磺化聚苯乙烯微球固体酸催化制备油酸乙酯研究

采用回流-沉淀聚合法制备单分散聚苯乙烯微球(PS)；然后以氯磺酸为磺化剂，通过磺化反应制备了磺化聚苯乙烯微球。测试其粒径、Zeta电位和酸密度，探讨磺化剂的最佳用量和最佳磺化时间，获得了酸密度为2.56mmol·g^-1的磺化聚苯乙烯微球；并用红外光谱、热重分析等对其化学组成和耐热性能进行表征。将其作为固体酸催化剂，在催化油酸和乙醇酯化制备油酸乙酯中表现出较高的催化活性。当醇酸比为6∶1、反应温度为80℃、反应时间为6 h、催化剂用量为油酸质量的2%时，酯化率可达88.90%。且该磺化聚苯乙烯微球循环使用3次后，催化活性仍可保持初始活性的95%，在工业制备生物柴油领域具有较好的应用前景。     

不同聚苯乙烯微球的磺化

胶体颗粒是研究凝聚态物理性质、生命物质组装的理想模型体系,对胶体颗粒的研究具有十分重要的理论价值。聚苯乙烯(PS)微球是目前应用最为广泛的胶体粒子,由于其在合成过程中粒径可控且形貌均匀,因此,受到了越来越多的关注。文章制备了未交联的和交联的2种PS微球,研究了磺化时间对这2种PS微球的Zeta电势和粒径的影响。结果表明,在一定的反应时间内,未交联PS微球的Zeta电势和粒径,随磺化时间增加至原粒径的2.5倍,最后溶解。交联PS微球的Zeta电势和粒径随磺化时间增加至原粒径的5.5倍,但不溶解,而是形成C型胶体粒子。掌握了聚苯乙烯微球的磺化规律,可以得到尺寸及带电量不同的磺化聚苯乙烯,对凝聚态的物理性质的等研究具有重要意义。     

聚苯乙烯增强的室温硫化硅橡胶的制备及表征

以过氧化苯甲酰(BPO)为引发剂,使苯乙烯(St)在α,ω-羟基聚二甲基硅氧烷(PDMS)的甲苯溶液中进行自由基聚合制备PDMS/聚苯乙烯(PS)共混物,在甲基三乙氧基硅烷与PDMS的质量比为1∶1时,制得PS增强的室温硫化硅橡胶。研究了原料配比、BPO用量和甲苯用量对硅橡胶力学性能的影响,并对其微观结构进行了表征。结果表明,当PDMS/St(质量比)为60/40、BPO为PDMS质量的2.5%、甲苯/PDMS(质量比)为2时,所得硅橡胶的拉伸强度可达到3.8 MPa,PS的增强效果明显;该室温硫化硅橡胶具有微相分离结构,PS作为分散相分布于PDMS连续相中,且具有2个玻璃化转变温度。     

聚苯乙烯/氧化石墨烯复合材料的制备及介电性能研究

采用Hummers法制备氧化石墨烯(GO),与含有聚苯乙烯(PS)微球的乳液共混得到PS/GO复合材料。对产物的结构形态进行表征,并研究了GO含量对复合材料介电性能的影响。结果表明:GO带有大量官能团,呈薄片状结构,与PS微球共混后粘附在微球表面;随着GO含量的增加,复合材料的介电常数增大,当GO含量为5wt%,100Hz时复合材料介电常数达到22.23,是纯PS的5倍,介电损耗始终保持在较低水平。     

磺化聚苯乙烯的制备及其催化性能的研究

以聚苯乙烯(PS)微球为载体,浓硫酸为磺化剂,制备磺化聚苯乙烯微球,并通过SEM、FTIR、XRD等方法对样品进行表征。结果表明,在磺化时间5 h,磺化温度50℃,固液比为1∶10的条件下,固体酸的酸量为0.750 mmol/g,酯化效果最佳。通过优化酯化条件,在反应醇酸比2∶1、温度为70℃、反应时间5 h的条件下,催化剂用量为乙酸质量的7%时,所得到的酯化率最高为69%。     

磺化聚苯乙烯的制备及其催化性能的研究

以聚苯乙烯(PS)微球为载体,浓硫酸为磺化剂,制备磺化聚苯乙烯微球,并通过SEM、FTIR、XRD等方法对样品进行表征。结果表明,在磺化时间5 h,磺化温度50℃,固液比为1∶10的条件下,固体酸的酸量为0.750 mmol/g,酯化效果最佳。通过优化酯化条件,在反应醇酸比2∶1、温度为70℃、反应时间5 h的条件下,催化剂用量为乙酸质量的7%时,所得到的酯化率最高为69%。     

图案化二维有序大孔SiC制备

以苯乙烯为单体,采用分散聚合法合成粒径不同且单分散性良好的聚苯乙烯微球.将1.5 μm聚苯乙烯微球排列在图案化聚二甲基硅氧烷模具(PDMS mold)中,以此为模板,经过浸渍SiC陶瓷前驱体(聚碳硅烷)、紫外固化和高温焙烧过程,成功制备了二维有序大孔SiC陶瓷阵列.扫描电镜(SEM)照片表明二维有序大孔SiC形貌受聚苯乙烯微球模板调控.通过改变聚碳硅烷涂层的厚度,能够进一步调控二维有序大孔SiC的孔径.     

聚苯乙烯/还原氧化石墨烯核壳微球的制备及表征

以阳离子聚苯乙烯微球(PS)为核,氧化石墨烯(GO)和PS之间通过静电和π-π作用力进行静电自组装,制备得到聚苯乙烯/氧化石墨烯核壳微球(PS/GO),然后采用氢碘酸(HI)进行还原得到聚苯乙烯/还原氧化石墨烯核壳微球(PS/rGO),采用XRD、SEM、TEM对PS/GO和PS/rGO进行了结构表征。探究了自组装过程条件,例如分散形式(搅拌或超声)、反应时间、GO质量浓度对核壳微球形貌的影响。对不同壳层还原氧化石墨烯(rGO)厚度的PS/rGO复合材料进行了导电性能和热稳定性测试,结果表明,改变壳层rGO的含量,会直接影响复合材料的导电和热性能。由于PS/rGO具有独特的核壳结构,其导电性能和热稳定性相比PS有所提高,电子电阻从PS的17.3Ω降到PS/rGO[m(PS)∶m(rGO)=50∶1]的8.3Ω,PS/rGO的起始热分解温度提高近120℃。     

石墨烯/聚苯乙烯导热复合材料的制备

以偶氮二异丁脒盐酸盐(AIBA)为引发剂,采用分散聚合的方法合成了表面带正电荷、粒径在600 nm的聚苯乙烯(PS)微球,通过自组装将氧化石墨烯包覆于PS微球表面,用化学还原法将氧化石墨烯还原为石墨烯,制备了石墨烯包覆聚苯乙烯微球的复合分散体和压制成型制备的石墨烯/聚苯乙烯导热复合材料。结果表明,随着初始氧化石墨烯投料量的增大,制备得到的石墨烯/聚苯乙烯复合材料的导热系数逐渐增大,投料量为20%时,复合材料的导热系数达到0.41 W/(m·K),相比纯PS本体提高了116%。     

无皂乳液聚合制备多孔聚苯乙烯纳米微球

苯乙烯(St)单体、过硫酸钾(KPS)和二乙烯基苯(DVB)通过无皂乳液聚合,在70℃下反应8 h,合成聚苯乙烯(PS)纳米粒子,PS磺化,得到磺化聚苯乙烯(SPS),通过正庚烷和乙醇溶胀后,水进入粒子内部发生相分离,形成多孔聚苯乙烯PS,在-30 k Pa负压条件下,负载缓蚀剂苯丙三氮唑(BTA)。考察单体量和反应时间对粒子形态的影响。结果表明,采用10 g St,0.05 g KPS,100 mL去离子水,反应2 h后加入0.05 g DVB,可以得到粒径合适、球形完整的PS纳米微球。PS微球磺化6 h,n(乙醇)∶n(水)∶n(正庚烷)=5∶5∶1,造孔10 h时,可得到形貌和孔径合适的多孔SPS纳米微球。SEM、TEM和FTIR表明,多孔SPS微球表面和内部负载上了一定量的缓蚀剂BTA。     

Electric field-driven preparation of elastomer/plastic nanoparticles gradient films with enhanced damping property

Polymeric gradient film consisting of the plastic nanoparticles in addition to an elastomer matrix was created by driving the charged sulfonated polystyrene (PS) nanoparticles in polydimethylsiloxane (PDMS) matrix under direct-current electric field. The gradient morphology was frozen by thermal curing. The morphology, composition, damping, and mechanical properties of cured PS/PDMS gradient film containing 10 wt % of PS nanoparticles were measured with scanning electron microscopy, energy-disperse spectroscopy, and dynamic thermal mechanic analysis and tensile test, respectively. In comparison with the isotropic PS/PDMS film, the gradient film shows a better damping property, and a higher tensile strength and elongation at breaking. The interpretation in terms of deformation and fracture mechanism of gradient structure was proposed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48401.     

Thermo-mechanical properties of the blend syndiotactic/atactic polystyrene after crystallization of the syndiotactic polystyrene

The thermo-mechanical properties of the blend syndiotactic polystyrene (sPS)/ atactic polystyrene (aPS) are characterized by studying the concentration depending softening behavior with thermo-mechanical analysis (TMA) and the temperature depending Young's modulus for different concentrations with dynamic mechanical analysis (DMA).     

Modified polydimethylsiloxane/polystyrene blended IPN pervaporation membrane for ethanol/water separation

In this article a modified polydimethylsiloxane (PDMS) blended polystyrene (PS) interpenetrating polymer network (IPN) membranes supported by Teflon (polytetrafluoroethylene) ultrafiltration membrane were prepared for the separation of ethanol in water by pervaporation application. The relationship between the surface characteristics of the surface‐modified PDMS membranes and their permselectivity for aqueous ethanol solutions by pervaporation are discussed. The IPN supported membranes were prepared by sequential IPN technique. The IPN supported membrane were tested for the separation performance on 10 wt % ethanol in water and were characterized by evaluating their mechanical properties, swelling behavior, density, and degree of crosslinking. The results indicated that separation performance, mechanical properties, density, and the percentage of swelling of IPN membranes were influenced by degree of crosslink density. Depending on the feed temperature, the supported membranes had separation factors between 2.03 and 6.00 and permeation rates between 81.66 and 144.03 g m^?2 h^?1. For the azeotropic water–ethanol mixture (10 wt % ethanol), the supported membrane had at 30°C a separation factor of 6.00 and a permeation rate of 85 g m^?2 h^?1. Compared to the PDMS supported membranes, the PDMS/PS IPN supported blend membrane ones had a higher selectivity but a somewhat lower permeability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

疏水SiO2填充PDMS膜分离水中乙酸正丁酯的性能

以聚偏氟乙烯（PVDF）为支撑层,选用疏水性纳米SiO₂粉体作为改性剂,制备出聚二甲基硅氧烷（PDMS）复合膜材料,并用于乙酸正丁酯/水溶液的渗透汽化分离。采用SEM、FTIR、XRD、拉伸实验、接触角及正电子湮没寿命谱测定等对膜材料物理化学性能进行了表征,考察了膜材料的溶胀行为及渗透汽化性能。结果表明,SiO₂在PDMS膜中分散均匀,且没有发生化学作用,并提高了膜材料的机械强度和疏水性。随着SiO₂添加量增加,膜在乙酸正丁酯溶液中的溶胀度先升后降,渗透通量呈下降趋势,而分离因子先增大后减小。当SiO₂添加量为4%（质量）时,随进料浓度的增加,渗透通量增大,分离因子先增大后减小;随着温度升高,渗透通量增大,分离因子减小;渗透通量和分离因子最大值分别为240 g·m^-2·h^-1和542。     

sPS/PBA-aPS共混物的结晶与熔融行为

通过熔融共混法制备了间规立构聚苯乙烯/聚丙烯酸丁酯无规立构聚苯乙烯核壳乳胶粒子（sPS/PBA-aPS）共混物,采用差示扫描量热仪、X射线衍射仪和偏光显微镜研究了PBA-aPS对sPS结晶性能、结晶形态的影响,以及共混物在不同降温速率下、等温结晶条件下所得试样的熔融行为。结果表明, PBA-aPS的引入对sPS的结晶起阻碍作用,sPS及其共混物存在明显熔融重结晶再熔融现象,sPS平衡熔点为293.2 ℃,共混物的平衡熔点随PBA-aPS含量增加而降低,sPS形成β型大球晶完善性变差,sPS/PBA-aPS共混物的冲击强度明显提高,sPS/PBA-aPS质量比为80:20时,冲击强度提高了117 %。     

Effect of HIPS on polymorphism,melting, and crystallization behavior of sPS crystallized dynamically from melting state

Syndiotactic polystyrene/highly‐impact polystyrene (sPS/HIPS) blends were prepared with a twin‐screw extruder. Differential scanning calorimetry and wide angle X‐ray diffractometry were used to investigate the effect of the maximal melting temperature, the content of HIPS and cooling rates on the melting and crystallization behavior and crystal forms of sPS. The experimental results indicated that the addition of low content of HIPS induced the formation of more α‐crystal, whereas the addition of high content of HIPS favored the formation of β‐crystal for sPS/HIPS blends crystallized dynamically from low melting temperature. Both sPS and its blends produced only β‐crystal as crystallized from high melting temperature. The crystallization temperatures of sPS and its blends decreased as the melting temperature increased, favoring the formation of β‐crystal. Higher temperature of sPS crystallization favored the formation of more content of α‐crystal while lower temperature of sPS crystallization produced more content of β‐crystal. Cooling rates showed no significant effect on the crystal form of sPS and its blends, but influenced the melting behavior of both sPS and its bends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3353–3361, 2007     

Grafted syndiotactic polystyrene synthesized via melting graft copolymerization used as a compatibilizer for immiscible syndiotactic polystyrene/polyadimide 66 blends

A new grafted syndiotactic polystyrene (g‐sPS), to be used as a compatibilizer for syndiotactic polystyrene (sPS)/polyadimide 66 blends, was prepared by the melting graft copolymerization of sPS and monomers composed of itaconic acid and dibutyl maleate with dicumyl peroxide as an initiator. The resulting g‐sPS possessed a side‐chain structure identified by IR spectra, and the results of mechanical testing show that a good impact strength and tensile strength were obtained for g‐sPS at a 7.16‐phr addition of monomer with a 3:1 proportion of dibutyl maleate and itaconic acid. Differential scanning calorimetry and scanning electron microscopy analysis indicated that the g‐sPS maintained a high glass‐transition temperature and a crystalline structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1659–1666, 2005     

Preparation and characterization of poly(dimethylsiloxane)-polytetrafluoroethylene (PDMS-PTFE) composite membrane for pervaporation of chloroform from aqueous solution

Hydrophobic polydimethylsiloxane — polytetrafluoroethylene (PDMS-PTFE) flat-sheet membranes for pervaporation (PV) of chloroform from aqueous solution were successfully fabricated by solution casting method. The structures and the performance of the membranes was characterized by X-ray diffraction (XRD), scanning electron microscope combined with energy dispersive X-ray spectroscopy (SEM-EDXS), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and the tests of contact angle and mechanical properties. The adding of PTFE particles (<4 μm) in the PDMS matrix enhanced the crystallinity, hydrophobicity, mechanical strength and thermal stability of the membranes. The examinations showed that the PTFE filled PDMS membranes exhibited striking advantages in flux and separation factor as compared with unfilled PDMS membranes. All the filled PDMS membranes with different PTFE content showed excellent PV properties for the separation of chloroform from water. When the content of the PTFE additive in PDMS composite membrane was 30 wt%, membrane performance was the best at feed temperature 50 °C and permeate-side vacuum 0.101MPa. For the 30% PTFE-PDMS membrane, with the increase of the feed temperature from 30 to 60 °C, the total, water and chloroform fluxes as well as the separation factor increased, the apparent activation energy (ΔEa) of total, chloroform and water were 21.08, 66.65 and 11.49 KJ/mol, respectively, with an increase of chloroform concentration in the feed from 50 to 950 ppm, total, water and chloroform fluxes increased but the separation factor decreased.     

Effect of the crystallization conditions on the phase behavior of syndiotactic polystyrene/poly(phenylene oxide) blends

Syndiotactic polystyrene (sPS) and poly(phenylene oxide) (PPO) blends, miscible in the melt state, were crystallized from the melt and the quenched state at different temperatures. The effect of the crystallization temperature on the phase behavior of the blends and the polymorphic changes in sPS was investigated by dynamic mechanical analysis (DMA), wide‐angle X‐ray diffraction (WAXD), and density measurements. In most blends, the crystallization of sPS induced segregation into two homogeneous amorphous phases of different compositions. The temperatures of the DMA relaxations of the neat homopolymers and crystallized blends were fit by the Gordon–Taylor relation to calculate the compositions of these phases. In melt‐crystallized blends, with slower crystallization, the major amorphous phase became sPS‐rich, whereas the minor phase became PPO‐rich. These major and minor amorphous phases could be tentatively assigned to interfibrillar and interlamellar regions, respectively. In cold‐crystallized blends, slower crystallization decreased the sPS concentration in both phases, and the scale of segregation was much smaller. WAXD studies and density measurements indicated a complex polymorphic behavior of sPS after it was blended with PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1975–1983, 2003     

Viscoelastic behavior of thermosetting epoxy mixtures modified with syndiotactic polystyrene during network formation

The rheological behavior of thermosetting epoxy mixtures modified with thermoplastic syndiotactic polystyrene (sPS) was monitored during the curing of the epoxy resin. The selected thermosetting system was diglycidyl ether of bisphenol A cured with 4,4′‐methylene bis(3‐chloro‐2,6‐diethylaniline) in the presence of various compositions of sPS (from 2.5 to 12.5 wt %). The storage and loss shear moduli of the systems were monitored during network formation. The validity of the Winter–Chambon criterion for the accurate determination at the gelation point from rheological data was demonstrated. The influence of the sPS concentration on the dynamic rheological properties of the samples was investigated. The experimental data showed that at sPS concentrations lower than 7.5 wt %, phase separation induced a quick increase in the viscosity, which was related to a crystallization‐induced phase separation of sPS. For sPS concentrations higher than 7.5 wt %, near the phase‐inversion composition, the rheological behavior of the mixtures was characteristic of a cocontinuous structure. After the viscosity jumped at the onset of phase separation, a decrease in the viscosity was found, and later on, the viscosity increased again because of gelation. Additionally, the influence of the cure temperature on the rheological properties was studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2348–2355, 2006