高交联大孔苯乙烯/二乙烯苯共聚物的合成及其孔结构的研究Ⅰ

利用纯化的二乙烯苯(含量≥95％)作交联剂,合成了一系列苯乙烯/二乙烯苯高交联大孔共聚物,而且较详细地研究了不同聚合条件(如致孔剂用量和组成)对共聚物孔结构的影响。结果表明,高交联共聚物一般都具有高的比表面积,通过调节致孔剂的组成、用量等聚合条件,可以调整和改变共聚物的孔结构。     

苯乙烯-二乙烯苯共聚物通过悬挂双键的后交联反应

本文对大孔苯乙烯－二乙烯苯（St-DVB)共聚物在无外加交联剂条件下的后交联反应进行了研究。通过改变起始St-DVB共聚物的DVB用量及聚合反应时间，比较了以无水三氯化铁、对甲苯磺酸（TSA）及过氧化苯甲酰（BPO）为后交联催化剂时，所得产物的孔结构和吸附性能。实验结果表明，采用FeCl3或TSA为催化剂时，后交联产物的比表面积及吸附能力都有很大提高，而前者比后者的提高幅度更大。在BPO存在下进行后交联时，产物比表面积及孔容的改变不明显，但孔结构稳定性提高。此外，对不同催化剂作用下的后交联反应机理进行了比较。研究结果进一步证明在无外加交联剂的条件下，后交联主要是通过悬挂双键参与的反应进行的。     

高交联苯乙烯-二乙烯苯大孔共聚物的后交联反应

采用工业和实验室合成的高交联大孔苯乙烯－二乙烯苯共聚物,对其对三氯化铁为催化剂,在二氯乙烷溶剂中的后交联反应进行了研究。结果表明,高交联大孔共聚物经后交联反应后,比表面积和孔容都明显增加,增加的幅度与后交联反应条件及大孔共聚物本身的合成条件有重要关系。进一步试验了简化的后交联共聚物的制备方法。所得后交联产物的比表面积仍可达１０００ｍ＾２／ｇ以上,影响后交联反应的因素与未简化的制备方法相同。     

高交联大孔苯乙烯-二乙烯苯共聚物的磺化反应

研究了高交联大孔苯乙烯－二乙烯本共聚物在有溶胀剂和无溶胀剂条件下,反应温度、 反应时间及共聚物合成时所用致孔剂对其磺化反应的影响．结果显示,当磺化反应在不同溶胀 剂介质中进行时,共聚物的交换容量随交联度变化可是现不同的关系．与低交联大孔共聚物（交 联度７％）比较,高文联大孔共聚物（交联度６０％）磺化反应速度更快,反应能在低得多的温度下 进行,同时溶胀介质对磺化产物的交换容量的影响变得很小．６０％交联的共聚物于３５Ｃ反应３ｈ, 可获得接近于表面磺化的产物．     

高交联大孔苯乙烯—二乙烯苯共聚物的磺化反应

研究了高交联大孔苯乙烯－二乙烯苯共聚物在有溶胀剂和无溶胀剂条件下,反应温度、反应时间及共聚物合成时所用致孔剂对其磺化反应的影响。结果显示,当磺化反应在不同溶胀剂介质中进行时,共聚物的交换容量随交联度变化可呈现不同的关系。与低交联大孔共聚物（交联度７％）比较,高交联大孔共聚物（交联度６０％）磺化反应速度更快,反应能在低得多的温度下进行,同时溶胀介质对磺化产物的交换容量的影响变得很小。６０％交联的共聚     

大孔苯乙烯—二乙烯苯共聚物孔结构稳定性的研究

通过溶剂处理和加热处理,研究了致孔剂种类、配比、用量及单体DVB中异构体组成对苯乙烯—二乙烯苯共聚物孔结构稳定性的影响,及其这种影响与共聚物交联度的关系。     

大孔高交联苯乙烯-双烯-A共聚物的合成及孔结构的研究

利用新型交联剂──双甲基丙烯酰氧苯基丙烷(双烯-A)与苯乙烯悬浮共聚合,以甲苯、异戊醇作致孔剂,合成了一系列大孔高交联共聚物。考察了双烯-A用量、甲苯/异戊醇配比、引发剂用量及分散剂用量对共聚物孔结构的影响,通过红外光谱、表现密度、全自动物理吸附仪及扫描电镜对干燥的共聚物小球进行了表征。结果表明,随交联利双烯-A含量的增加,苯乙烯-双烯-A共聚物的表面孔结构明显增大。共聚物的比表面积、孔容及孔径均随致孔剂中不良溶剂异戊醇含量的增加而明显增大。     

甲基丙烯酸缩水甘油酯大孔共聚物的合成、结构及性能研究

以甲基丙烯酸缩水甘油酯为单体,二乙烯苯/三烯丙基异氰脲酸酯作为混合交联剂,甲苯和正庚烷为混合致孔剂,通过悬浮聚合,合成了一系列GMA-DVB-TAIC大孔共聚物,考察了不同反应阶段共聚物的孔结构,通过调节交联剂的用量、致孔剂的用量和比例,可以得到具有较大孔容和孔径、较高热稳定性和性能优良的GTD大孔共聚物.     

丙烯腈系大孔螯合树脂的合成及研究 Ⅱ.AS树脂的FT-IR研究

<正> 二乙烯基苯(DVB)用于树脂的合成时,并非所有的乙烯基都参与交联反应,共聚物中总存在一些悬挂双键。用红外及拉曼光谱对聚合过程中DVB悬挂双键含量变化的动力学研究已有报道。作者用Nicolet 170 SX:付里叶变换红外光谱仪(FT-IR),以积分强度法测定及研究了大孔型丙烯腈-苯乙烯-二乙烯基苯共聚物(大孔AS树脂)中悬     

大孔标准苯乙烯—二乙烯苯共聚物的合成及其结构的研究

本文利用前文分离提纯的对位及间位二乙烯苯作为交联剂,合成了大孔标准苯乙烯—二乙烯苯共聚物,系统地研究了共聚物的交联度,致孔剂的种类和用量以及良溶剂—非良溶剂致孔剂配比的变化对共聚物孔结构的影响。实验结果表明:不同结构的二乙烯苯作交联剂所合成的共聚物,他们的孔结构参数都随共聚物的合成条件的变化呈现规律性的变化,但它们彼此间在结构性能上存在着明显的差异。     

一种后交联大孔吸附树脂的合成及其对苯酚和维生素B_(12)吸附性能研究

工业二乙烯苯悬浮聚合制备的大孔树脂,在二氯乙烷溶剂中以无水三氯化铁为催化剂进行悬挂双键后交联反应,得到的后交联树脂的比表面积和孔容都有显著增加.低温氮气吸附/脱附等温线得到的孔径分布曲线证明初始共聚物PDT-55(polydivinylbenzene,toluene as porogen)和PDH-55(polydivinylbenzene,heptane andtoluene as porogen)经后交联反应,所形成的新孔以微孔为主.树脂对水溶液中苯酚和维生素B12(VB12)的静态吸附研究发现树脂经后交联后,对苯酚的吸附量有显著提高,但对VB12的吸附量增加不大,原因是分子尺寸较大的VB12无法进入由悬挂双键后交联反应所形成的微孔.树脂PDT-55pc对苯酚的吸附量大于商品树脂XAD-4;后交联前后树脂PDT-55、PDT-55pc(post-crosslinking of PDT-55)、PDH-55、PDH-55pc(post-crosslinking ofPDH-55)对VB12的吸附量均大于树脂XAD-4.在本研究的实验条件下,Langmiur和Freundlich吸附等温线方程能很好地拟合树脂对水溶液中苯酚和VB12的吸附,相关系数在0.99以上.静态吸附动力学实验结果表明后交联前后树脂对苯酚的吸附较VB12更容易达到吸附平衡.吸附动力学数据的拟合结果显示,McKay二级吸附动力学模型符合树脂对苯酚的吸附,而对VB12的吸附更符合Lagergren一级吸附动力学模型.     

Friedel–crafts reactions of pendant vinyl groups in macroporous monosized poly(meta‐divinylbenzene) and poly(para‐divinylbenzene) particles

Residual vinyl groups in macroporous monosized polymer particles of poly(meta‐DVB) and poly(para‐DVB) prepared with toluene and 2‐EHA as porogens have been reacted with aluminum chloride as Friedel–Crafts catalyst with and without the presence of lauroyl chloride. In the reaction between aluminum chloride and pendant vinyl groups a post‐crosslinking by cationic polymerization takes place. A reaction occurring simultaneously is the addition of HCl to the double bonds. The progress of these reactions was studied by characterization of vinyl group conversion, pore size distribution, specific surface area, morphology, and swelling behavior. In the reaction with aluminum chloride the poly(para‐DVB) particles showed a substantially higher conversion of pendant vinyl groups than the particles made of poly(meta‐DVB) independent of porogen type. The reaction with aluminum chloride led to a reduced swelling in organic solvents and an increased rigidity of the particles prepared with toluene as porogen. This is confirmed by an increase in the total pore volume in the dry state and a change in the pore size distribution of these particles. Also in the reaction with lauroyl chloride poly(para‐DVB) particles have shown a higher conversion of pendant vinyl groups than poly(meta‐DVB) particles and the acylation was almost complete at the early stage of the reaction. The swelling in organic solvents is reduced as a result of the incorporation of acyl groups into the particles prepared with toluene as porogen. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1366–1378, 2000     

A hyper-cross-linked polystyrene with nano-pore structure

Chloromethylated polystyrene (CMPS) beads were prepared by suspension polymerization of vinylbenzyl chloride (VBC), divinylbenzene (DVB) and styrene (St) in the presence of porogen. The same feed volume ratio of DVB leads to similar cross-linking degree for all CMPS, but decreasing VBC content provided a progressively reduced content of chloromethyl groups in each CMPS. Hyper-cross-linked polystyrene (HCLPS) beads were obtained by post cross-linking reaction of CMPS in dichloroethane (DCE) containing Friedel-Crafts catalyst. The role of porogen and its influence on nano-pore structure of HCLPS were investigated. The results showed that different types of porogen had significant effect on the nano-pore structure of the final products, such as specific surface area, average pore size and total pore volume. Using the mixture of toluene and cyclohexanol as inner porogen can yield the highest specific surface area for HCLPS beads. Moreover, higher amount of VBC lead to greater specific surface area and total pore volume. It was therefore indicated that nano-pore structure of HCLPS can be controllably prepared via changing porogen type and VBC concentration. Finally, the unprecedented swelling capacity was found for the hyper-cross-linked species derived from different porogen types.     

SYNTHESIS OF MACROPOROUSCOPOLYMER OF VCA AND DVB

1.INTRODUCTIONVinylacetate(VAc)isacommonandcheapmonomeLUsuallyitisusedtopreparelinearhomopolymerorcopolymeLHowever,becauseoftheusefulestergrouppresentinVAc,italsoat'tractsthegreatinterestsofsomescientistswhoworkintheareaoffunctionalpolymers.Recently,alotofreporthaveappearedusingVAcasamainmonomertopreparecrosslinkedpolymersII~sl.ThesereportsmainlyfocustheinterestsonthesynthesisandapplicationoftheVAccontainingcrosslinkedpolymers.Noreportshavebeenfoundtostudythekineticsofthesynthesisofc…     

Anionic copolymerization of 2,3,4,5,6-pentafluorostyrene and divinylbenzene

Anionic copolymerizations of 2,3,4,5,6-pentafluorostyrene (PFS) with 1,3-divinylbenzene (m-DVB) and 1,4-divinylbenzene (p-DVB) were performed by using lithium diisopropylamide as an initiator in order to synthesize the fluorine-containing linear polymer with pendant vinyl groups. The products were soluble copolymers possessing both PFS and DVB monomeric units, and the DVB monomeric unit in copolymer had pendant vinyl group. This copolymerization reaction took a much longer time than that of styrene with DVB. The copolymerization parameter of this system was examined from copolymer composition curves. In this system, m-DVB was found to be more reactive than p-DVB. The reactivity of copolymerization was largely influenced by the reactivity of active species. © 1993 John Wiley & Sons, Inc.     

Ion‐exchange resins. III. Functionalization–morphology correlations in the synthesis of some macroporous,strong basic anion exchangers and uranium‐sorption properties evaluation

The synthesis and characterization of a series of macroporous, strong basic anion exchangers (SBAEs), with an average pore radius higher than 50 nm, and the evaluation of their sorption properties for uranyl chlorocomplexes from HCl solutions are reported. Finely divided macroporous styrene–divinylbenzene (S–DVB) copolymers with a narrow distribution of beads sizes, diameters within the range of 90–200 μm, were prepared for this purpose with 2‐ethyl‐1‐hexanol as a porogen, at a high dilution of monomers (D ≥ 0.55 mL/mL). Chloromethyl groups were introduced with (CH₂O)_n/Me₃SiCl as a chloromethylation agent in the presence of a Lewis acid as a catalyst (TiCl₄, SnCl₄, and FeCl₃) in CHCl₃ as a reaction medium. SnCl₄ and FeCl₃ gave comparable chloromethylation degrees in the same reaction conditions. TiCl₄ was not efficient as a catalyst in the chloromethylation with this reagent. Diethyl‐2‐hydroxyethylamine was used as a tertiary amine to prepare SBAEs. Structural and morphological characteristics were determined after every functionalization step of the macroporous network. Both the chloromethylation, in the presence of FeCl₃ as a catalyst, and the amination reactions determined a significant decrease of the pore volume, in the whole range of the nominal crosslinking degree, comparative with the starting copolymer. The specific surface area and the average pore radius varied in a different way as a function of the nominal crosslinking degree. Thus, the specific surface area increased and the average pore radius decreased after chloromethylation and amination for copolymers with a DVB content lower than 10 wt %. Small decreases of the specific surface area and the average pore radius were observed after chloromethylation and amination reactions for copolymers with a DVB content higher than 10 wt %. SBAEs were also characterized by thermogravimetric analysis and sorption capacity for uranyl chlorocomplexes. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2451–2461, 2004     

SYNTHESIS OF MACROPOROUS COPOLYMER OF VCA AND DVB

The reactivity ratios of vinyl acetate(VAc) and divinyl benzene (DVB) were calculated from the Q and e values.The possibility of the copolymerization of these two monomers was predicted and the copolymerization was carried out by suspension polymerization technique in the presence of pore producing agent (toluene and gasoine).The relative ratio of acetoxy group and benzene ring in the copolymer were monitored by IR measurement during the polymerization.The variation of pore properties,such as spectific surface area,porosity and average pore diameter,with polymerization time were determined.The copolymers at various polymerization time were alcoholyzed and thus the variation of the hydroxyl group content with polymerization time was studied.     

高度交联聚苯乙烯吸附剂的结构与吸附性能研究

在通过Ｆｒｉｅｄｅｌ—Ｃｒａｆｔｓ后交联反应制备高度交联聚苯乙烯吸附剂的过程中，向反应体系中加入非极性芳香化合物甲苯，当加入少量甲苯时，吸附剂的比表面积、孔容等变小，但其吸附能力却明显提高；当加入甲苯超过某一量时，其吸附能力又随加入甲苯的量的增加而降低，这说明孔结构和骨架结构共同影响着高度交联聚苯乙烯吸附剂的吸附性能．     

Metamorphosis of ordered mesopores to micropores: periodic silica with unprecedented loading of pendant reactive organic groups transforms to periodic microporous silica with tailorable pore size

Ordered porous silicas with unprecedented loadings of pendant vinyl groups have been synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and triethoxyvinylsilane (TEVS) under basic conditions in the presence of cetyltrimethylammonium surfactant. The resulting organosilicate-surfactant composites exhibited at least one low-angle X-ray diffraction (XRD) peak up to the TEVS:TEOS molar ratio of 7:3 (70% TEVS loading) in the synthesis gel. The surfactant was removed from these composites without any structural collapse. Nitrogen adsorption provided strong evidence of the presence of uniformly sized pores and the lack of phase separation up to TEVS:TEOS ratios as high as 13:7 (65% TEVS loading), whereas (29)Si MAS NMR and high-resolution thermogravimetry showed essentially quantitative incorporation of the organosilane. Thus, a hitherto unachieved loading level for pendant groups, considered by many to be impossible to achieve for stable organosilicas because of the expected framework connectivity constraints, has been obtained. The resulting vinyl-functionalized silicas exhibited gradually decreasing pore diameter (from 2.8 to 1.7 nm for TEVS loadings of 25-65%) and pore volume as the loading of pendant groups increased, but the specific surface area was relatively constant. Because of the reactivity of vinyl groups, ordered silicas with very high loadings of these groups are expected to be robust starting materials for the synthesis of other organic-functionalized ordered microporous materials. Herein, we demonstrate that these starting materials can also be transformed via calcination into ordered microporous silicas with pore diameters tailorable from 2.5 to as little as 1.4 nm simply by using an appropriate loading of the vinyl-functionalized precursor. This ease of the micropore size adjustment and the attained degree of structural ordering (as judged from XRD) have not been reported before. The novel ordered microporous materials reported herein are promising as adsorbents and catalyst supports.