纳米胶囊化二元复合相变材料的制备及热性能

以正十八烷(C18)和硬脂酸丁酯(BS)为复合芯材(PCMs),聚甲基丙烯酸甲酯(PMMA)为壁材,通过无皂乳液聚合法制备纳米胶囊化相变材料,探讨了乳化剂种类和用量、引发剂种类和用量、芯壁比对纳米胶囊的影响,并采用TEM、SEM、FTIR、XRD、DSC和TGA对纳米胶囊的形貌、化学结构和热性能进行了测试表征。结果表明:当烷基乙烯基磺酸盐(AVS)用量占油相总质量的3.0%,过硫酸铵(APS)用量占单体MMA质量的1.2%,芯材与壁材质量比(芯壁比)为2∶4时,制备的纳米胶囊单体转化率最高、粒径最小、球形形貌最规整。相变纳米胶囊的熔融焓和结晶焓分别为56.89和54.02 J/g,具有良好的储热能力和耐热性能,且整理于棉织物上有较好的调温效果。     

Preparation and characterization of nano-encapsulated n-tetradecane as phase change material for thermal energy storage

Nanocapsules used as phase change material (PCM) were prepared by using in situ polymerization methods. N-Tetradecane was used as the core material. Urea and formaldehyde were used for the shell polymerization. Sodium dodecyl sulfate was used as the emulsifier and resorcin was used as the system modifier. The morphology of the nanocapsules was observed by a scanning electronic microscope (SEM). The thermal properties were investigated by a differential scanning calorimeter (DSC) and a thermogravimetry analysis (TGA). The SEM analysis indicated that the nanocapsules had general size of about 100 nm and the core material was well encapsulated. DSC analysis indicated that the mass content of n-tetradecane was up to 60%, which resulted in a high latent heat of fusion of 134.16 kJ/kg. TGA showed the thermal stability of the nanocapsules could be improved by the additives (NaCl) used in the polymerization. The nanocapsules could be applied for thermal energy storage and heat transfer enhancement.     

Fabrication and characterization of nanoencapsulated epoxy resin/crosslinked PMMA shells with in situ polymerization via phase inversion emulsion (PIE) method

Encapsulated epoxy resin healing agents with poly(methyl methacrylate (PMMA) as a thermoplastic polymeric shell are suffered from leakage of the core after a while. This problem leads to loss of their performance and its ability in self-healing systems. One way to stop or reduce the leakage of the core is crosslinking the PMMA shell. In this study, nanoencapsulation of epoxy healing agent with crosslinked PMMA as shell was carried out by in situ polymerization via phase inversion emulsion method. Ethylene glycol dimethacrylate was employed as crosslinking agent. Nonionic (SPAN 60) and ionic (sodium dodecyl sulfate) surfactants were used for competitive adsorption and phase inversion in emulsion system. Chemical structures, morphologies, and thermal properties of nanocapsules were characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis, respectively. SEM investigations showed that nanocapsules had a particle size of less than 100 nm with a narrow particle size distribution. Efficiency of nanoencapsulation was equal to 83.5%. And synthesized nanocapsules had at least 37% core contents. Nanocapsules with crosslinked shell were able to maintain liquid core up to 18 weeks, while, noncrosslinked shell lost core content after 14 weeks. It seems that low crosslink density has no effect on capsule durability. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48793.     

粒径可控的聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳乳液的制备及表征

采用种子乳液聚合法制备了聚丙烯酸丁酯(PBA)乳液,然后通过第二单体甲基丙烯酸甲酯的预溶胀法聚合制备了PBA/聚甲基丙烯酸甲酯(PMMA)乳液,用激光散射粒度仪和透射电子显微镜对乳液粒径和结构进行了表征.结果表明,当乳化剂十二烷基硫酸钠质量分数为丙烯酸丁酯的1.5%时,可制备粒径为53.6 nm且分布窄的PBA种子乳液;通过调整补加乳化剂、单体与种子乳液的用量,可制得粒径为53.6～443.8 nm的一系列单分散PBA乳液;PBA/PMMA乳液具有完善的核壳结构,且在核壳两相间存在着一个过渡层.     

聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子的制备

由种子乳液聚合法制备了聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子。以过硫酸钾(KPS)为引发剂,辛基酚聚氧乙烯醚(OP-10)为乳化剂,合成了聚苯乙烯(PS)种子核;连续滴加甲基丙烯酸甲酯(MMA),在核表面富集MMA,制备了粒径范围在0.16~0.67μm的核-壳粒子;当单体苯乙烯与甲基丙烯酸甲酯(St/MMA)的比为30∶70(质量比)时,所得粒径在0.18μm,粒径分布为0.012。差示扫描量热(DSC)研究显示,复合粒子的玻璃化转变温度(Tg)为97.2℃,峰形单一,表现出良好的热性能。     

The inverse emulsion polymerization of acrylamide using poly(methyl methacrylate)‐graft‐polyoxyethylene as the stabilizer

Inverse emulsion polymerization of an aqueous solution of acrylamide (AM) in toluene is carried out using poly(methyl methacrylate)‐graft‐polyoxyethylene (PMMA‐g‐PEO) as an emulsifier. The kinetics of polymerization, morphology of the particle, and particle size of the inverse emulsion have been investigated. The rates of polymerization are found to be proportional to the initiator concentration, the monomer concentration, and the emulsifier concentration. The morphology of particles shows a spherical structure. The mechanism of inverse emulsion polymerization using amphipathic graft copolymer as the emulsifier is proposed. The resulting molecular weights of polyacrylamide are extremely high, and relate to the amphipathic graft copolymer structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 528–534, 2001     

Synthesis of bifunctional nanoencapsulated phase change materials with nano‐TiO2 modified polyacrylate shell for thermal energy storage and ultraviolet absorption

A novel kind of bifunctional nanoencapsulated phase change material with thermal energy storage and ultraviolet absorption functions was successfully prepared through surfactant‐free emulsion polymerization with reactive emulsifiers. These nanocapsules consisted of n‐octadecane and n‐butyl stearate as binary core materials and polyacrylate supplemented with titanium dioxide nanoparticles (nano‐TiO2) as hybrid shell materials. The experimental results show that the monomer conversion and thermal conductivity increased and the particle size and distribution decreased with increase in nano‐TiO2 content when the nano‐TiO2 dosage was below 0.2 wt%. Fourier transform infrared spectroscopy and XRD confirmed that the binary phase change materials were well encapsulated inside the polyacrylate‐TiO2 hybrid shell and nano‐TiO2 was also successfully crosslinked in the nanocapsules. TEM demonstrated that the synthesized nanocapsules exhibited a regular spherical profile and a well‐defined core–shell structure with diameter ranging from 70 to 100 nm. In addition, the results obtained from DSC, TGA and UV–visible spectrophotometry showed that the as‐prepared nanocapsules had good thermal storage capacity, thermal stability and ultraviolet absorption properties. It can be considered that the resultant nanoencapsulated phase change materials with polyacrylate‐TiO2 hybrid shell may have high feasibility and hold good promise in the applications of intelligent thermoregulation fabrics. © 2019 Society of Chemical Industry     

Studies on synthesis and characterization of poly(methyl methacrylate)‐bentonite clay composite by emulsion polymerization and simultaneous in situ clay incorporation

Well‐dispersed poly(methyl methacrylate) (PMMA)–bentonite clay composite was synthesized by emulsion polymerization using methyl methacrylate (MMA) monomer and 3% sodium carbonate treated bentonite clay. The composite lost its transparency normally encountered with the neat PMMA. The composite was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), vicat softening point (VSP), dynamic mechanical thermal analysis (DMTA), and tensile studies. The morphology was investigated by scanning electron microscopy (SEM) and atomic forced microscopy (AFM) as well. The crystallography was studied to estimate the changes in crystallographic planes by X‐ray diffraction (XRD) analysis. The particle size distribution was compared amongst neat bentonite clay, neat PMMA and the composite. The FTIR spectra reveal the fact that no new primary valence bond is formed between the clay and PMMA. The thermal stability of the composite is significantly improved, as indicated by the TGA and VSP studies. A substantial increase in glass transition temperature (T_g) approximately, 10°C was recorded from the DMTA as both the storage modulus and tan δ values underwent inflexion at higher temperatures in case of the composite compared with the pristine PMMA. The XRD pattern indicates increase in basal “d” spacing for the composite. The morphology from both the SEM and AFM is quite supportive to well‐dispersed exfoliation. The incorporation of nanosized activated clay particles in PMMA during its in situ polymerization from MMA led to the formation of nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Fluoro-silicone Modified Polyacrylate Latex Emulsified with Green Surfactants

Fluoro‐silicone modified polyacrylate latex was successfully prepared by semi‐continuous seeded emulsion polymerization in the presence of a green mixed emulsifier consisting of cashew phenol polyoxyethylene ether sulfonate (BCE‐10B) anionic surfactant and alkyl polyglycoside (APG) nonionic surfactant, in which the mixed monomers were initiated with potassium persulfate (KPS). The structure and properties were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA), respectively. Results show that the optimal conditions of synthesizing the novel emulsion are as follows: the total concentration of mixed emulsifiers is 5.0%; the optimum mass ratio of APG to BCE‐10B is 2:1; the amount of initiator is 0.6%; the composition of main monomers of MMA:BA = 1:1; and the concentrations of HFMA and VTES are 4.0 and 6%, respectively. In this case, the resultant emulsion showed good thermal stability and hydrophobicity.     

Effects of preparation methods on the property of PMMA/SBA-15 mesoporous silica composites

In the paper, poly(methyl methacrylate)(PMMA)/SBA-15 composite materials were prepared by four different methods, that is, in-situ batch emulsion polymerization in the presence of mesoporous SBA-15, PMMA emulsion mixed with SBA-15 powder or dispersion in water, PMMA powder mixed with SBA-15 powder, and the properties of the composite materials were determined and compared. The composites were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanics analysis (DMA) and scanning electron microscope (SEM). The results showed that the glass transition temperatures (Tg), the storage modulus and tensile strength of the PMMA/SBA-15 composites were all improved obviously, while the thermal decomposition temperature did not influenced apparently. The composite made by in-situ batch polymerization exhibited the most improvement in the mechanical properties and Tg while the composite prepared by mixing PMMA emulsion and SBA-15 dispersion gave rise to the least improvement in the mechanical properties and Tg. These results were contributed to introducing different amount of voids into polymer matrix which were demonstrated by dielectric constant measurement and SEM morphology observation.     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly(acrylonitrile) microspheres with a narrow size distribution: Synthesis by single-step swelling and properties

Poly(acrylonitrile)-poly(styrene) micrometer-sized composite particles with a narrow size distribution are prepared by single-step swelling of poly(styrene) uniform template microspheres in emulsion droplets of methylene chloride containing an acrylonitrile monomer and a benzoyl peroxide initiator. Methylene chloride is carefully evaporated with subsequent polymerization of acrylonitrile at a temperature of 70°C inside the shrunken template particles. Acrylonitrile is also polymerized at the particle surface due to the interaction of surface poly(acrylonitrile) oligoradicals with acrylonitrile dissolved in the aqueous phase. Uniform poly(acrylonitrile) particles with a larger surface area are formed by dissolving template poly(styrene) of the composite particles. The surface and bulk properties of the particles are investigated using Fourier transform IR (FTIR) spectroscopy, elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction, X-ray photoelectron spectroscopy (XPS), contact-angle measurements, optical microscopy, scanning electron microscopy (SEM), and cross-sectional transmission electron microscopy (TEM).Original Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Boguslavsky, Margel.     

Tuning the particle size and charge density of the crosslinked polystyrene particles

We report the synthesis of charged spherical colloidal particles of poly [styrene‐(co‐2‐propene sulfonic acid)] crosslinked with divinylbenzene by emulsion polymerization. The effects of concentration of both the emulsifier and initiator on the polymerization, particle size, and charge density are studied. The particle size is found to be dependent on both the emulsifier and initiator concentration and their power dependencies are different. Below critical micelle concentration (CMC), the particle size varies significantly within a small range of emulsifier concentration. In contrast, particle size decrease is not very pronounced at the heterogeneous (micellar) particle nucleation regime where the emulsifier concentration is well above of the CMC. The power dependencies of the number of particles on surfactant concentration are explained in the light of conversion–time profile of the polymerization. The surface charge density of the colloidal particles also varies with both the emulsifier and initiator concentration. Both the particle size and charge density show an inverse relation with the molecular weight of the polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

苯乙烯-对氯甲基苯乙烯共聚物胶乳微球的制备及表征

以苯乙烯（St）和对氯甲基苯乙烯（VBC）为共聚单体,过硫酸钾（KPS）为引发剂,十二烷基苯磺酸钠（SDBS）为乳化剂,采用乳液聚合法制备了富含氯甲基的苯乙烯-对氯甲基苯乙烯共聚物功能微球。采用红外光谱（FT-IR）、扫描电镜（SEM）、激光粒度仪和X射线光电子能谱（XPS）对样品进行表征,研究了乳化剂用量、单体用量、引发剂用量、反应时间、反应温度等因素对微球粒径、乳液转化率的影响。结果表明,产物微球粒径均一,表面光滑、富含氯甲基功能基团,采用此方法可以制备粒径在100～250 nm的功能高分子微球。     

自聚甲基丙烯酸甲酯的结构及性能

通过核磁共振波谱、热失重分析仪、差示扫描量热仪及凝胶渗透色谱研究了自聚甲基丙烯酸甲酯(PMMA)的分子链结构、热稳定性、相对分子质量及其分布,并对PMMA的自引发聚合机理进行了探讨。结果表明,与引发剂引发合成PMMA相比,自聚PMMA的相对分子质量更高,分布更宽;自聚PMMA分子链内均含有热不稳定的过氧键,致使其在130 ℃便开始降解,但它对PMMA的热稳定性没有影响;自聚合是由氧与甲基丙烯酸甲酯单体（MMA）反应形成低相对分子质量过氧化物引发的。     

Effects of mesoporous SBA-15 contents on the properties of polystyrene composites via in-situ emulsion polymerization

Different loading of mesoporous molecular sieve SBA-15 was used to prepare polystyrene (PS)/SBA-15 composite materials via in-situ emulsion polymerization. The influence of SBA-15 silica on the styrene emulsion polymerization was studied regarding to the monomer conversion, particle size and particle size distribution, stability and viscosity of the resulting emulsion. The structure and properties of the composites were investigated by infrared spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and gel permeation chromatography (GPC). In addition, the glass transition temperature (T_g), thermal mechanical property and thermal stability of the composite film were measured by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively. The results indicated that the composite emulsion showed high monomer conversion, thick viscosity, low coagulum, uniform particle size and broad size distribution. Molecular weight of the polymer decreased with the increase of mesoporous silica. SBA-15 silica was dispersed evenly in PS matrix at a loading of 5 %. The PS/SBA-15 composite material containing 10 % silica maintained a certain ordered structure. DMA results demonstrated that PS/SBA-15 composite exhibited greater storage modulus and high T_g compared to pure PS. The improved thermal stability and T_g of the composite were also confirmed by the TGA and DSC.     

含氟丙烯酸酯四元共聚核壳乳液的合成与表征

采用半连续种子乳液聚合的方式,以十二烷基硫酸钠(SDS)和OP-10为复合乳化剂,甲基丙烯酸十二氟庚酯(Acty-flon-Go4)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为原料制备了壳层含氟的核壳型丙烯酸酯共聚物乳液。研究了引发体系和聚合温度对聚合反应转化率的影响;通过透射电镜(TEM)、FTIR、示差扫描量热(DSC)对共聚物乳胶粒径、形态及结构进行了研究。     

有机硅氧烷改性醋酸乙烯酯-丙烯酸酯乳液的合成与性能

采用种子乳液聚合,引入乙烯基三甲氧基硅烷(A-171),以十二烷基苯磺酸钠(DSB)和壬基酚聚氧乙烯(20)醚(OP-10)作复合乳化剂,以过硫酸钾(KPS)为引发剂,在反应温度为78±2℃条件下,合成了A-171改性醋酸乙烯酯(VAc)-丙烯酸酯共聚乳液。实验采用单体滴加工艺,考察了配方中丙烯酸丁酯(BA)、甲基丙烯酸(MAA)和A-171用量对共聚物性能和乳液聚合过程的影响,并用红外光谱仪(FTIR)、粒度仪和差示量热扫描仪(DSC)对共聚物的结构及性能进行了表征。结果表明,引入w(BA)=10%~15%(相对于配方中单体总质量,下同)、w(MAA)=4%、w(A-171)=1%到VAc-丙烯酸酯共聚物乳液中,共聚物乳液涂膜的吸水率<5.0%,耐寒性通过10个循环,60℃加速贮存稳定性>100 d。     

有机硅氧烷改性丙烯酸酯微乳液的合成与表征

采用种子乳液聚合法,以阴离子乳化剂DF-2和非离子乳化剂OP-10作为复合乳化剂,以FeSO4、K2S2O8和甲醛合次亚硫酸氢钠(SFS)作为氧化-还原引发剂,在65℃合成了有机硅改性丙烯酸酯聚合物微乳液。实验采用单体滴加工艺,用COULTERLS粒度仪和傅里叶变换红外光谱仪分别测定了共聚乳液的粒径分布和产物的结构,研究了加料方式、配方组成及操作方式对聚合稳定性、乳液的粒径分布以及产物性能的影响。结果表明,采用单体滴加工艺能得到平均粒径为50～80nm的单峰窄分布微乳液,并有效地将有机硅氧烷引入到共聚物大分子中。     

Facile preparation and thermal performances of hexadecanol/crosslinked polystyrene core/shell nanocapsules as phase change material

In this study, we report the synthesis of nanoencapsulated phase change material (PCM) with hexadecanol as core and crosslinked polystyrene (PS) as shell material via facile one‐pot emulsion polymerization and its thermal performances. By this method, no high shear homogenization is required to create nanocapsules in emulsion polymerization. The nanosized core/shell structure of the hexadecanol/PS capsules was confirmed by scanning electron microscopy and transmission electron microscope. Thermal performances of the nanoencapsulated PCM were determined using differential scanning calorimetry and thermogravimetry. The results indicated that the hexadecanol/PS nanocapsules had relatively high latent heat of fusion and good thermal stability, which make them attractive for thermal energy storage and heat transfer applications. POLYM. COMPOS., 35:2154–2158, 2014. © 2014 Society of Plastics Engineers