端羟基超支化聚酯的稳定化改性及热分解行为

以长链烷基酸为改性剂,对以三羟甲基丙烷为核、二羟甲基丙酸为支化单体合成的端羟基超支化聚酯进行端基稳定化改性。采用羟值滴定和核磁共振氢谱(1H-NMR)表征超支化聚酯的改性程度;采用热重-微商热重分析(TG-DTG)研究了代数、端基类型以及改性程度对超支化聚酯热稳定性和热分解行为的影响。结果表明,将不稳定的端羟基转变为热稳定的端烷基后,超支化聚酯的热稳定性明显提高,且改性程度越高,或长烷烃链越短,聚合物的热稳定性越好。超支化聚酯的热分解主要包括两个失重阶段,分别对应于由大量端基所组成的"壳"的破坏以及由大量C-C单键所组成的骨架(即"核")解体。极性端羟基的含量越小或非极性端烷基的含量越大,第一失重峰越不明显。     

含羧基超支化聚酯丙烯酸酯的合成及其性能研究

以季戊四醇为"核",二羟甲基丙酸为AB2单体,利用逐步聚合方法合成了不同代数超支化聚酯。将得到的不同代数超支化聚酯用丁二酸酐和六亚甲基二异氰酸酯与丙烯酸羟乙酯的半加成产物按不同比例进行改性,得到了含羧基超支化聚酯丙烯酸酯。对得到的含羧基超支化聚酯丙烯酸酯的结构用傅里叶红外光谱、核磁共振波谱等手段进行了表征。紫外光谱表明,所有超支化低聚物在210 nm处有强紫外吸收;差示扫描结果表明,所有超支化聚酯丙烯酸酯都具有低的玻璃化转变温度;热重分析测试结果显示,随着超支化聚酯代数增加,超支化聚酯丙烯酸酯固化膜耐热性能提高。     

脂肪族超支化聚酯的端链结晶行为

以长链烷基酸为改性剂,对以三羟甲基丙烷为核、二羟甲基丙酸为支化单体合成的第三代端羟基超支化聚酯进行端基改性,采用羟值滴定和核磁共振氢谱(1H-NMR)表征超支化聚酯的改性程度,采用差示扫描量热分析(DSC)和广角X射线衍射(WAXD)研究了端烷烃链长度和端基改性程度对超支化聚酯相转变行为和结晶行为的影响。结果表明,超支化聚酯的结晶归因于长链端烷烃的有序排列,端烷烃链越长,端烷基超支化聚酯的冷结晶温度、热结晶温度和熔融温度均逐渐升高;端烷烃链越长或改性程度越高,衍射峰强度越大,晶粒尺寸变小。进一步用DSC研究了端十八烷基超支化聚酯的非等温结晶行为并用Ozawa法对其非等温结晶动力学进行了分析,发现其成核方式为异相成核,生长方式为针状晶体的一维生长。     

棕榈酸对脂肪族超支化聚酯的端基改性研究

采用准一步法,以三羟甲基丙烷为核,2,2-二羟甲基丙酸为AB2型单体合成超支化聚酯。为了拓宽其使用范围,用棕榈酸(十六碳酸)对超支化聚酯进行端基改性,成功地找出了提纯的方法,并进行了表征。测试结果表明,聚酯的端羟基大约有97%被酯化,说明方法可行。与用棕榈酰氯进行改性相比,大大节约了成本。     

超支化聚酯对环氧 -聚酯混合型粉末涂料耐冲击性的改性研究

首先通过准一步法以三羟甲基丙烷（ TMP）为核,以 2,2-二羟甲基丙酸（ DMPA）为 AB2单体,制备了端羟基超支化聚酯（HBPE-OH）。然后采用邻苯二甲酸酐对端羟基超支化聚酯进行端基改性制备了端羧基超支化聚酯（ HBPE-COOH）。研究了上述 2种超支化聚酯对环氧 -聚酯体系固化性能及环氧 -聚酯混合型粉末涂料增韧效果的影响。研究结果表明： HBPE-COOH可使环氧 -聚酯体系的固化程度增大,而 HBPE-OH使环氧 -聚酯体系的固化程度略有降低。由于超支化聚酯分子内存在大量的空腔, 2种 HBPE均可有效提高涂层的耐冲击性能。其中, HBPE-COOH的增韧效果更佳。     

渗透汽化法汽油脱硫用乙基纤维素膜制备工艺的优化

为了进一步提高乙基纤维素(EC)膜的脱硫性能,利用光引发交联反应将丙烯酸酯单体和EC聚合物合成交联EC膜,用红外光谱仪、扫描电镜对该膜的膜结构进行了表征。采用模拟汽油评价了EC膜的脱硫性能,研究了EC质量分数、交联剂质量分数、成膜温度、脱硫温度对EC膜渗透汽化性能的影响。结果表明,随着EC质量分数和交联剂质量分数的增加,硫富集因子和通量均先增大后减小,存在极大值;随着成膜温度和脱硫温度的升高,硫富集因子逐渐降低,通量一直增加。综合考虑两者对汽油脱硫的贡献,选取EC质量分数为18%,交联剂质量分数为21%~22%,成膜温度为50℃,脱硫温度为80℃为最佳脱硫条件。     

超支化聚氨酯丙烯酸酯的合成及其紫外光固化膜性能研究

以季戊四醇为核、2,2-二羟甲基丙酸为臂,采用一步熔融法合成了含16个端羟基的超支化聚酯(HBPE)。利用异佛尔酮二异氰酸酯和丙烯酸-2-羟乙酯的半加成产物改性HBPE,制备了一系列末端含有不同数量C=C的超支化聚氨酯丙烯酸酯(HBPUA),并对HBPUA涂料固化过程和固化膜性能进行研究。结果表明,HBPUA改性度越大、用量越多,涂料固化时间越短,C=C转化率增大,固化膜的硬度增强,柔韧性和抗冲击性能减弱;当HBPUA质量分数超过60%时,涂料固化速度快,C=C转化率大于90%,固化膜综合性能优异。     

超支化聚酯的端基改性及其涂膜性能

以三羟甲基丙烷为核多元醇,二羟甲基丙酸为AB₂型单体,对甲苯磺酸为催化剂准一步法合成了第二代超支化聚酯(HBP-0)。HBP-0分别经己内酯和月桂酸改性得到改性超支化聚酯(HBPs)。采用FT-IR、¹H NMR和GPC对HBP-0的结构和相对分子质量进行表征,发现超支化聚酯的支化度为0.43,相对分子量与理论相对分子量比较接近, 相对分子质量分布系数只有1.72。以甲苯二异氰酸酯加成物为交联剂,考察了改性超支化聚酯交联涂膜性能,结果表明,3种改性超支化聚酯的涂膜性能在光泽度、耐冲击性、附着力和柔韧性方面表现十分优异。其中HBP-3同时用己内酯和月桂酸改性具有最佳性能,黏度最低为7500 mPa·s,涂膜表干40 min,且硬度达到F。而单独用己内酯或月桂酸改性的HBP-1和HBP-2的相应数据分别为7×10⁵ mPa·s、20 min和HB及17500 mPa·s、90 min和2B。     

端环氧基超支化聚酯的合成及应用

本文以季戊四醇为心核结构、2,2-二羟甲基丁酸为重复单元、对苯甲磺酸为催化剂,合成了端羟基超支化聚酯;然后,采用环氧氯丙烷对超支化聚酯的端羟基进行环氧官能化,合成端环氧基超支化聚酯,采用GPC、13CNMR及1H-NMR图谱对结构进行表征。采用端环氧基超支化聚酯做增韧剂,研究其对双酚A环氧树脂力学性能的影响,探讨了端环氧基超支化聚酯对环氧树脂固化体系力学性能及韧性的影响。     

端环氧型超支化聚酯对聚（3-羟基丁酸戊酸共聚酯）的改性研究

以2,2二羟甲基丙酸（DMPA）和三羟甲基丙烷（TMP）为原料,以对甲苯磺酸（P-TSA）为催化剂,通过“一步法”合成三代超支化聚酯（HBPE）,然后采用环氧氯丙烷对HBPE进行改性,得到了具有端环氧基的三代超支化聚酯（EHBP-G3）目标产物,最后采用熔融共混法制备了EHBP改性的聚（3-羟基丁酸酯-co-3羟基戊酸酯）（PHBV）树脂;通过差示扫描量热仪、偏光显微镜、力学性能和熔体流动速率等分析方法对制备的PHBV/EHBP共混物进行表征。结果表明,加入1.5 %(质量分数,下同)三代超支化聚酯（EHBP-G3）时,PHBV/EHBP共混物的结晶度下降了16.1 %,冲击强度提高了34.3 %。     

γ-(2,3环氧丙氧)丙基三甲氧基硅烷改性壳聚糖渗透蒸发杂化膜的制备及乙醇脱水性能研究

通过γ-缩水甘油醚氧丙基三甲氧基硅(KH-560)对壳聚糖进行交联改性制备乙醇脱水渗透蒸发杂化膜.实验结果表明偶联剂的加入能有效提高壳聚糖膜的分离效果,随着偶联剂含量的增加,杂化膜的对水的选择性先增加后下降,在2％(质量分数)时有最好的选择性.膜的分离因子随着进料温度的增大而降低,随着乙醇浓度的增大而增大;通量随着进料温度的增大而增大,随着乙醇浓度增大而减小.硅烷偶联剂/壳聚糖杂化膜呈现出良好的渗透蒸发分离性能,当进料乙醇浓度为95％(质量分数),温度为35℃时,通量和分离因子分别为134g/(h·m2)和97214.     

Characterization,separation performance,and model analysis of STPP‐chitosan/PAN polyelectrolyte complex membranes

Polyelectrolyte complex membranes (PCMs) were prepared using sodium tripolyphosphate (STPP) solution surface‐crosslinking chitosan/polyacrylonitrile (PAN) composite membranes. Fourier transform infrared (FTIR) was used to characterize the surface‐crosslinking. The effects of different surface‐crosslinking time on morphologies, element distribution, and crystal structures were investigated by scanning electron microscopy (SEM), energy dispersion of X‐ray (EDX), and X‐ray diffraction (XRD). The effect of crosslinking ratio on swelling ratio was analyzed. The separation performances of PCMs in terms of permeation flux and separation factor were measured by dehydrating ethyl acetate aqueous solutions. A kinetic model of crosslinking reaction was proposed to investigate the effect of crosslinking agent concentration and surface‐crosslinking time on the crosslinking ratio of PCMs. It was found that the membrane possessed the excellent performance when surface crosslinked for 15 min. The permeation flux and separation factor were 336 g/(m² h) and 6270 in 97 wt % ethyl acetate aqueous solution at 313 K. The crosslinking ratio of PCM exponentially increased as time increased, while linearly increased as concentration and diffusion coefficient of crosslinking agent STPP solution increased. And the effect of crosslinking agent concentration on crosslinking ratio was inversely proportional to surface‐crosslinking time. The experimental results matched well with the kinetic model when STPP concentration was lower than 5 wt %. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pervaporation separation of water/isopropanol mixtures through crosslinked carboxymethyl chitosan/polysulfone hollow‐fiber composite membranes

Carboxymethyl chitosan (CMCS)/polysulfone (PS) hollow‐fiber composite membranes were prepared through glutaraldehyde (GA) as the crosslinking agent and PS hollow‐fiber ultrafiltration membrane as the support. The permeation and separation characteristics for dehydration of isopropanol were investigated by the pervaporation method. Pure chitosan, carboxymethyl chitosan, and crosslinked carboxymethyl chitosan membranes were characterized by Fourier transform infrared (FT‐IR) spectroscopy and X‐ray diffraction (XRD) to study the crosslinking reaction mechanism and degree of crystallinity, respectively. The effects of feed composition, crosslinking agent, membrane thickness, and feed temperature on membrane performance were investigated. The results show that the crosslinked CMCS/PS hollow‐fiber composite membranes possess high selectivity and promising permeability. The permeation flux and separation factor for isopropanol/water is 38.6 g/m²h and 3238.5, using 87.5 wt % isopropanol concentration at 45°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1959–1965, 2007     

Effect of ethylene vinyl acetate content on the performance of VMD using HDPE co-blending membrane

Membranes were fabricated with high-density polyethylene(HDPE) and ethylene vinyl acetate(EVA) blend through thermally induced phase separation and were then used for vacuum membrane distillation(VMD).The membranes were supported by nonwoven polyester fabric with a special cellular structure. Different membrane samples were obtained by adjusting the polymer concentration, HDPE/EVA weight ratio, and coagulation bath temperature. The membranes were characterized by scanning electron microscopy(SEM) analysis, contact angle test, and evaluation of porosity and pore size distribution. A series of VMD tests were conducted using aqueous NaCl solution(0.5 mol·L~(-1)) at a feed temperature of 65 ℃ and permeate side absolute pressure of 3 kPa. The membranes showed excellent performance in water permeation flux, salt rejection, and long-term stability. The HDPE/EVA co-blending membranes exhibited the largest permeation flux of 23.87 kg·m~(-2)·h~(-1) and benign salt rejection of ≥99.9%.     

Poly(vinyl alcohol)/Carboxyl Graphene Membranes for Ethanol Dehydration by Pervaporation

Carboxyl graphene (CG) with two functions of hybridization and crosslinking was incorporated into poly(vinyl alcohol) (PVA) matrix to form PVA/CG mixed-matrix membranes (MMMs). The membranes demonstrated excellent mechanical properties and thermal stability. The improved hydrophilicity and formed crosslinking structure led to moderate swelling. The membrane crystallinity decreased and the free volume was promoted with increasing CG loading amount. The pervaporation (PV) separation performance for ethanol dehydration indicated that both permeation flux and separation factor were enhanced simultaneously at the optimum CG loading. Subsequently, the permeation flux continued to increase while the separation factor declined at higher CG loadings.     

Modification of poly(vinyl alcohol) membranes using sulfur-succinic acid and its application to pervaporation separation of water–alcohol mixtures

For the purposes of the water-selective membrane material development for pervaporation separation, we crosslinked poly(vinyl alcohol) (PVA) with sulfur-succinic acid (SSA), which contains —SO₃OH, by heat treatment and investigated the effect of the crosslinking density on the separation of water–alcohol mixtures by pervaporation technique. The crosslinking reaction between PVA and SSA was characterized through Fourier transform infrared spectroscopy and differential scanning calorimetry tests by varying the amount of the crosslinking agent, the reaction temperature, and the swelling measurements of each pure component. The separation performance of the water–methanol mixture is not good due to the existence of sulfonic acid, hydrophilic group, in the crosslinking agent. However, for the water–ethanol mixture, the flux of 0.291 kg/m²h and the separation factor of 171 were obtained at 70°C when PVA-crosslinked membrane containing 7 wt % SSA was used. The same membrane also showed flux of 0.206 kg/m²h and a separation factor of 1969 at the same operating temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1717–1723, 1998     

Separation of Water/Ethanol Vapor Mixtures through Chitosan and Crosslinked Chitosan Membranes

Abstract

The separation of water/ethanol vapor mixtures through chitosan membranes and crosslinked chitosan membranes was studied by means of the vapor permeation technique. The permeation performance was discussed in terms of separation factor and permeation flux. Crosslinking the chitosan membrane by glutaraldehyde enhanced the selectivity. The highest separation factor obtained was 6000 for a crosslinked chitosan membrane with a degree of deacetylation of 100%.     

Preparation of crosslinked alginate composite membrane for dehydration of ethanol–water mixtures

The purpose of this article was to develop new membranes with a high selectivity and permeation rate for separation of an alcohol/water system. Crosslinked alginate composite membranes were prepared by casting an aqueous solution of alginate and 1,6‐hexanediamine (HDM) onto a hydrolyzed microporous polyacrylonitrile (PAN) membrane. The influence of hydrolysis of the support membrane and crosslinking agent content in a dense layer on the selectivity and flux was studied and it was shown that both could improve the separation performance of the composite membrane greatly. The countercation of alginate coatings as a dense separating layer also influenced the separation properties of the membrane, which was better for K⁺ than for Na⁺. This novel composite membrane with K⁺ as a counterion has a high separation factor of 891 and a good permeation rate of 591 g m⁻² h⁻¹ for pervaporation of a 90 wt % ethanol aqueous solution at 70°C. At the same time, SEM micrographs showed that the pore structure of the PAN microporous membrane is changed by hydrolysis. The reason for the influence of the preparation conditions on the separation performance of the novel membrane is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3054–3061, 2000     

β-环糊精/聚醚共聚乙酰胺填充膜的制备及渗透汽化分离水中微量苯酚

将β-环糊精（β-CD）添加到聚醚共聚乙酰胺（PEBA）中制备β-环糊精/聚醚共聚乙酰胺填充膜（β-CD-f-PEBA）,用于苯酚-水的渗透汽化分离研究。SEM、FTIR表明β-环糊精在膜中分散均匀且与膜结合紧密,与膜间只有氢键相互作用而未发生化学交联。拉伸实验表明膜的拉伸强度和断裂强度均随着β-CD添加量的增加先减小后增大。采用基团贡献法计算了PEBA、苯酚及水的溶解度参数,证明PEBA膜对苯酚具有较高的选择吸附性。通过溶胀验证膜对苯酚的选择吸附性能,膜对苯酚的吸附量度随着料液中苯酚浓度和膜中β-CD添加量的增加而增加。考察了PEBA和β-CD-f-PEBA膜的渗透汽化性能,当β-CD填充量为0.5%（质量）时,分离效果最佳,渗透通量和分离因子分别为3062.9 g·m^-2·h^-1和43.3。通过Arrhenius方程计算苯酚和水的渗透活化能分别为97.19和52.12 kJ·mol^-1。重复实验表明β-CD-f-PEBA膜的操作稳定性良好。     

有机硅烷交联PDMS/陶瓷复合膜的制备及渗透汽化汽油脱硫性能

采用有机硅烷γ-氨丙基三甲氧基硅氧烷（APTMS）,对聚二甲基硅氧烷（PDMS）进行交联改性,以ZrO₂/Al₂O₃陶瓷复合膜为支撑体,制备了一系列有机硅烷交联的PDMS/陶瓷复合膜。通过扫描电镜（SEM）、傅里叶红外光谱（FTIR）、热重分析（TGA）对改性效果和膜结构进行了表征。将所制备的PDMS/陶瓷复合膜应用于渗透汽化脱除模拟汽油中的有机硫化物（噻吩）,考察了交联剂APTMS含量、操作温度、料液含硫量等因素对复合膜渗透汽化脱硫性能的影响。实验结果表明,有机硅烷交联的PDMS膜相比于传统正硅酸乙酯（TEOS）交联的PDMS膜,通量和硫富集因子均有所提高。随着进料温度和原料液中硫含量的升高,膜的渗透通量均增大,而硫富集因子均减小。当APTMS质量分数为15%、进料温度为25℃、噻吩质量浓度为100mg/kg时,渗透通量为0.46 kg/（m²·h）,硫富集因子达到3.5。