Liquid Polybutadiene Research Articles

Influence of high cis-1,4-liquid polydienes on properties of carbon-black filled composites

High cis-1,4 liquid polybutadiene (cLBR) and polyisoprene (cLIR) with narrow molecular weight distribution were prepared by the chain-transfer coordination polymerization. The effects of cLBR and cLIR on the physical and dynamic mechanical properties of carbon-black filled composites containing single polybutadiene (PBR) or a blend of PBR/polyisoprene (PIR), were investigated. The results showed that cLBR and cLIR effectively ameliorated filler dispersion compared with the treated distillate aromatic extract (TDAE) oil. The wet skid resistance and rolling resistance of vulcanized PBR/PIR composites plasticized with 5 phr cis-1,4 liquid rubbers were significantly improved. Therefore, a new type of plasticizers cLBR and cLIR that are environmental benign and highly compatible with matrix rubbers, has been discovered to replace the conventional TDAE oil used in fabricating the “green” tyres.

Study of Styrene Butadiene Rubber Reinforced by Polybutadiene Liquid Rubber-Modified Silica.

The dispersion of silica in rubber systems and its interaction with rubber are two key factors in the preparation of rubber composites with excellent properties. In view of this, silica modified with terminal isocyanate-based polybutadiene liquid rubber (ITPB) is used to improve the dispersion effect of silica in rubber and enhance its interaction with the rubber matrix to improve the rubber's performance. The impact of different modification conditions on the dispersion of silica and the properties of modified silica-filled rubber composites were studied by changing the amount of ITPB and the modification method of silica, including blending and chemical grafting. The experimental results show that ITPB is successfully grafted onto silica, and the use of modified silica improves the cross-linking density of rubber, promotes the rate of rubber vulcanization, and overcomes the shortcomings of the delayed vulcanization of silica itself. When the ratio of ITPB liquid rubber to silica equals 1:20, the comprehensive performance of rubber is the best, the ITPB-modified silica has a better dispersion effect in rubber, and the rolling resistance is slightly improved, with tensile strength reaching 12.6 MPa. The material demonstrates excellent overall performance and holds promise for applications in the rail, automotive, and electrical fields.

Trapping Ions to Enhance High-Field Energy Harvesting Performance by Filling Polar Macromolecular Dielectrics.

In the quest for sustainable and renewable energy sources, researchers and engineers have explored innovative technologies to harvest energy from various environmental sources. Dielectric elastomer generators (DEGs) with high energy harvesting performance have been proven to be promising energy collectors, but achieving a high dielectric constant (ε') and low electrical conductivity (EC) under high electric fields of dielectric elastomer (DE) simultaneously is a struggle, which poses significant challenges. In this study, high-content carboxyl group-grafted liquid polybutadiene (HCPB) is synthesized and then adopted as an organic dielectric filler to blend and cocross-link with a butadiene rubber (BR) matrix to prepare DE composites with high energy harvesting performance. The introduction of carboxyl groups enhances polarization while trapping free Al3+ in the matrix, which revolutionarily achieves a significant increase in ε' under extremely low EC. Ultimately, the contradiction between increased ε' and decreased EC under high electric fields is reconciled, resulting in a 30 HCPB/BR composite with high energy density (w = 91.9 mJ/cm3) and fine power conversion efficiency (PCE = 24.1%). This advancement paves the way for the development of HCPB/BR composite-based DEGs with enhanced ε' and energy harvesting performance.

Enhanced DC Breakdown Strength of XLPE via Denser Cross-Linking Network Formation with Liquid Polybutadiene

Enhanced DC Breakdown Strength of XLPE via Denser Cross-Linking Network Formation with Liquid Polybutadiene

Preparation and Application of CO2-Resistant Latex in Shale Reservoir Cementing

With the application of CO2 fracturing, CO2 huff and puff, CO2 flooding, and other stimulation technologies in shale reservoirs, a large amount of CO2 remained in the formation, which also lead to the serious corrosion problem of CO2 in shale reservoirs. In order to solve the harm caused by CO2 corrosion, it is necessary to curb CO2 corrosion from the cementing cement ring to ensure the long-term stable exploitation of shale oil. Therefore, a new latex was created using liquid polybutadiene, styrene, 2-acrylamide-2-methylpropanesulfonic acid, and maleic anhydride to increase the cement ring’s resistance to CO2 corrosion. The latex’s structure and characteristics were then confirmed using infrared, particle size analyzer, thermogravimetric analysis, and transmission electron microscopy. The major size distribution of latex is between 160 and 220 nm, with a solid content of 32.2% and an apparent viscosity of 36.8 mPa·s. And it had good physical properties and stability. Latex can effectively improve the properties of cement slurry and cement composite. When the amount of latex was 8%, the fluidity index of cement slurry was 0.76, the consistency index was 0.5363, the free liquid content was only 0.1%, and the water loss was reduced to 108 mL. At the same time, latex has a certain retarding ability. With 8% latex, the cement slurry has a specific retarding ability, is 0.76 and 0.5363, has a free liquid content of just 0.1%, and reduces water loss to 108 mL. Moreover, latex had certain retarding properties. The compressive strength and flexural strength of the latex cement composite were increased by 13.47% and 33.64% compared with the blank cement composite. A long-term CO2 corrosion experiment also showed that latex significantly increased the cement composite’s resilience to corrosion, lowering the blank cement composite’s growth rate of permeability from 46.88% to 19.41% and its compressive strength drop rate from 27.39% to 11.74%. Through the use of XRD and SEM, the latex’s anti-corrosion mechanism, hydration products, and microstructure were examined. In addition to forming a continuous network structure with the hydrated calcium silicate and other gels, the latex can form a latex film to attach and fill the hydration products. This slows down the rate of CO2 corrosion of the hydration products, enhancing the cement composite’s resistance to corrosion. CO2-resistant toughened latex can effectively solve the CO2 corrosion problem of the cementing cement ring in shale reservoirs.

Efficient synthesis of high vinyl polybutadiene based on continuous flow microchannel reactor

AbstractThe traditional batch synthesis of liquid rubber faces issues such as low monomer polymerization concentration, poor uniformity of the reaction system, and inadequate heat dissipation, resulting in an unsatisfactory synthesis efficiency. This study presents a method for the rapid and efficient synthesis of high vinyl 1,2‐polybutadiene liquid rubber using butadiene as the monomer and n‐butyllithium as the initiator. By applying continuous flow microchannel reactors, the limitation of traditional synthesis method can be overcome. The addition of a modifier in the raw material promotes the formation of high vinyl structure. The preparation of liquid rubber requires the addition of a large amount of metal lithium initiator. However, for aerospace sealants, there is a requirement for low metal ion content. To address this, we employed different methods to reduce the metal ion content in the liquid rubber and increase its purity. Ultimately, we achieved the synthesis of high‐purity polybutadiene liquid rubber with 1,2‐vinyl content exceeding 88%, narrow molecular weight distribution, and tunable molecular weights. This research will provide technical guidance for the industrial application of polybutadiene synthesis in continuous flow microchannel reactors.

Liquid polybutadiene reinforced inverse vulcanised polymers

Adding liquid polybutadiene to inverse vulcanised polymers is shown to increase their flexural strength, modulus, and impact strength, while maintaining recyclability.

SYNTHESIS OF AMINATED EPOXY DERIVATIVES OF POLYBUTADIENE AND THE STUDY OF THEIR ANTI-CORROSION PROPERTIES IN THE COMPOSITION OF CONSERVATION LIQUIDS

The synthesis of amino derivatives of epoxidized polybutadienes was carried out by the amination reaction. The composition and structure of the amino derivatives were confirmed by NMR and IR spectroscopy. It has been established that the synthesized amine derivatives have a synergistic effect, accelerate the solubility in mineral oils and significantly improve the anticorrosion properties of conservation fluids. Samples of aminated epoxidized polybutadienes were tested for corrosion resistance in a hydro chamber, in sea water and in a sulfuric acid environment. Their high efficiency against corrosion has been established. Keywords: liquid polybutadiene, epoxidation, amination, corrosion inhibitor.

Effect of Functionalized Liquid Rubber on Mechanical Properties of an Epoxy Resin

AbstractIn this study, an epoxy resin has been modified with different weight ratios of carboxyl‐terminated polybutadiene liquid rubber. The introduction of a pre‐reaction catalyst has been necessary to promote the reaction between the epoxy groups and the carboxylic acid groups of carboxyl‐terminated butadiene acrylonitrile copolymer. The occurred reaction has been confirmed by infrared spectroscopy analysis. The analysis of the mechanical properties has shown that the presence of elastomeric domains allows obtaining a matrix with greater flexibility. This allows making the material competitive for many applications such as adhesives and composite matrices where a high fracture toughness is required.

Synthesis and application of styrene butadiene latex powder for cementing

AbstractTo address the problems of brittleness and poor elastic deformation ability of oil‐well cement stone, styrene‐butadiene latex powder was prepared using emulsion polymerization with styrene, liquid polybutadiene, 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid, and fumaric acid as raw materials. The dispersion properties of styrene‐butadiene latex powder in water were investigated, as well as the elastic enhancement effect of the powder in cement. The test results showed that styrene‐butadiene latex powder has good dispersion performance in water and is not easy to agglomerate, which can improve the fluidity of cement slurry. The elastic modulus of cement stone mixed with styrene butadiene latex powder is 43.1% and 27.8% lower than that of blank cement stone without styrene‐butadiene latex powder and the cement stone mixed with commercially available latex powder, respectively. The results of the mechanism analysis showed that the styrene‐butadiene latex powder can be filled in the cement stone, improved the compactness of the cement stone, buffered the external stress impact, and improve the elasticity of the cement stone.

Network formation of low molecular weight ‘liquid’ polymers studied by gel permeation chromatography and stress-strain analysis according to Mooney-Rivlin

The rheological and mechanical properties of elastomers are defined by their different networks: The crosslink network and the filler network. The crosslink network is influenced by the polymer structure. The filler network – particularly in case of silica as filler – depends on the interaction between the filler particles and the polymer. Liquid polymers can affect these networks by their lower molecular weight and with certain types by their functional groups. The goal of the present work is to gain a better understanding of the network formation: 1. During the sulfur curing of pure liquid polybutadienes with different concentrations of sulfur and curatives, and 2. Through differently added liquid polymer-silica-masterbatches in sulfur cured silica/SSBR mixtures. For the first point, the pre-cured liquid polymer samples were analyzed by gel permeation chromatography. The results indicate an association between weight concentration and the polymer chain length. For the second point, stress-strain analysis according to Mooney-Rivlin provides information about the interaction of liquid polymers with silica and the main polymer when it is added differently throughout the masterbatch approach.

Dispersion Mechanism of Styrene–Butadiene Rubber Powder Modified by Itaconic Acid and Its Toughening Effect on Oil Well Cement

Styrene-butadiene rubber (SBR) has been extensively applied to enhance the toughness of hardened cement. The instability of existing liquid latex leads to difficulties in storage and transportation, and even performance regression. Thus, the well-dispersed carboxylated butylbenzene (SISBR) latex powders were fabricated through the seed emulsion polymerization of liquid polybutadiene (LPB), styrene (St), itaconic acid (IA), and sodium p-styrenesulfonate (SSS) to overcome the difficulties. The dispersion performance of latex powders with various IA amounts was quantitatively evaluated using particle size distribution, zeta potential, and ultraviolet-visible spectrophotometry. Results showed that the carboxylic ionic (COO-) from IA enhanced the dispersing abilities of SISBR latex powders, which ensured the uniform distribution in water. Based on this, the influence of latex powder on cement was assessed mainly by fluidity, isothermal heat flow calorimetry, X-ray diffraction (XRD), and triaxial mechanical testing. Results showed the fluidity and dispersion performance of cement were improved with more IA in latex, while the hydration of cement was retarded due to excessive adsorption of carboxyl (-COOH) groups in IA. Triaxial mechanical testing showed that cement with SISBR-3 (latex containing 3% IA) exhibited the minimal elastic modulus of 3.16 GPa, which was lower than that of plain cement (8.34 GPa).

Solvent-free electrospinning of liquid polybutadienes and their in-situ photocuring

A single-step approach to rapidly convert low molecular weight polybutadienes into fine rubber crosslinked fibers and nonwoven mats without using any heat or solvent was described. This environmentally friendly method consisted in the electrospinning at room temperature of liquid polybutadiene and polybutadiene-graft-maleic anhydride polymers without any solvent; the flying jet was irradiated to trigger the in-situ curing of the forming fibers at ambient conditions, obtaining a good control over the fibrous morphology and enhancing the performance of the membranes. The kinetics of the photo-crosslinking reaction was studied through FT-IR spectroscopy. Liquid polybutadiene-graft-maleic anhydride polymers demonstrated a faster rate of photocuring, compared to neat polybutadienes. In order to further speed up the reaction, a thiol-based crosslinker and a photoinitiator were introduced into the formulations. The photo-induced crosslinking was more efficient as different reactions concomitantly took place: besides the thiol-ene crosslinking involving the multifunctional thiol crosslinker, the oxidation of the polybutadiene chains and the esterification of the maleic anhydride moieties occurred. Moreover, a polar additive was used to control the electrospinning process by lowering the viscosity and increasing the electrical conductivity. The structural, thermal and surface properties of the fabricated polybutadiene-based electrospun membranes were assessed. The membranes exhibited an excellent morphology stability, high insolubility, good thermal properties and a pronounced hydrophobic character.

Study on Nitrile Oxide for Low-Temperature Curing of Liquid Polybutadiene.

As a significant component of composite solid propellants, the cross-link alkenyl polymers need to cure at high temperatures and the current isocyanate curing systems are highly humidity sensitive. This paper presented a low-temperature curing method for a cross-linked polymer (polybutadiene) with stable wettability by using cycloaddition of the nitrile oxide of tetramethyl-terephthalobisnitrile oxide (TTNO) and the C=C group of liquid polybutadiene (PB). The TTNO was synthesized in four steps from 1,2,4,5-tetramethylbenzene and evaluated as a low-temperature hardener for curing liquid PB. To characterize the reaction ability of TTNO at 25 °C, the cross-linked rubber materials of various contents (8%, 10%, 12%, 14%, 16%) of curing agent TTNO were prepared. The feasibility of the curing method can be proved by the disappearance of the absorption peak of the nitrile oxide group (2300 cm−1) by FT-IR analysis. Contact angle, TG-DTA and tensile-test experiments were conducted to characterize the wettability, thermo-stability and mechanical properties of the obtained cross-linked rubber materials, respectively. The results showed that the curing agent TTNO could cure PB at room temperature. With the growing content of the curing agent TTNO, the tensile strength of the obtained cross-linked rubber material increased by 260% and the contact angle increased from 75.29° to 89.44°. Moreover, the thermo-stability performances of the cross-linked rubber materials have proved to be very stable, even at a temperature of 300 °C, by TGA analysis.

A Sprayable and Visible Light Rapid-Cured Strippable Film for Surface Radioactive Decontamination.

Strippable film is effective for removing radioactive contamination. However, it still has some limitations, such as the long curing time (about 30 min~24 h) and the requirement of organic solvents. To address these issues, we report a simple protocol to prepare strippable decontamination films using liquid polybutadiene (LPB) and tert-butyl acrylate (TBA) as the raw materials without solvent and using camphorquinone/ethyl 4-dimethylaminobenzoate (CQ/EDB) as a photoinitiator, where the film was formed under household LED panel light or daylight irradiation for about 540 s. After a thorough study of viscosity, real-time Fourier transform infrared (RT-FTIR spectra), gel and volatile organic compound (VOC) contents, mechanical properties and decontamination efficiency, the optimum composition and curing conditions were determined for the decontamination strippable film. VOC content is as low as 12.7 ± 0.7% and the resultant strippable film exhibits good mechanical performances with a tensile strength of up to 5.4 ± 0.4 MPa and elongation of up to 66.6 ± 13%. Most important, the decontamination efficiencies of this strippable film for 133CsCl on glass, ceramic and metal surfaces reach up to 98.1%, 94.3% and 97.6%, respectively.

Influence of liquid polybutadiene on crosslinking network and mechanical properties of SSBR/BR

AbstractThe treated distillate aromatic extract (TDAE) is widely used in tread compounds. However, polycyclic aromatic hydrocarbons (PAHs) contained in TDAE is serious harm to the environment and human. In this paper, liquid polybutadiene (LPB) of different brands was used to replace TDAE to plasticize solution polymerized styrene‐butadiene rubber/cis‐1,4‐polybutadiene rubber (SSBR/BR). The effects of liquid polybutadiene instead of TDAE on crosslinking network and mechanical properties of matrix rubber were studied. LPB could participate in vulcanization reaction (different from TDAE). The results showed that LPB effectively reduced the critical strain amplitude of Payne effect (ameliorated filler dispersion) compared with TDAE plasticizing SSBR/BR. The degree of crosslinking decreased slightly, but there was no significant difference in rolling resistance and wet skid resistance at the same sulfur content. Changing the sulfur content, the wet skid resistance of tread and tensile strength of SSBR/BR vulcanizate plasticized by LPB were significantly improved, and the effect of LPB with high 1,2‐vinyl content was better. In a word, LPB as a new environmental protection plasticizer can be used to effectively replace the TDAE plasticizing SSBR/BR.

Development of Liquid Diene Rubber Based Highly Deformable Interactive Fiber-Elastomer Composites.

The preparation of intelligent structures for multiple smart applications such as soft-robotics, artificial limbs, etc., is a rapidly evolving research topic. In the present work, the preparation of a functional fabric, and its integration into a soft elastomeric matrix to develop an adaptive fiber-elastomer composite structure, is presented. Functional fabric, with the implementation of the shape memory effect, was combined with liquid polybutadiene rubber by means of a low-temperature vulcanization process. A detailed investigation on the crosslinking behavior of liquid polybutadiene rubber was performed to develop a rubber formulation that is capable of crosslinking liquid rubber at 75 °C, a temperature that is much lower than the phase transformation temperature of SMA wires (90–110 °C). By utilizing the unique low-temperature crosslinking protocol for liquid polybutadiene rubber, soft intelligent structures containing functional fabric were developed. The adaptive structures were successfully activated by Joule heating. The deformation behavior of the smart structures was experimentally demonstrated by reaching a 120 mm bending distance at an activation voltage of 8 V without an additional load, whereas 90 mm, 70 mm, 65 mm, 57 mm bending distances were achieved with attached weights of 5 g, 10 g, 20 g, 30 g, respectively.

LIQUID POLYBUTADIENE EXTENDED ESBR/SILICA WET-MASTERBATCH COMPOSITES FOR IMPROVING ABRASION RESISTANCE AND DYNAMIC PROPERTIES OF TIRE TREAD COMPOUNDS

ABSTRACT Silica wet-masterbatch (WMB) is a well-known technique for manufacturing high-content, highly dispersed silica-filled compounds. Emulsion styrene–butadiene rubber (ESBR)/silica WMB offers several advantages, including excellent silica dispersion and reduced hysteresis, as compared with conventional dry masterbatch (DMB) compound. However, because of the residual emulsifiers in ESBR latex, it can exhibit a decrease in the crosslink density and reductions in its mechanical properties. Moreover, the abrasion resistance cannot be significantly enhanced because of the tradeoff between the improvement in silica dispersion and decrease in crosslink density. Accordingly, the objective of this study was to improve the silica dispersion and abrasion resistance of ESBR/silica WMB compounds by using liquid polybutadiene rubber (LqBR) extended WMB. In detail, three types of LqBR were emulsified to LqBR emulsions, and three types of LqBR extended WMBs were produced by co-coagulating ESBR latex, silane-modified silica, and the LqBR emulsion. A thorough characterization was conducted with emphasis on the silica content, cure characteristics, mechanical properties, abrasion resistance, and dynamic viscoelastic properties. Based on the results, silane-terminated LqBR extended WMB vulcanizate showed a 58% improvement in the 300% modulus, 48% reduced DIN abrasion loss, and a 23% improvement in dynamic properties.

Adjusting silica/rubber interfacial interactions and properties via the click reactions between liquid polybutadiene and silane

The silica dispersion and interfacial interactions are two essential factors for preparing silica/rubber composites with excellent dynamic performances. In this work, the thiol−ene click reactions between triethoxysilane-terminated liquid polybutadiene (TTPB) and 3-mercaptopropyl-ethoxy-bis(tridecyl-pentaethoxy-siloxane) (Si747) were applied to adjust silica/natural rubber (NR) interfacial interactions, and the silica dispersion and properties of the resulting rubber composites were also investigated. The results of transmission electron microscopy (TEM), dynamic mechanical analyzer (DMA) and rubber process analyzer (RPA) demonstrated that TS2-NR composite with the mole ratio 2 of Si747 to TTPB exhibited the best silica dispersion and the lowest Payne effect due to the synergistic effects of TTPB and Si747; Solid NMR revealed that the interfacial interaction is the strongest for TS2-NR. Thus, TS2-NR exhibited excellent static and dynamic properties.

Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene

Two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for non-swollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation. • Swollen ITQ-1 can self-disassemble in liquid hydroxyl-terminated polybutadiene. • Interaction between zeolite and hydroxyl group of the polybutadiene is crucial. • The presence of Al in the framework is unfavorable for the exfoliation. • Presence of a bulky OSDA in the interlayer spacing promotes the exfoliation.