surface coverage of the PBD-NH₂ on the PSBT particles in the latex films. A film formation and crosslinking mechanism was proposed for the PSBT/PBD-NH₂ latex blend system. In the absence of crosslinking reactions, the two incompatible polymers tended to completely phase separate during the film formation. However, with the crosslinking reactions, the PBD-NH₂ will be bound to the PSBT particle surfaces, forming a PSBT-PBD copolymer interphase. This interphase facilitates the diffusion of the PBD-NH₂ into the PSBT particles. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 985–993, 1998     

不同微观结构聚丁二烯橡胶的自由基接枝反应

以过氧化苯甲酰(BPO)为引发剂,2,2,6,6-四甲基哌啶-1-氧基自由基(TEMPO)为自由基捕捉剂,进行3种低相对分子质量模型聚丁二烯,即高乙烯基聚丁二烯橡胶(HVPB)、高反式聚丁二烯橡胶(HTPB)及高顺式聚丁二烯橡胶(HCPB)的自由基接枝反应,并利用傅里叶变换红外光谱和核磁共振氢谱对模型聚丁二烯接枝产物的...     

Synthesis and application of nonionic polyacrylamide with controlled molecular weight for fracturing in low permeability oil reservoirs

Nonionic polyacrylamide (NPAM) with controlled molecular weight was successfully synthesized as a gel fracturing fluid by aqueous solution polymerization. The effects of the monomer concentration, initiator concentration, reaction time, feeding temperature and reaction temperature on the molecular weight were systematically investigated through single‐factor and orthogonal experiments. The NPAM molecular weight can be controlled by adjusting these factors. The decisive factor is the acrylamide concentration, whereas the initiator concentration and feeding temperature are secondary factors. These synthetic NPAMs can be crosslinked with zirconium acetate to produce a gel fracturing fluid for use in low permeability oil reservoirs. Gel fracturing fluids based on synthetic NPAMs have high shear resistance, low filtration performance, easy gel breaking performance, good proppant carrying capability and low core damage capability. By adjusting the NPAM or crosslinker concentrations, the gel fracturing fluid can be adapted for use in low permeability oil reservoirs for a wide temperature range (60–120°C). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41637.     

Crosslinking of isocyanate functional acrylic latex with telechelic polybutadiene. I. Synthesis and characterization

An ambient curable isocyanate functional acrylic latex was synthesized by incorporating dimethyl meta-isopropenyl benzyl isocyanate (TMI®), an isocyanate monomer, into styrene/n-butyl acrylate copolymer. An artificial latex of amino-terminated telechelic polybutadiene was prepared and blended with the acrylic latex as a curing agent. The isocyanate content in the blended latex was determined by titration and FTIR measurements. The latex blend properties, in terms of particle size and latex viscosity, and the latex film properties, in terms of stress–strain behavior and solvent swelling behavior, showed no significant change after 30 days' storage of the latex blend at 50°C. The good storage stability was attributed to the stable nature of the latex blend in which there was little chance for the isocyanate-containing particles to come into contact with the curing agent particles, thus preventing premature contact of the acrylic chains with the telechelic chains. The reactivity of different functional groups in the telechelic polymer was studied; the amino group was found to be the most reactive toward the TMI. In addition, a shorter chain telechelic crosslinker was found to result in a higher degree of crosslinking, but this was more intraparticle than interparticle in nature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 965–975, 1998     

Room temperature spontaneous exfoliation of organo-clay in liquid polybutadiene: Effect of polymer end-groups and the alkyl tail number of organic modifier

Disorderly exfoliated telechelic liquid polybutadiene/organo-clay nanocomposite gel was, for the first time, successfully prepared at room temperature of 26 °C by simply compounding of carboxyl-terminated polybutadiene (CTPB) with organo-clay containing surfactant modifier with two alkyl tails. The dispersion behavior of organo-clay in liquid polybutadiene/organo-clay nanocomposite gels were systematically investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), rheology and compatibility experiments, focusing on the influence of the functional end-groups of the liquid rubber and the alkyl tails number of the organic modifier on the clay exfoliation. A unique liquid-like reversible rheological behavior was observed for CTPB/exfoliated clay nanocomposite gels with organic modifier having two alkyl tails, which is totally different with that of other samples (HTPB/C18-clay, HTPB/D18-clay and CTPB/C18-clay). And it is noteworthy that CTPB exhibits a higher level of dispersion with an organo-clay with two alkyl tailed surfactant than that with one alkyl tail.     

Evaluation of pH‐sensitive hydrogels to control the permeability anisotropy of oil reservoirs

In stratified or fractured oil reservoirs, the oil recovery efficiency tends to be low as the injected fluid flows mainly through the matrix's most permeable regions, leaving behind part of the displaceable oil in the matrix's unswept zones. Given this issue, this study aims to evaluate the potential of applying seven commercial samples, based on poly(acrylic acid), to control the anisotropic permeability profile of reservoirs. To perform this study, first, continuous and oscillatory shear tests were conducted to characterize the hydrogel's rheological and viscoelastic behavior in various subsurface conditions (salinity, temperature, and/or pH value). Second, polymer dispersion elution tests were performed in a porous medium to evaluate the matrix's permeability reduction after treatment with hydrogels. The seven commercial samples were classified as pseudoplastic fluids at pH values ranging from 1 to 10. Under typical reservoir conditions, PAAr 70 (which has intermediate molar mass and intermediate number of crosslinks) was the only sample to behave as a strong gel (G′/G″ > 10). Elution tests confirmed that the PAAr 70 hydrogel gelified inside the consolidated sandstone plugs and reduced the matrix's permeability four‐fold. Therefore, samples based on poly(acrylic acid) with high crosslink density proved to be the most promising for controlling the anisotropic permeability profile of heterogeneous oil reservoirs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40665.     

Polyurethane elastomers made from linear polybutadiene diols

Segmented polyurethane elastomers made from linear polybutadiene diols terminated with primary (Krasol LBH‐P) or secondary (Krasol LBH) hydroxy groups, alicyclic diisocyanate, and aliphatic chain extender were prepared and tested. The system was chemically crosslinked either through isocyanurate, that is, hexahydro‐1,3,5‐triazine‐2,4,6‐trione groups (formed by catalyzed cyclotrimerization of isocyanate groups), or by low molecular weight triols. The best balance of stress‐strain properties and reasonable thermal stability was obtained for systems in which only a small amount of chemical crosslinks was present in predominantly physically crosslinked networks. The influence of the type of polymer diol, chemical crosslinking, diisocyanate, and technique of preparation on mechanical, thermal, and swelling properties is discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 84–91, 2002     

Evaluation by various experimental approaches of the crosslink density of urethane networks based on hydroxyl‐terminated polybutadiene

Crosslink density (CLD) is an important characteristic for elastomeric polymer networks. The mechanical and viscoelastic properties of the elastomers are critically dependant on the CLD. Several methods have been adopted for its determination, but swelling and stress–strain methods continue to be more popular because of the convenience associated with these techniques. In this article, the determination of CLD of allophanate–urethane networks based on hydroxyl‐terminated polybutadiene and toluene diisocyanate with swelling and stress–strain methods is reported. The Flory–Rhener relationship was applied to calculate CLD from the swelling data. CLDs were also calculated from the initial slope of the stress–strain curve (Young's modulus), Mooney–Rivlin plots, equilibrium relaxation moduli, and dynamic mechanical properties. A comparison was drawn among the values obtained with the various methods. Although the CLD values obtained from Mooney–Rivlin plots were slightly lower than those obtained from swelling data, the values obtained with Young's modulus and storage modulus were considerably higher. The values obtained with swelling and equilibrium relaxation moduli data were very close to each other. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3129–3133, 2007     

Novel technique for crosslinking and reinforcing high‐cis polybutadiene rubber using a silanized silica nanofiller

A large amount of a precipitated amorphous white silica nanofiller was mixed with a high‐cis polybutadiene rubber. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl)tetrasulfide (TESPT). TESPT is a sulfur‐containing bifunctional organosilane that chemically adheres silica to rubber. The rubber was cured primarily with sulfur in TESPT, and the cure was optimized by the addition of a sulfenamide accelerator, which helped to form sulfur chemical bonds between the rubber and the filler. The hardness, tensile properties, tear strength, abrasion resistance, modulus, and cyclic fatigue life of the cured rubber improved substantially when the filler was added. Interestingly, this new technique produced a rubber with good mechanical properties, and only one accelerator was needed to optimize the chemical bonding between the rubber and the filler and fully cure the rubber. As a result, a substantial reduction in the use of the curing chemicals was achieved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Biocomposites composed of epoxidized soybean oil cured with terpene‐based acid anhydride and cellulose fibers

Epoxidized soybean oil (ESO) was cured with a terpene‐based acid anhydride (TPAn) at 150°C, and the thermal and mechanical properties of the cured product were compared with ESO cured with hexahydrophthalic anhydride (HPAn), maleinated linseed oil (LOAn), or thermally latent cationic polymerization catalyst (CPI). The ESO‐TPAn showed a higher glass transition temperature (67.2°C) measured by dynamic mechanical analysis than ESO‐HPAn (59.0°C), ESO‐LOAn (?41.0°C), and ESO‐CPI (10.0°C). The storage modulus at 20°C of ESO‐TPAn was higher than those of ESO‐LOAn and ESO‐CPI. Also, ESO‐TPAn showed higher tensile strength and modulus than the other cured ESOs. Regarding the biodegradability measured by biochemical oxygen demand in an activated sludge, ESO‐TPAn possessed some biodegradability, which was lower than that of ESO‐LOAn. Next, biocomposites composed of ESO‐TPAn and regenerated cellulose (lyocell) fabric were prepared by compression molding method. The tensile strength of ESO‐TPAn/lyocell composites increased with increasing fiber content. The tensile strength and modulus of ESO‐TPAn/lyocell composite with fiber content 75 wt % were 65 MPa and 2.3 GPa, which were three times higher than those of ESO‐TPAn. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

高乙烯基聚丁二烯交联四丙氟橡胶性能的研究

采用不同量的高乙烯基聚丁二烯橡胶(HVBR)作为助交联剂,以过氧化二异丙苯引发交联四丙氟橡胶(FEPM),制备具有新型交联结构的FEPM/HVBR共混胶,同时表征该橡胶的硫化特性、物理性能、断面形貌、溶胀度和热性能。结果表明:随着HVBR用量的增大,共混胶的硬度和拉伸强度增大,拉断伸长率降低,加工安全性和流动性变优;共混胶的玻璃化温度与FEPM接近,且随着HVBR用量的增大,共混胶的玻璃化温度升高,耐热性能提高。     

镍系充油顺丁橡胶BR9073的应用

介绍了充油顺丁的发展情况、性能特点和用途,对齐鲁BR9073的应用开发状况进行了叙述,并提出几点建议。     

Research of phenolic crosslinker gel for profile control and oil displacement in high temperature and high salinity reservoirs

To further enhance oil recovery of high temperature and high salinity reservoir at Tahe Oilfield, field test results from profile control and oil displacement of gel were carried out in this article. Static and dynamic evaluations were performed through gel strength code method, environment scanning electron microscope, and physical simulation experiment devices. The field test results show that, under the conditions of high temperature (100.8 °C) and salinity (19.8 × 10⁴ mg/L), the stable gel system was formed with gelling time range from 26 to 45 h, gel strength ranging from E to H, and dehydrating amount lower than 3.0% after ageing 60 days. Meanwhile, the microstructure is very stable. When the permeability and gel strength ranges from 0.212 to 0.970 μm² and E to H, respectively, the plugging ratio is larger than 85%, and the plugging performance becomes better with the increase of permeability or gel strength. Due to the profile improvement rate of 99.8% and the oil recovery up to 28.5%, profile control and oil displacement technology of gel can effectively promote fluid diverting. The water cut reduced from 95.2% to 89.0% during field test carried out in Tahe Oilfield, which means that profile control and oil displacement technology of gel could stabilize oil production by water control effectively. Also, this technology has a wide application prospective that provides with strong technical support for further enhanced oil recovery in high temperature and high salinity reservoirs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46075.     

充油顺丁橡胶充油混合过程的研究

对高芳烃油、高门尼顺丁胶液及充油胶液分别进行了流变特性的到试，通过冷模试验模拟充油工艺过程，研究了不同静态混合器的压力降与混合程度，考察了不同搅拌器的混合效果，通过间断和连续充油试验研究，确定了静态混合器和搅拌釜的搅拌器的类型以及充油工艺。     

Network structure and reaction mechanisms in high pressure and peroxide vulcanization of polybutadiene: Microstructural changes studied by 13C solid-state NMR

This article is concerned with the microstructural changes during peroxide and high pressure vulcanization of polybutadiene that is unfilled and filled with carbon black. The main tool is ¹³C solid-state NMR; it shows that vinyl unsaturations are consumed in both filled and unfilled samples under peroxide and high pressure vulcanization. Chemical shift calculations of unvulcanized polybutadiene show good agreement with the observed peaks. Calculations of proposed structures, based on a possible reaction mechanism, suggest that a large number of peaks will appear, each at very low intensity. Nevertheless, some changes can be seen as a result of the crosslinking reaction, and the results provide support for the suggested reaction mechanism. Thus, the proposed addition crosslinking mechanism over vinyl unsaturations seems to be a reasonable explanation of the crosslink formation in high pressure vulcanization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2799–2806, 1999     

Preparation and properties of zeroTrans soybean oil margarines

Experimental margarines were prepared in the pilot plant from interesterified soybean oil-soybean trisaturate blends and compared to a product made from hydrogenated soybean oil. Penetration, yield values, and water/oil off-data were determined. Margarine prepared from an interesterified soy-soy trisaturate blend (80:20) tended to crystallize slowly after votation and resulted in a somewhat harder than desirable product. However, addition of 20% liquid soybean oil to the interesterified oil yielded a softer product. The experimental products showed excellent oil and water loss properties under accelerated storage conditions.