Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Synthesis and Characterization of Poly (Methyl Methacrylate)/Polyethylenimine Grafting Core-Shell Nanoparticles for CO2 Adsorption Using Soap-Free Emulsion Copolymerization

Unlike previous emulsion polymerization, we used grafting reactions in soap-free emulsion systems. In this study, we synthesized grafted PMMA/PEI core-shell nanoparticles by varying the MMA/PEI content and molecular weight of PEI (Mn = 600, 8000, and 10,000). The size and morphology of the core-shell nanoparticles were characterized by a particle size analyzer and scanning electron microscopy. The nanoparticles were 178 - 408 nm in diameter and swelled in water or methanol by 30 - 75 nm. The size of the nanoparticles increased with MMA contents, whereas the size distribution progressively became homogeneous with increasing molecular weight of PEI. Lastly, we measured CO2 adsorption capacity of the grafted PMMA/PEI core-shell nanoparticles, and we found the capacity to be limited at a level of 0.69 mg, which occurred for nanoparticles prepared from emulsions at a pH value of 11.

NARROW-DISPERSED CROSSLINKED CORE-SHELL POLYMER MICROSPHERES PREPARED BY SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)microspheres were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as stabilizer.The surfaces of PDVB microspheres werechloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzeneinitiating core sites for subsequent ATRP grafting of styrene using CuCl/bpy as catalytic system.Polystyrene was found to begrafted not only from the particle surfaces but also from within a thin shell layer,resulting in the formation of particles sizeincreased from 2.38-2.58 μm,which can further grow to 2.93 μm during secondary grafting polymerization of styrene.Thisdemonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature.All of the preparedmicrospheres have narrow particle size distribution with coefficient of variation around 10%.

MICRON CORE-SHELL PARTICLES PREPARED BY GRAFTING POLYMERIZATION OF METHYL METHACRYLATE FROM NARROW DISPERSE SURFACE OF CHLOROMETHYLATED POLYDIVINYLBENZENE VIA ATRP

Grafting of poly(methyl methacrylate)from narrow disperse polymer particles by surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)particles were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as the stabilizer.Chloromethylated PDVB was used as initiating coresites for subsequent ATRP of methyl methacrylate with CuBr/bpy as catalyst system.It was found that poly(methylmethacrylate)was grafted not only from the particle surfaces but also from within a thin shell layer,leading to particles sizeincreases from 2.38-3.00 μm with a core-shell structure particles.The grafted core-shell particles were characterized withFTIR,SEM,DSC.

SYNTHESIS AND PROPERTIES OF ORGANO-FLY ASH/POLY ANILINE WITH CORE/SHELL STRUCTURE BASED ON EMULSION POLYMERIZATION

Organo-fly ash （OFA） was prepared with pretreated fly ash （FA） and hexadecyltrimethyl ammonium bromide （HDTMAB）, and the composites composed of OFA and polyaniline were obtained by emulsion polymerization at different OFA weight ratios （2.0 wt%, 5.0 wt%, 10.0 wt%, 15.0 wt% and 20.0 wt%） in the presence of dodecylbenzenesulfonic acid as dopant and emulsifier. A polymerization procedure was supposed. The electrical conductivities of the composites were tested by the four-probe technique. The chemical structure and crystallinity of the composites were confirmed by FT-IR and X-ray diffraction, respectively. Morphologies of FA, OFA and the composites were observed by SEM. The element analysis was performed by energy dispersive spectrometry. The thermal stability of the composites was analyzed by TGA. The results showed that the electrical conductivity of the composites decreased with increasing the feed weight ratio of OFA, and the lowest value was 0.62 S/cm. HDTMAB and PAn were just adsorbed on the surface of FA and OFA, respectively according to the physical adsorption without destroying the crystalline structure of FA or OFA. The surface became smoother after organification of FA by using HDTMAB, and its content on FA surfaces was about 26.9 wt%. The core/shell structure of the composite was observed by SEM analysis. The composites showed a higher thermal stability than pure PAn by introduction of OFA into this polymerization system, the heat stability of PAn was increased by decreasing 31.8 wt% of weight loss after introducing 20 wt% of OFA.

THE PREPARATION AND CHARACTERIZATION OF SBR/PS CORE-SHELL PARTICLES BY GAMMA IRRADIATION

A kind of core(SBR)-shell(PS)particles was synthesized by using SBR latex and grafting with St under gammairradiation.The influences of absorbed dose and dose rate on the grafting yield of PS on SBR seed latex have beeninvestigated.Results show there was a transition layer which contained the SBR/PS graft copolymer between the SBR coreand PS shell.Dynamic laser scattering(DLS)and differential scanning calorimetry(DSC)results confirm the existence ofgrafted polystyrene,and transmission electron microscope(TEM)observation verifies the core-shell structure of SBR-g-PSlatex.Such SBR/PS core-shell latex could be processed easily to ultrafine rubber powders by using spray drying andexpected to be used as an impact modifier for PS.

Synthesis and Characterization of Core-shell Hydroxyapatite/chitosan Biocomposite Nanospheres

Novel core-shell hydroxyapatite/chitosan biocomposite nanospheres were synthesized in a multiple emulsion. The multiple emulsion was a w/o/w emulsion, made of diammonium phosphate solution as an inner aqueous phase, cyclohexane as an oil phase, and calcium nitrate solution and chitosan solution as an outer aqueous. The forming mechanism of core-shell spheres and the influence of temperature on the morphology of the nanospheres were investigated. The diameter of the resulting core-shell nanospheres was 100-200 nm and the thickness of the chitosan shell was about 10 nm. And it concluded that at different reaction temperature the morphologies of the products would be changed. The core-shell nanospheres have potential applications for the development of new biomedical materials.

Synthesis and Structure Control of A New Kind of Inelastomer Impact Modifier with Core-shell Structure and Impact Modification to PVC/CPE

A new kind of inelastomer impact modifier with a coreshell structure was synthesized by employing a multistep composite emulsion polymerization technique, the size and morphology structure of the coreshell particles could be controlled by the multistep composite emulsion polymerization technique. The study of the impact strength and the elongation at break of the PVC/CPE blend with different contents of coreshell particles(CS) indicated that the mechanical properties of PVC/CPE/CS composite were the best when the concentration of the particle was 25%(mass fraction) which showed the different regularities and characteristics of elastomer toughening plastic.

Effects of Silica Sol on Structure and Properties of Core-Shell Silicon-Acrylic Materials

Silica sol prepared by sol-gel method was introduced into poly (butyl acrylate) (PBA)/poly (butyl acrylate-styrene-methacryloxypropyl trimethoxysilane) (PSBM) core-shell emulsions to prepare a series of paper surface sizing agents. The rheological measurement indicated that PSBM emulsions exhibited shear-thinning behavior, and the phenomena became more pronounced with increasing silica sol concentration. Dynamic mechanical analysis (DMA) demonstrated that the stronger interfacial interaction between silica sol and polymer matrix, but microphase separation took place with excess silica sol. Thereby the tensile strength and thermal stability of emulsion films were increased with desirable silica sol concentration, and when silica sol concentration was greater than 6 wt%, the tensile strength leveled off and the decomposition temperature decreased from 351.19℃ to 331.63℃. The degree of crystallinity increased from 5.12% to 10.98% with 4% silica sol addition, resulting in enhanced rigidity of films. Furthermore, the interaction between polymer and fiber was improved with certain amount of silica sol, resulting in improved sizing degree, ring crush strength, surface strength and folding strength. However, excessive crosslinking will be harmful for the properties of sized paper.

Preparation of Core-shell Structured Particles and Their Nucleation in Polyester:I. Preparation of Monodisperse SiO_2/PS Core-shell Composite Particles

To enhance the nucleation and crystallization properties of polyester (e.g., polyethylene terephthalate, PET), core-shell structured particles are used to improve these properties by controlling the inorganic dispersion properties in the polymers. In the paper, monodisperse particles of silica/polystyrene (PS) are prepared with both dispersion and emulsion polymerization techniques. The monodisperse silicon dioxide particles are first prepared with the seed growth method and modified by the coupling agents. Silica is properly modified with KH-570, and its size deviation is 3.0% or so. The modified silica then reacts with the mixture of ethanol, water medium, and monomer of styrene under dispersion polymerization. Results show that the dispersion polymerization technique is more suitable for monodisperse core-shell SiO2/PS particles than that of the emulsion. The morphology and molecular structure of the core-shell particles are investigated with the transmission electron microscope (TEM), and fourier transform infra-red spectroscopy (FTIR). The results show that the modified silica particles are successfully encapsulated with polystyrene. The average number of silica particles encapsulated into each polystyrene sphere decreases when the size of silica particles increases from 50 nm to 600 nm, and will approach one when the silica is greater than 380nm in size. The mass ratio for silica/PS particles in emulsion polymerization is 4.7/1, lower than that of 6.8/1 for dispersion polymerization, which is the first reported optimized data for preparing the similar monodisperse composite particles. Thus, the PS shell in the former is thinner than that in the latter.

Single Emulsion Microfluidic Production of Janus and Core-Shell Particles via Off-chip Polymerization

In this work, we describe a straightforward approach to produce monodisperse Janus and core-shell particles by using organic solvent free single emulsion droplet-based microfluidic device combining with off-chip polymerization. To accomplish this, methyl methacrylate（MMA） was used as both the oil phase and solvent to dissolve a polymerizable PEGbased macromolecular surfactant, instead of traditional surfactant, and the photo-initiator. Janus particles can be easily obtained by off-chip UV polymerization due to polymerization induced phase separation between PEG and the formed poly（methyl methacrylate）. At the same time, core-shell particles can also be easily attained by inverting the original collecting tube several times and then exposing to UV light. These results may extend the scope of microfluidic technology and the studies on polymerization induced self-assembly/phase-separation into easy fabrication of various new functional materials.

不同引发体系合成有机硅-聚苯乙烯核壳结构微球的研究

以羟基硅油、苯乙烯为主要原料,采用半连续乳液聚合方法制得具有核壳结构的有机硅-聚苯乙烯聚合物乳液,将其进行喷雾干燥制得聚合物粉末,考察了3种不同引发体系对聚合物乳液稳定性和单体转化率的影响,并对其进行了红外光谱、透射电子显微镜分析。结果表明,3种引发体系均成功合成了有机硅-聚苯乙烯共聚物,且制得的聚合物乳液有较明显的核壳结构和较好的稳定性;采用过硫酸铵、亚硫酸氢钠和过氧化二苯甲酰组成的复合引发体系(APS+NaHSO3+BPO)制备的聚合物乳液单体转化率最高,可达93.24%。对由APS+NaHSO3+BPO复合引发体系制备的聚合物粉末进行了扫描电镜和热失重表征,结果显示,在-50~180℃内有机硅-聚苯乙烯粉末没有明显的失重峰,在500~580℃区间内,粉末热失重达61.91%,表明该聚合物具有良好的耐高低温性能,可在较宽温度范围内使用并仍旧保持良好的性能。

自交联核壳丙烯酸乳液的构建及对水性油墨的影响

以丙烯酸(AA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、丙烯酸羟丙酯、甲基丙烯酸羟乙酯为单体,乙二醇二甲基丙烯酸酯(EGDMA)、甲基丙烯酸缩水甘油酯(GMA)为交联单体,采用两步乳液聚合法制备了自交联核壳丙烯酸乳液,以其为连接料制备了水性油墨。考察了核壳特性影响油墨耐水性和附着力的因素。利用TEM、FTIR、TG、DSC、光学接触角测量仪、万能试验机对自交联核壳丙烯酸乳液及其胶膜进行了表征,考察了壳层单体中GMA质量分数对乳液粒径、稳定性和油墨附着力、耐水性的影响。结果表明,核层中AA与壳层中AA的质量比(核壳AA比)对油墨附着力影响显著,核层中MMA与BA的质量比与壳层中MMA与BA的质量比之比(核壳软硬比)对油墨耐水性影响显著。自交联核壳丙烯酸乳液最佳配方为:核层混合单体与壳层混合单体的质量比(核壳质量比)2.00∶3.00、核壳软硬比3.00∶0.75、核壳AA比0.50∶2.50、内交联单体EGDMA用量0.75 g。当壳层单体中GMA质量分数为1.5%时,自交联核壳丙烯酸乳液平均粒径为112.2 nm,多分散性指数为0.108,胶膜最大热分解速率在409℃,核层与壳层的玻璃化转变温度分别为28.5和51.7℃,乳液分散稳定性最佳,胶膜吸水率为34.55%,油墨附着力为99%,耐水性达50次。

磁性核壳微球的制备及其性能

以苯乙烯、甲基丙烯酸为单体,在偶氮二异丁腈引发下通过分散聚合合成了羧基化纳米单分散共聚微球。用化学沉淀法在共聚微球表面生成均匀分散的纳米四氧化三铁壳层,采用FTIR、SEM、DLS、HR-TEM、XRD、XPS及VSM对微球进行形貌及结构表征。结果显示微球均有良好单分散性且在水相中分散性良好。以BSA为模型研究了核壳微球蛋白分离性能,在体系pH值为4.7时微球对蛋白分离效果最佳,吸附等温线符合Langmuir等温吸附模型,微球的蛋白分离性能达到239.5 mg/g。

聚醋酸乙烯酯基光固化核壳乳液的合成及其在水性木器涂料中的应用

为解决水性木器涂料涂装效率低的问题,首先构建了双键功能化PVAc基核壳乳胶粒,然后通过预乳化将多活性单体(TMPTA)在乳胶粒合成后期加入乳液,制备了PVAc基光固化复合乳液,并对其稳定性、光固化性能和漆膜性能等进行了研究。结果表明:所制备的PVAc基核壳乳胶粒壳层含有活性双键,且粒径远小于紫外光波长,可实现UV固化;通过调控活性单体的加入量,可显著加快PVAc基光固化复合乳液的成膜速度,应用于木器漆涂饰时,最快可在20 s内完成固化;同时乳胶膜性能可调控,在活性单体TMPTA与壳层双键的物质的量比为3∶1时,光固化乳胶膜的力学性能最佳,其拉伸强度为0.91 MPa,断裂伸长率为1.29%,弹性模量为70.54 MPa;此外,木器涂料漆膜硬度、附着力、光泽和粗糙度分别为4H、0级、23.7、1.15μm。所制备的PVAc基光固化复合乳液将在水性木器涂料具有广阔的应用前景。

硅烷偶联剂改性核壳丙烯酸酯乳液的合成

为了解决传统丙烯酸乳液“热黏冷脆”的问题,以甲基丙烯酸甲酯(MMA)、苯乙烯(St)和丙烯酸丁酯(BA)为主单体,硅烷偶联剂为改性单体,制备了软核硬壳粒子的核壳结构丙烯酸酯乳液。设计结构,探究交联单体对乳液性能的影响。采用FTIR、TG、DSC对其进行了表征,测试了乳液的粒径。结果表明,当w(St)=15.0%(以核层和壳层所有单体的质量为基准,下同),核层与壳层的理论玻璃化转变温度(T_(g))分别为–10.0和30.0℃,核层交联单体乙烯基三乙氧基硅烷(A-151)和壳层交联单体γ-甲基丙烯酰氧基丙基三甲氧基硅烷(A-174)的质量分数分别为3.0%和2.0%时,乳液的稳定性和成膜性较好。与未加交联单体的均相粒子结构相比,核壳结构聚合物的最大热黏温度提高90℃,吸水率降低10.77%,缓解了水墨涂层的高温回黏问题,提高了涂膜的耐水性和耐热性。

Poly(methyl methacrylate)/Poly(N-isopropylacrylamide) Core-Shell Particles Prepared by Seeded Precipitation Polymerization: Unusual Morphology and Thermo-sensitivity of Zeta Potential

Poly（methyl methacrylate）/poly（N-isopropylacrylamide） （PMMA/PNIPAM） core-shell particles were synthesized by seeded precipitation polymerization of N-isopropylacrylamide （NIPAM） in the presence of PMMA seed particles. The anionic potassium persulfate was used as initiator, and acrylic acid as functional comonomer. It was shown that the weight ratio of the PNIPAM shell to the PMMA core can be greatly increased through continuous addition of NIPAM monomer at a relatively slow rate. PMMA/PNIPAM particles with different shell thickness were obtained by varying the amount of charged NIPAM monomers. These particles exhibited unique nonspherical core-shell morphology. PMMA core was partially coated by dense hair-like or antler-like PNIPAM shell depending on the shell thickness. The measurement of these particles＇ zeta potential at different temperatures showed that the absolute value of zeta potential unusually decreased as the particle size decreased with temperature.

微胶囊固体酸酸化压裂技术应用及展望

常规酸化压裂工作液体系存在酸岩反应过快、有效作用距离短等问题,微胶囊固体酸是解决该问题的有效手段之一,其常用于对非常规油气藏进行深度酸化压裂。此次研究阐述了微胶囊固体酸的作用机理、结构和性能特点,总结了微胶囊固体酸酸化压裂技术的研究进展,指明了微胶囊固体酸酸化压裂技术未来的主要研究方向。该研究可为超高温碳酸盐岩油藏的增产改造提供技术支持,并为微胶囊固体酸酸化压裂技术的研究与应用推广提供理论指导。