交联剂分子量对高吸水性树脂性能的影响

通过丙烯酰氯对聚乙二醇的封端反应合成了一系列分子量不同、结构类似的交联剂———聚乙二醇二丙烯酸酯 (PEGDA) ,并用于聚丙烯酸高吸水性树脂的制备 .运用FTIR对PEGDA进行了分析 .吸水性能实验结果表明 ,交联剂的分子量越大 ,则高吸水性树脂的吸水倍率越高 ,吸水速率越大 ,而相对吸水速率降低 .同时 ,PEGDA与常用的交联剂N ,N′ 亚甲基双丙烯酰胺 (MBA)相比 ,前者制备的高吸水性树脂的吸水倍率远高于后者 ;线型可溶性聚合物及残留单体的含量 ,前者也低于后者     

耐电解质高吸水性树脂

在简述高吸水性树脂吸水机理的基础上,综述了改善高吸水性树脂耐电解质性能的四种途径,结合聚合方法重点讨论了提高亲水性、引入长链疏不性单体以及合成两性聚合物三种改性途径。     

碳纳米管复合聚丙烯酸钠的制备及吸水性能

以过硫酸铵(APS)为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,采用水溶液聚合法制备了碳纳米管/聚丙烯酸钠高吸水树脂。系统考察了碳纳米管质量分数、引发剂、交联剂和聚合温度对树脂吸水性能的影响。结果表明,以单体丙烯酸质量为基准,当交联剂,引发剂和碳纳米管质量分数分别为0.04%、0.3%和0.3%,聚合温度75℃时,所合成树脂的吸水性能最佳。添加碳纳米管后树脂表面粗糙和形成孔结构导致了其吸水性能的变化,使得碳纳米管/聚丙烯酸钠的吸水量和吸水速率明显提高,其吸去离子水和生理盐水能力分别达到1423和104g/g。该树脂重复吸水5次后,其吸水能力为1081.5g/g,达到最大吸水倍数的76.0%。     

淀粉基高吸水性树脂吸水性能的测定条件评价

研究了测定条件对淀粉基高吸水性树脂吸水性能的影响,分别考察了测定方法、树脂粒径、初始加水量、水介质pH、温度及溶液中盐的质量分数对树脂吸水倍率和吸水速率的影响.结果表明,采用100目网筛过滤法测定树脂的吸水性能结果较准确;当吸水介质与干树脂的质量比为2 400∶1,pH为7时,可以使树脂达到最大饱和吸水倍率;在树脂粒径96～180μm范围内,随着树脂粒径的减小、水介质温度的升高及盐浓度的降低,树脂的吸水倍率和吸水速率增大.     

P(AA／AMPS)耐盐性高吸水树脂的合成及吸水性能北大核心CSCD

采用反相悬浮聚合法合成了丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物(P(AA/AMPS))耐盐性高吸水树脂,利用正交试验、单因素分析确定了合成树脂的最佳实验工艺条件,并对树脂的吸水性、保水性、反复吸水性能进行研究。结果表明,树脂在最佳条件下吸水倍率为1753.4g/g;树脂具有良好的耐盐性,吸盐水倍率达到189.64g/g;在一定温度范围内,树脂具有良好的保水性能。     

P(AA/AMPS)耐盐性高吸水树脂的合成及吸水性能

采用反相悬浮聚合法合成了丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物(P(AA/AMPS))耐盐性高吸水树脂,利用正交试验、单因素分析确定了合成树脂的最佳实验工艺条件,并对树脂的吸水性、保水性、反复吸水性能进行研究。结果表明,树脂在最佳条件下吸水倍率为1753.4g/g;树脂具有良好的耐盐性,吸盐水倍率达到189.64g/g;在一定温度范围内,树脂具有良好的保水性能。     

DSC研究高吸水树脂吸水性能与分子结构的关系

以丙烯酸(AA)、丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为共聚单体合成了聚丙烯酸-丙烯酰胺-2-丙烯酰胺基-2-甲基丙磺酸(PAA-AM-AMPS)三元共聚物高吸水树脂.利用茶叶袋法测定了其最大吸水倍率,通过差示扫描量热仪(DSC)测定并比较了含水量为50%,75%和91%的各种水凝胶的自由水和结合水含量.结果表明在蒸馏水和生理盐水中高吸水树脂的最大吸水倍率分别为1900g/g和185g/g,共聚物的结合水含量随着AMPS和AA含量增加及AM含量的减少而增大;在0.9%生理盐水中,结合水含量随着AMPS和AM含量增加及AA含量的减少而增大,共聚物和均聚物高吸水树脂的最大吸水倍率呈现出与结合水含量相同的变化规律.     

富含纤维素类农作物秆与丙烯酸接枝共聚制备高倍率吸水树脂

用棉花秆、麦秆和玉米秆等富含纤维素类农作物秆与丙烯酸接枝共聚制备了高倍率的吸水树脂. 研究了不同水质(去离子水、自来水及雨水)对接枝产物吸水性能的影响. 采用棉花秆、麦秆、玉米秆与丙烯酸的接枝产物对去离子水的吸水倍率分别为930, 790和630 g/g, 对自来水的吸水倍率分别为670, 350和250 g/g, 用玉米秆/地瓜淀粉混合物制备的接枝产物对雨水的吸水倍率为540 g/g. 为棉花秆、 麦秆及玉米秆等富含纤维素的农作物秆的深加工与应用开辟了一条途径.     

腐植酸钠/聚丙烯酰胺/粘土杂化水凝胶的研究

以过硫酸钾为引发剂、N,N′-亚甲基双丙烯酰胺为交联剂、丙烯酰胺单体和腐植酸钠、Laponite RD粘土为原料,用溶液聚合交联法合成了腐植酸钠/聚丙烯酰胺/粘土(SH-PAM-Clay)系列水凝胶.用场发射扫描电镜对其表面形貌进行了研究,并对水凝胶的吸水性和流变性能进行了测试和研究.结果表明这系列水凝胶都具有致密的网络结构和优良的吸水性能.     

高吸水性树脂性能缺陷及其改性策略的研究进展

高吸水性树脂凭借其优越的吸水和保水性能,已成为国民经济各个领域中不可或缺的重要材料,但传统的高吸水性树脂吸水速度慢、耐盐性差、凝胶强度低等问题限制了其发展。针对高吸水性树脂日益明显的缺陷,科研人员开始着手研究合成和加工新方法,以降低树脂生产成本低,提高树脂生物降解性、凝胶强度、吸水性和耐盐性等性能,从而推广产品使用范围。本文基于近年来该领域的研究,概括了高吸水性树脂目前主要存在的性能缺陷,并提出相应的改性策略来提高吸水性树脂的综合性能。     

Fire retardancy and biodegradability of poly(methyl methacrylate)/montmorillonite nanocomposite

The poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposite was prepared by emulsifier-free emulsion technique and its structure and properties were characterized with infra red, X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, and cone calorimetry. The highly exfoliated MMT layers with dimension 1-2 nm in thickness were randomly dispersed in the polymer matrix containing MMT lower than 5% w/v, whereas the intercalated structure was predominant with MMT content higher than 5% w/v. Consequently, the fine dispersion of the MMT and the strong interactions between PMMA and MMT created significant improvement of the thermo-stability and fire retardancy of the nanocomposite. The combustion behavior has been evaluated using oxygen consumption cone calorimetry. In addition, a scheme was proposed to describe fire retardancy of PMMA and MMT as well as the correlation between the interaction and structure in polymer/clay systems. The biodegradability of the nanocomposite fire-retardant was tested for its better commercialization.     

Synthesis of exfoliated polystyrene/montmorillonite nanocomposite by emulsion polymerization using a zwitterion as the clay modifier

Montmorillonite (MMT) was modified with zwitterion aminoundecanoic acid (AUA). First AUA was protonized to facilitate molecules to get into the galleries of the montmorillonite to accomplish ion exchange, and the carboxyl groups were then ionized in the alkaline aqueous media to enable exfoliation of the clay. It was demonstrated by rheological measurements and atomic force microscopic studies that exfoliation of the clay driven by the electrostatic repulsion took place in an alkaline medium. Polystyrene/montmorillonite (PS/MMT) nanocomposite was synthesized via emulsion polymerization in the presence of the modified MMT. The exfoliated microstructure of the composites was studied by the X-ray diffraction and transmission electron microscopy. The exfoliated PS/MMT nanocomposite showed a greatly improved modulus, a higher glass transition temperature and a better thermal stability compared to the neat polystyrene and the intercalated PS/MMT composites.     

精氨酸插层氧化锰纳米结构材料的制备和表征

应用氧化法水热合成了Na型层状氧化锰[BirMO(Na)], 通过离子交换反应在0.1 mol/L HCl溶液中Na型层状氧化锰转化成H型层状氧化锰[BirMO(H)]. BirMO(H)在四甲基氢氧化铵[(CH3)4NOH]溶液中搅拌处理7 d后, 剥离生成了MnO2纳米层胶体分散液. 剥离的MnO2纳米层胶体分散液在pH＝4.0～11.0的精氨酸溶液中搅拌2 d, 得到了层间距为1.49 nm的精氨酸插层氧化锰纳米结构材料. 通过XRD, DSC-TGA, SEM, IR及元素分析对合成试样进行了分析表征. 结果表明精氨酸在氧化锰层间的插入量及插入形式与重组溶液的pH值密切相关, 其最大插入量为1.80 mmol/g.     

Synthesis of poly(methyl methacrylate) nanocomposites via emulsion polymerization using a zwitterionic surfactant

The synthesis of nanocomposites via emulsion polymerization was investigated using methyl methacrylate (MMA) monomer, 10 wt % montmorillonite (MMT) clay, and a zwitterionic surfactant octadecyl dimethyl betaine (C18DMB). The particle size of the diluted polymer emulsion was about 550 nm, as determined by light scattering, while the sample without clay had a diameter of about 350 nm. The increase in the droplet size suggests that clay was present in the emulsion droplets. X-ray diffraction indicated no peak in the nanocomposites. Transmission electron microscopy showed that emulsion polymerization of MMA in the presence of C18DMB and MMT formed partially exfoliated nanocomposites. Differential scanning calorimetry showed an increase of 18 degrees C in the glass transition temperature (Tg) of the nanocomposites. A dynamic mechanical thermal analyzer also verified a similar Tg increase, 16 degrees C, for the partially exfoliated nanocomposites over poly(methyl methacrylate) (PMMA). Thermogravimetric analysis indicated a 37 degrees C increase in the decomposition temperature for a 20 wt % loss. A PMMA nanocomposite with 10 wt % C18DMB-MMT was also synthesized via in situ polymerization. This nanocomposite was intercalated and had a Tg 10 degrees lower than the emulsion nanocomposite. The storage modulus of the partially exfoliated emulsion nanocomposite was superior to the intercalated structure at higher temperatures and to the pure polymer. The rubbery plateau modulus was over 30 times higher for the emulsion product versus pure PMMA. The emulsion technique produced nanocomposites of the highest molecular weight with a bimodal distribution. This reinstates that exfoliated structures have enhanced thermal and mechanical properties over intercalated hybrids.     

Conformational behavior of dodecyldiamine inside the confined space of montmorillonites

We have investigated the change of the intercalated amount and conformational behavior of dodecyldiamine (C(12)H(28)N(2), di-C(12)amine) inside the confined space of the montmorillonite (MMT) intergallery at different pHs of the intercalation solution (H(2)O/ethanol/Na(+)-MMT/di-C(12)amine), and these results were compared with those of dodecylmonoamine (C(12)H(27)N, mono-C(12)amine). The mono-C(12)amine with one end-functional amine (-NH(2)) has a constant intercalated amount independent of the pH of the intercalation solution, confirming the tail conformation in the MMT intergallery. On the other hand, the intercalated amount of di-C(12)amines remains quite low at low pH due to the long-range Coulombic repulsion among protonated amines. The di-C(12)amines dominantly take the bridge conformation inside the MMT intergallery up to pH 9.5 and adopt a fraction of the tail conformation at pH 11.5, which is verified by Fourier transform infrared spectra with an abrupt frequency shift of the CH(2) stretching band and the emergence of a new NH(2) scissoring band at 1598 cm(-)(1) related to unanchored free amines. The d-spacing and the square of the half-width at half-maximum of the MMT based on X-ray diffraction measurements are also constant up to pH 9.5, while these two variables are suddenly increased at pH 11.5. The bridge conformation of di-C(12)amines in the confined space of the MMT intergallery prevents poly(ethylene oxide) chains from intercalation into the MMT intergallery, called the gluing effect.     

Immobilization of poly(fluorene) within clay nanocomposite: an easy way to control keto defect

Blue light emitting cationic polyfluorene polymer(PF)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation and exfoliation method to evaluate the effect of MMT on the nanocomposite structures, properties and morphologies. The properties of PF-MMT composites, containing 1-50 mass% MMT, were characterized unambiguously with the help of multiple analytical techniques, with focus on the keto defect and photostability of PF in the nanocomposites. XRD and HRTEM studies reveal both exfoliation of MMT galleries at lower content of MMT in composites and intercalation of PF chains into the MMT galleries at higher MMT content. The nanocomposites show higher thermal stability than pristine PF as anchorage of nanoclay in PF matrix occur through the electrostatic interaction between nanoclay and polymer. The decrease in Si-O-Si stretching frequency during exfoliation is much higher than in intercalation, as Si-O-Si experience lesser hindrance to vibrate in exfoliated MMT galleries. The gradual redshift of π-π(*) transition peak of PF with increasing MMT content in composites confirms the uncoiling of PF in clay galleries. The photoluminescence characteristics reveal interruption of interchain interaction in this intercalated and exfoliated organic/inorganic hybrid system, which reduces the low-energy emission that results from keto defect. Due to very high aspect ratio of MMT, it can act as an efficient exciton blocking layer and a barrier to oxygen diffusion, which may lead to a device with high color purity and enhanced photostability. Again current-voltage characteristics of nanocomposite films confirm the retention of LED properties after nanocomposite formation.     

PMMA/MMT nanocomposites prepared by one-step in situ intercalative solution polymerization

Poly(methylmetacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by one-step in situ intercalative solution polymerization involving simultaneous modification of MMT with quaternary ammonium salts (QAS), polymerization and polymer intercalation. Polymerization proceeded at 70 °C in a mixture of ethanol and water, whereas the nanocomposite was precipitated with only water. Four QAS’s with different alkyl chain lengths, as well as a QAS with an additional acrylic group, were used to study the influence of the type of quaternary ammonium salt on intercalation. The largest extent of intercalation was achieved in nanocomposites with the QAS having one long alkyl (C16) chain. The obtained PMMA/MMT intercalated nanocomposites exhibited a higher glass transition temperature, better thermal stability, and improved solvent resistance than the pure PMMA.     

Poly(vinyl acetate)/poly(vinyl alcohol)/montmorillonite nanocomposite microspheres prepared by suspension polymerization and saponification

Poly(vinyl acetate) (PVAc)–poly(vinyl alcohol)–montmorillonite (MMT) nanocomposite microspheres were prepared through suspension polymerization followed by the heterogeneous saponification. The effects of MMT on the polymerization rate and the saponification rate of PVAc were studied. It was found that the rate of polymerization decreased when MMT content was increased. However, the saponification rate of PVAc significantly increased in the presence of nanoclay particles. The XRD measurement illustrated that the clay particles are intercalated in the polymer matrix.     

Poly(styrene‐b‐tetrahydrofuran)/clay nanocomposites by mechanistic transformation

Synthesis of poly(styrene‐block‐tetrahydrofuran) (PSt‐b‐PTHF) block copolymer on the surfaces of intercalated and exfoliated silicate (clay) layers by mechanistic transformation was described. First, the polystyrene/montmorillonite (PSt/MMT) nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Then, the PSt‐b‐PTHF/MMT nanocomposite was prepared by mechanistic transformation from ATRP to cationic ring opening polymerization (CROP). The TGA thermogram of the PSt‐b‐PTHF/MMT nanocomposite has two decomposition stages corresponding to PTHF and PSt segments. All nanocomposites exhibit enhanced thermal stabilities compared with the virgin polymer segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2190–2197, 2009     

Gas barrier of polystyrene montmorillonite clay nanocomposites: Effect of mineral layer aggregation

Three polystyrene (PS)/clay hybrid systems have been prepared via in situ polymerization of styrene in the presence of unmodified sodium montmorillonite (Na‐MMT) clay, MMT modified with zwitterionic cationic surfactant octadecyldimethyl betaine (C18DMB) and MMT modified with polymerizable cationic surfactant vinylbenzyldimethyldodecylammonium chloride (VDAC). X‐ray diffraction and TEM were used to probe mineral layer organization and to expose the morphology of these systems. The PS/Na‐MMT composite was found to exhibit a conventional composite structure consisting of unintercalated micro and nanoclay particles homogeneously dispersed in the PS matrix. The PS/C18DMB‐MMT system exhibited an intercalated layered silicate nanocomposite structure consisting of intercalated tactoids dispersed in the PS matrix. Finally, the PS/VDAC‐MMT system exhibited features of both intercalated and exfoliated nanocomposites. Systematic statistical analysis of aggregate orientation, characteristic width, length, aspect ratio, and number of layers using multiple TEM micrographs enabled the development of representative morphological models for each of the nanocomposite structures. Oxygen barrier properties of all three PS/clay hybrid systems were measured as a function of mineral composition and analyzed in terms of traditional Nielsen and Cussler approaches. A modification of the Nielsen model has been proposed, which considers the effect of layer aggregation (layer stacking) on gas barrier. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1733–1753, 2007