Synthesis and thermal properties of poly(n‐butyl acrylate)/n‐hexadecane microcapsules using different cross‐linkers and their application to textile fabrics

This study focused on the preparation, characterization, and determination of thermal properties of microencapsulated n‐hexadecane with poly(butyl acrylate) (PBA) to be used in textiles with heat storage property. Microcapsules were synthesized by emulsion polymerization method, and the particle size, particle size distribution, shape, and thermal storage/release properties of the synthesized microcapsules were analyzed using Fourier‐transform infrared spectroscopy, scanning electron microscopy, and differential scanning calorimetry techniques. Allyl methacrylate, ethylene glycol dimethacrylate, and glycidyl methacrylate were used as cross‐linkers to produce unimodal particle size distribution. MicroPBA microcapsules produced using allyl methacrylate cross‐linker were applied to 100% cotton and 50/50% cotton/polyester blend fabrics by pad‐cure method. The mean particle size of microcapsules ranges from 0.47 to 4.25 μm. Differential scanning calorimetry analysis indicated that hexadecane in the microcapsules melts at nearly 17°C and crystallizes at around 15°C. The contents of n‐hexadecane of different PBA microcapsules were in the range of 27.7–50.7%, and the melting enthalpies for these ratios were between 65.67 and 120.16 J/g, respectively. The particle size and thermal properties of microcapsules changed depending on the cross‐linker type. The cotton and 50/50% cotton/polyester blend fabrics stored 6.56 and 28.59 J/g thermal energy, respectively. The results indicated that PBA microcapsules have the potential to be used as a solid‐state thermal energy storage material in fabrics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

界面聚合聚脲/聚氨酯复合壳体香精微胶囊的制备及性能

以茉莉香精为芯材,以异氟尔酮二异氰酸酯（IPDI）分别与二乙烯三胺（DETA）、β-环糊精（β-CD）及β-CD/DETA反应物为壁材,采用界面聚合法制备了聚脲、聚氨酯、聚脲/聚氨酯3种不同结构壳体的香精微胶囊。探究了不同微胶囊壳体对微胶囊表观形貌、热稳定性、香精微胶囊缓释性的影响并通过动力学模型分析了香精扩散方式。结果表明,以β-CD/DETA制备的聚脲/聚氨酯复合壳体微胶囊成囊性优异,壳体致密完整,热稳定性和缓释性能最好,经其整理的纺织品可保持较浓香味90多天。3种香精微胶囊在100℃、120℃高温缓释数据均符合零级、一级、Ritger-Peppas及Higuchi动力学模型。聚脲/聚氨酯复合壳体Ritger-Peppas方程拟合后n值更加接近0.45,更符合Fick扩散,缓释性能更好。     

Preparation of phase change materials microcapsules by using PMMA network‐silica hybrid shell via sol‐gel process

Encapsulation of phase change materials (PCM) using a poly(methyl methacrylate) network‐silica hybrid as the shell material has been developed. n‐Octadecane melted at 28°C was used as PCM. Based on the suspension polymerization process, the microcapsules were prepared successfully by mixing and by the reaction of ethylene glycol dimethacrylate with precopolymer solution with tetraethoxysilane (TEOS), whose resultant microcapsules had higher latent heat (ΔH = 151 J/g) than those without TEOS (ΔH = 88.3 J/g). The average size of the PCM microcapsules was about 10 μm. The silica content, n‐octadecane content, and latent heat of microcapsules were changed with varying ageing conditions, ageing time, and temperature. The highest amount of latent heat (ΔH = 178.9 J/g) and n‐octadecane content (73.3%) of the microcapsule were obtained when the inorganic/organic ratio of the microcapsule was 5%. It was difficult to increase n‐octadecane content (74% to 55.7–67.9%) and latent heat (180.5 J/g to 135.9–165.7 J/g) of the microcapsules by introducing different functional groups of coupling agents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate (BA) without added initiator has been studied. The experimental results show that high conversion of BA can be reached in a short time by employing an ultrasonic irradiation technique with a high purge rate of N₂. The viscosity average molecular weight of poly(n‐butyl acrylate) (PBA) obtained reaches 5.24 × 10⁶ g mol^?1. The ultrasonically initiated emulsion polymerization is dynamic and complicated, with polymerization of monomer and degradation of polymer occurring simultaneously. An increase in ultrasound intensity leads to an increase in polymerization rate in the range of cavitation threshold and cavitation peak values. Lower monomer concentration favours enhancement of the polymerization rate. ¹H NMR, ¹³C NMR and FTIR spectroscopies reveal that there are some branches and slight crosslinking, and also carboxyl groups in PBA. Ultrasonically initiated emulsion polymerization offers a new route for the preparation of nanosized latex particles; the particle size of PBA prepared is around 50–200 nm as measured by transmission electron microscopy. © 2001 Society of Chemical Industry     

Expansion space and thermal stability of microencapsulated n‐octadecane

5.0–50.0 vt% of cyclohexane was mixed with 95.0–50.0 vt% of n‐octadecane as the oil‐phase during the emulsion process in the in situ polymerization of melamine‐formaldehyde. By heat‐treating the microcapsules in an oven at 100°C, the cyclohexane was removed and expansion space was formed inside the microcapsules. The microcapsules were characterized by using FTIR, SEM, DSC, TGA, and gas chromatography. When the microcapsules are heat‐treated at temperatures higher than 180°C, Tm, ΔHm, Tc, and ΔHc of the microcapsules decrease. The attenuation of enthalpy of the microcapsules containing expansion space is obviously lower than that of the control sample, however. The permeability of the microcapsule shell decreases with the increase of cyclohexane content. There is a maximum between the thermal stabilities of the microcapsules and the cyclohexane contents. The microcapsules synthesized with 30.0–40.0 vt% of cyclohexane have the highest thermal stabilities, with 230°C and 289°C in air and nitrogen atmosphere, respectively. The thermal stable temperatures are approximately 67°C and 102°C higher than that of the control sample, respectively. The expansion space inside the microcapsules allows the n‐octadecane to expand in the temperature rising process and exert lower pressure to the shell, therefore keeping the shell intact and increasing the thermal stabilities of the microcapsules. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 390–396, 2005     

Radical polymerization of n‐butyl methacrylate initiated by stibonium ylide

1,2,3,4‐Tetraphenylcyclopentadiene triphenyl stibonium ylide initiated radical polymerization of n‐butyl methacrylate (n‐BMA) in dioxane at (60 ± 0.2)°C for 90 min under nitrogen atmosphere has been carried out. The system follows nonideal kinetics, i.e., R_p α [ylide]^0.2 [n‐BMA]^1.8. The value of k/k_t and overall energy of activation have been computed as 0.133 × 10^?2 L mol^?1 s^?1, 33 kJ/mol, respectively. The FTIR spectrum shows a band at 1745 cm^?1 due to acrylate group of n‐BMA. The ¹H NMR spectrum shows a peak of two magnetically equivalent protons of methylene group at 2.1 δ ppm. The DSC curve shows glass transition temperature (T_g) as 41°C. The presence of six hyperfine lines in ESR spectrum indicates that the system follows free radical polymerization and the initiation is brought about by phenyl radical. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2457–2463, 2007     

Modelling lipase‐catalysed transesterification of fats containing n‐3 fatty acids monitored by their solid fat content

Transesterification of fat blends rich in n‐3 polyunsaturated fatty acids (n‐3 PUFA), catalysed by a commercial immobilised thermostable lipase from Thermomyces lanuginosa, was carried out batch‐wise. Experiments were performed, following central composite rotatable designs (CCRDs) as a function of reaction time, temperature and media formulation. Mixtures of palm stearin, palm kernel oil and a commercial concentrate of triacylglycerols rich in n‐3 PUFA (“EPAX 2050TG” in CCRD‐1 and “EPAX 4510TG” in CCRD‐2) were used. The time‐course of transesterification was indirectly followed by the solid fat content (SFC) values of the blend at 10 °C, 20 °C, 30 °C and 35 °C. A decrease in all SFC values of the blends at 10 °C, 20 °C, 30 °C and 35°C was observed upon transesterification. The SFC_{10 °C} and SFC_{20 °C} of transesterified blends varied between 18 and 48 and SFC_{35 °C} between 6 and 24. These values fulfil the technological requirements for the production of margarines. Under our conditions, lipid oxidation may be neglected. However, the accumulation up to 8.3% free fatty acids in reaction media is a problem to overcome. The development of response surface models, describing both the final SFC value and the SFC decrease, will allow predicting results for novel proportions of fats and oils and/or a novel combination time‐temperature.     

Preparation and characterization of polyurea/polyurethane double‐shell microcapsules containing butyl stearate through interfacial polymerization

Double‐shell microcapsules containing butyl stearate were prepared through interfacial polymerization. The outer shell is polyurea formed through polymerization of toluene‐2,4‐diisocyanate (TDI) and diethylene triamine, and the inner shell is polyurethane (PU) formed through polymerization of TDI and polypropylene glycol 2000 (PPG2000). Styrene maleic anhydride copolymer was used as emulsifier. The effects of core to monomer ratio and dosage of PPG2000 on core content and encapsulation efficiency of microcapsules were investigated. The core content has a maximum at core to monomer ratio of 3–4, and the encapsulation efficiency has a maximum value of 95% at core to monomer ratio of 2. The prepared microcapsules were smooth and compact and have an obvious latent heat of 85 J/g. The shell structure of microcapsules was polyurea and PU. The average diameter of the microcapsules was 1–5 μm. The stabilities of the double‐shell microcapsule, such as anti‐ethanol wash and antiheat properties are obviously improved than those of single‐shell microcapsule. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Organometallic synthesis of n‐type π‐conjugated polymers with dopant cation trapping sites and stability of n‐doping state against air

n‐Type π‐conjugated polymers comprising a 1,2,4‐triazole ring substituted by a benzo‐15‐crown 5‐ether (benzo15C5) subunit at the 4‐position of the 1,2,4‐triazole ring and n‐type aromatic rings such as pyridine‐2,5‐diyl and 2,1,3‐benzothiadiazole‐4,7‐diyl rings were synthesized by organometallic polycondensation. The UV‐visible spectra of the polymers exhibited absorption maxima (λ_max values) at a longer wavelength than that exhibited by 3,5‐bis(2‐bromopyridyl)‐4‐benzo15C5‐1,2,4‐triazole, revealing that their π‐conjugation system was expanded along the polymer chain. The polymers with the benzo15C5 subunit underwent an electrochemical reduction (n‐doping), and the corresponding oxidation (n‐dedoping) occurred at an unusually high potential in an acetonitrile solution of NaClO₄; the factor responsible for the unusually high oxidation potential was the stabilized n‐doping state that was attributed to the inclusion of Na⁺ in the 15C5 ring. The polymers with the benzo15C5 subunit exhibited a considerably higher stability of the n‐doping state in air than did those without this subunit. Copyright © 2012 Society of Chemical Industry     

Two‐dimensional NMR studies of styrene/n‐butyl acrylate copolymers synthesized by atom transfer radical polymerization

Copolymers of styrene and n‐butyl acrylate were prepared by atom transfer radical polymerization (ATRP) using CuBr/N,N,N′,N′,N″‐pentamethyl‐diethylenetriamine as catalyst and Methyl 2‐bromopropionate as initiator. The polydispersity of the copolymers is quite low (1.1–1.3). ¹³C {¹H} NMR spectra of these copolymers show that the methylene and methine signals of the main chain are compositional sensitive and highly overlapped. Even the distortionless enhancement by polarization transfer (DEPT) was not able to assign the complex and overlapping signals. Assignments of the various resonance signals were done with the help of heteronuclear single quantum coherence (HSQC), total correlation spectroscopy (TOCSY), and heteronuclear multiple bond correlation (HMBC) experiments. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Functionally gradient silicone sheet made by treatment of swelling and polymerization with n‐butyl methacrylate

A silicone sheet was dipped into n‐butyl methacrylate monomer including benzoyl peroxide and was swollen for 0.5 h at 23°C. Then, the sheet was put into a glass tube equipped with a three‐way stopcock and was deoxygenated by freezing under dry nitrogen. Polymerization was carried out by heating at 80°C for 2 h under dry nitrogen. The resultant sheet was a component gradient silicone sheet with poly‐n‐butylmethacrylate. The content of poly‐n‐butylmethacrylate increased gradually from either surface to the middle of the sheet. This phenomenon was assumed to occur because of the volatilization of n‐butyl methacrylate monomer during the polymerization. The properties of the sheet include increased tear strength and decreased gas permeability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3152–3155, 2002; DOI 10.1002/app.10177     

Improvement of interfacial shear strengths of polybenzobisoxazole fiber/epoxy resin composite by n‐TiO2 coating

Smooth polybenzobisoxazole (PBO) fiber has limited interfacial interaction with resin matrix. In this article, nano‐TiO₂ coating on PBO fiber is applied to improve the interfacial adhesion between PBO fiber and epoxy resin. The test results suggest that the PBO fiber had good interaction with epoxy resin matrix after its treatment with n‐TiO₂ sol. Nano TiO₂ particle embedded onto PBO fiber surface, acting as a chock, which made fiber implanted into the resin better. This greatly improved the shear strengths (IFSS) of PBO fiber/epoxy resin composite. It has been found that a 56% increase in interfacial IFSS has achieved without sacrificing mechanical properties of fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology of micron‐sized,monodisperse, nonspherical polystyrene/poly(n‐butyl methacrylate) composite particles produced by seeded dispersion polymerization

Nonspherical polystyrene (PS)/poly(n‐butyl methacrylate) (PBMA) composite particles with uneven surfaces were produced by seeded dispersion polymerization of BMA with 1.65‐μm, monodisperse, spherical PS seed particles. The composite particles consisted of a PS core and an incomplete PBMA shell. The formation mechanism of such nonspherical particles was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2013–2021, 2002     

Perfume‐containing polyurea microcapsules with undetectable levels of free isocyanates

Core‐shell polyurea microcapsules with a 40% fragrance load were prepared by interfacial polymerization of guanidine and a technical polyisocyanate prepolymer containing mainly the biuret trimer derived from hexamethylene di‐isocyanate (HDI). Residual free polyisocyanates were still present at a level slightly above 100 mg NCO functional group per kg as determined by liquid chromatography hyphenated with tandem mass spectrometry of HDI and of its biuret trimer. This level was decreased by a factor of about 10 when the polymerization process was allowed to proceed for a longer time and by a factor of about 500 when guanidine or NaOH were added to the microcapsule suspension to act as scavengers. In these cases, polyisocyanate conversion was observed to proceed for about one month when the microcapsules were stored at room temperature before reaching a plateau at a level below 1 mg NCO/kg. Overall, ammonia was the most efficient polyisocyanate scavenger as no residual HDI biuret trimer and only less than 2 μg NCO/kg as HDI were detected at the end of the process, a level which had dropped below the limit of detection of 0.25 μg NCO/kg after about 40 days of aging at room temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of shell crosslinking on polyurea microcapsules containing a free‐radical initiator

Microencapsulation of a material is often used when a controlled release of a substance is desired. This study examines the effects of crosslinking in polyurea microcapsule shells on stability of microcapsules containing the free‐radical initiator cumene hydroperoxide (CHP). Crosslinking of polyurea shells was varied by using amine monomers containing different amine functionalities, and/or changing the isocyanate/primary amine ratio. Thermogravimetric analysis was performed to determine thermal properties of these microcapsules, and the pot lives of monomer systems containing these microcapsules were measured. Thermal stability is greater with a moderate degree of crosslinking from a trifunctional amine, and decreases when crosslinking is increased through use of higher amine functionality. Stability in monomer media generally increases with increased crosslinking through higher amine functionality, but is less predictable due to crosslinks formed between capsules. Generally, increasing crosslinking through altering the isocyanate to primary amine ratio decreases capsule stability in both dry and monomer storage. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42408.     

Kinetic study of the atom transfer radical polymerization of n‐docosyl acrylate

The atom transfer radical polymerization (ATRP) of n‐docosyl acrylate (DA) was studied at 80°C in N,N‐dimethylformamide using the carbon tetrabromide/FeCl₃/2,2′‐bipyridine (bpy) initiator system in the presence of 2,2′‐azobisisobutyronitrile (AIBN) as the source of reducing agent. The rate of polymerization exhibits first‐order kinetics with respect to the monomer. The linear relationship between the molecular weight of the resulting poly(n‐docosyl acrylate) with conversion and the narrow polydispersity of the polymers indicates the living characteristics of the polymerization reaction. The significant effect of AIBN on the ATRP of DA was studied keeping [FeCl₃]/[bpy] constant. A probable reaction mechanism for the polymerization system is postulated to explain the observed results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2147–2154, 2005     

Reactive extraction of propionic acid using tri‐n‐octylamine,tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as diluent

BACKGROUND : Propionic acid is widely used in chemical and allied industries and can be produced by biocultivation in a clean and environmentally friendly route. Recovery of the acid from the dilute stream from the bioreactor is an economic problem. Reactive extraction is a promising method of recovering the acid but suffers from toxicity problems of the solvent employed. There is thus a need for a non‐toxic solvent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. RESULTS: The effect of different extractants (tri‐n‐butylphosphate (TBP), tri‐n‐octylamine (TOA) and Aliquat 336) and their mixed binary solutions in sunflower oil diluent was studied to find the best extractant‐sunflower oil combination. Equilibrium complexation constant, K_E, values of 4.02, 3.13 and 1.87 m³ kmol^?1 were obtained for propionic acid extraction using Aliquat 336, TOA and TBP, respectively, in sunflower oil. The effect of different modifiers (1‐decanol, methylisobutyl ketone, butyl acetate and dodecanol) on the extraction was also studied and it was found that modifiers enhance extraction, with 1‐decanol found to be the best. CONCLUSION: The problem of toxicity in reactive extraction can be reduced by using a non‐toxic diluent (sunflower oil) or a modifier in a non‐toxic solvent, with the extractant. The addition of modifiers was found to improve the extraction. Copyright © 2008 Society of Chemical Industry     

Well‐defined polymers containing 1,3‐dichloro‐tetra‐n‐butyl‐distannoxane moiety: Synthesis,mechanism, and applications in catalysis

A series of well‐defined different chain lengths polymers, which contain the organometallic 1,3‐dichloro‐tetra‐n‐butyl‐distannoxane core in the main chain, was obtained in one‐pot via a novel 1,3‐dichloro‐tetra‐n‐butyl‐distannoxane (complex A )/azobisisobutyronitrile (AIBN) initiating system used in reverse atom transfer radical polymerization of styrene in different concentrations. The introduction of organotin complex A was supported by ¹H‐NMR, ¹³C–NMR, and the Inductive Coupled Plasma Emission Spectrometer analysis of the organotin‐containing polymer. Moreover, the mechanism of polymerization was investigated by changing the ratio of complex A to AIBN. It was concluded that the complex A not only acted as an important part of the initiator system but also introduced the functional organometallic group into the polymer chain. Additionally, the organotin‐containing polymer could be used as catalyst for esterification, and the reaction products' conversion could reach high up to 99% and does not decrease after four successive cycles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of polyurethane microcapsules containing n‐octadecane with styrene‐maleic anhydride as a surfactant by interfacial polycondensation

A series of polyurethane microcapsules containing a phase change material (PCM) of n‐octadecane was successfully synthesized by an interfacial polymerization in aqueous styrene‐maleic anhydride (SMA) dispersion with diethylene triamine (DETA) as a chain extender reacting with toluene‐2,4‐diisocyanate (TDI). The average diameter of microPCMs is in the range of 5–10 μm under the stirring speed of 3000–4000 rpm. Optical and SEM morphologies of microPCMs had ensured that the shell was regularly fabricated with the influence of SMA. FTIR results confirmed that the shell material was polyurethane and the SMA chains associated on core material reacted with TDI forming a part of shell material. The shell thickness was decreasing in the range of 0.31–0.55 μm with the molar ratio of DETA/TDI from 0.84 to 1.35 and the weight of core material increasing from 40 to 80% (wt %). By controlling the weight ratio of PCM as 40, 50, 60, 70, and 80% in microPCMs, it was found using DSC that the T_m and T_c of microPCMs were in the range of 29.8–31.0^oC and 21.1–22.0°C and an obvious phase change had been achieved nearly the same temperature range of that of PCM. The results from release curves of microPCM samples prepared by 1.4, 1.7, and 2.0 g of SMA indicated the release properties were affected by the amount of the dispersant, which attributed to the emulsion effect and shell polymerization structure. The above results suggest that the shell structure of microPCMs can be controlled and the properties of microPCMs determined by shell will perform proper practical usage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4996–5006, 2006     

A model for microencapsulation in polyurea shell by means of interfacial polycondensation

A quasi-steady state model, based on two parallel modes of diffusion and a polycondensation reaction at the inside surface of a microcapsule, is formulated to compute the time of this microencapsulation process. The predicted times of encapsulation are in agreement with observed values reported in patents. It is also shown that, for small shell thickness, the process is reaction-controlled.