Kinetic study of HTPB (Hydroxyl Terminated Polybutadiene) Synthesis Using Infrared Spectroscopy

A kinetic study of HTPB synthesis by radical polymerization of butadiene with hydrogen peroxide initiator was conducted using infrared spectroscopy. HTPB conversion was determined based on the conjunction termination rate constant, and all polymerization kinetics were evaluated to identify the constant. All polymerization steps (decomposition, initiation, propagation, conjunction, and proportional termination) can be evaluated based on polymer conversion and functionality from data provided by infrared spectroscopy. The investigation variables included the initial molar ratio of initiator to monomer (H2O2/butadiene) and the reaction temperature. These steps were assumed as the first-order reactions, giving constant reaction rates of kd, ka, kp, kt, ktc, and ktd. The reaction rates obtained for these constants were 4.2 × 10–5 sec–1, 8.9 × 10–4, 7.7 × 103, 8.5 × 107, 3.2 × 107 and 5.3 × 107 L mol–1 sec–1, respectively, with activation energy of 7608, 14188, 2247, 105, 87 and 135 kJ mol–1, respectively. The determining step of the reaction rate was identified as the initiation reaction. HTPB conversion can be measured if all polymerization kinetics constants have been evaluated.

Photocontrolled Synthesis of N-Type Conjugated Polymers

Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition metal-mediated methods. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces all-conjugated n-type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor-acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n-type conjugated polymers without the need for transition metal catalysis.

Photocontrolled Synthesis of N-Type Conjugated Polymers

Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition metal-mediated methods. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces all-conjugated n-type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor-acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n-type conjugated polymers without the need for transition metal catalysis.

Photocontrolled Synthesis of N-Type Conjugated Polymers

Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition metal-mediated methods. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces blocky all-conjugated copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor-acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n-type conjugated polymers without the need for transition metal catalysis.

Thermally induced 1D to 2D polymer conversion accompanied by major packing changes in single-crystal-to-single-crystal transformation

The molecular packing in crystals is highly sensitive to temperature and pressure. We report a thermally-induced H-bonded 1D → 2D polymer formation via SCSCT.

Influence of dye and nylon fibers on microwave-cured acrylic resin properties

ABSTRACT Objective: The aim of this study is to analyze if both color and nylon fibers have an influence on microwave-cured acrylic resin properties. Methods: Rectangular and disk-shaped specimens were prepared using acrylic resins; medium pink with and without nylon fibers and colorless without nylon fibers. To obtain the rectangular specimens, a stainless steel die was used with the following dimensions: 64 X 10 x 3 mm (± 0.5mm). To obtain disk-shaped specimens, a die 50mm (±0.5mm) in diameter and 0.5mm (±0.05mm) thick was employed. They were randomized to form groups: control (colorless acrylic) and experimental (medium pink, with and without nylon fibers), with each group consisting of ten (10) specimens rectangular in shape and five (5) disk-shaped. They were analyzed in six (6) assays (izod impact strength, n=10; Knoop hardness, n=10; glass transition temperature, n=3; water sorption and solubility, n=5; degree of monomer/polymer conversion, n=1; flexural strength and flexural modulus, n=10). All variables were subjected to the analysis of variance test followed by Tukey's multiple comparison test, at a 5% level of significance. Results: The analysis of the monomer/polymer degree of conversion did not reveal any difference between the three groups of resins (medium pink, with and without nylon fibers and colorless resin); it was approximately 88%. The results did not show significant differences between the groups for each variable (p>0.05). Conclusion: The results showed that color and presence of nylon fibers in acrylic resins did not affect the properties analyzed in this study.

Analysis of new additive manufacturing technology based on selective composite formation using finite element method approach

Purpose Over the past few years, the number of related research to additive manufacturing (AM) has risen. The selective composite formation (SCF) can also be found among the new technologies that were developed. This technology was first introduced in 2013, and because of its innovative character, there are still many challenges to be overcome. Therefore, the main aim of this study is to present a finite element method which allows to investigate the processing of the material during the selective formation of a composite material based on cellulose and acrylic. Design/methodology/approach In the beginning, we introduced a brand new finite element method approach which is based on light transmittance network and photopolymerisation in transient state. This method is mainly characterised by internal light absorption, transversal reflectance, light transmittance coefficient and photopolymerisation kinetics. The authors defined experimentally the main model coefficients besides investigating the formation of composite material in six case studies. The main variables evaluated in those studies were the number of layers and the number of lines. By the end, the degree of polymer conversion and the preliminary evaluation of adherence between layers were identified in addition to the formation profile of composite material. Findings The presented method evidence that the SCF resulted in a profile of polymerisation which is different from profiles found in vat polymerisation processes. It was shown that the light diffraction increases polymerisation area to outside of laser limits and reduces the penetration depth. It was also exposed that the selective formation of composite material on the top layer interferes with the polymerisation of previous layers and might increase the polymerised area in about 25 per cent per layer. By the end, adherence between layers was evidenced because of a high-pass filter that limited polymer conversion to over 60 per cent. In this case, the adherence between the top layers was provided by the interface between layers, while the deeper layers resulted in a solid formed by composite. Originality/value This paper presents research results related to a very new AM technology and also proposes a new method to characterise this concept. Because of this new analytic approach, the process planning can be simulated and optimised, in addition to being a useful tool for other researches related to photocurable polymers and AM technologies.