新型耐腐蚀含氟环氧乙烯基酯树脂的合成与性能

以含氟环氧树脂(F-EP)、丙烯酸(AA)和甲基丙烯酸(MAA)为单体,用顺丁烯二酸(MA)进行改性,合成了含氟环氧乙烯基酯树脂(F-EVER)。采用傅里叶红外光谱、热重分析、力学性能分析等手段对产物进行表征,研究了树脂的耐腐蚀性能。结果表明:当以N,N-二甲基甲酰胺(DMF)为催化剂,羧基与环氧基摩尔比为0.9,MA与F-EP摩尔比大于0.1,阻聚剂质量分数为0.03%时,合成的含氟环氧乙烯基酯树脂性能较好;同时,氟元素的引入较好地增强了环氧乙烯基酯树脂的耐热性和耐化学腐蚀性能。     

纤维素基磁性聚偕氨肟树脂吸附Mn（Ⅶ）

用酸处理的纤维素基磁性聚偕氨肟树脂（AMAO）在溶液中吸附KMnO4，发生氧化还原反应的几率在2％以下；用碱处理的树脂（BMAO）作吸附剂，KMnO4还原为Mn（OH）4的比例剧增，达到或超过10％，并且与溶液的pH有关。但是，Mn（Ⅶ）被还原为Mn（Ⅳ）的量基本上不受KMnO4起始浓度、吸附剂添加量和吸附时间变化的影响。BMAO树脂吸附KMnO4的量是树脂偕氨肟基含量的5倍以上。超当量吸附现象反映了物理吸附的本质。     

辛巴蓝FEG—A固载的交联聚乙烯醇作为亲和色谱填料

以乙酸丁酯和正庚烷作为致孔剂,乙酸乙烯酯与异氰酸三烯丙基酯进行悬浮共聚、经碱性水解得到大孔交联聚乙烯醇树脂。交联聚乙烯醇与环氧氯丙烷在碱性条件下反应,得到含有环氧基的树脂。含有环氧基的树脂与6-氨基已基-N'-辛巴蓝FEG-A反应,制得固载辛巴蓝FEG-A（一种三嗪染料）的交联聚乙烯醇树脂。将固载辛巴蓝FEG-A的交联聚乙烯醇树脂作为亲和色谱填料,对五种蛋白质（细胞色素c、溶菌酶、牛血清白蛋白、胰岛素和乳酸脱氢酶）进行了色谱分离。     

聚正己基三苯乙炔基硅烷树脂的合成及其热稳定性能

以正己基三氯硅烷、镁条、溴乙烷和苯乙炔为原料,通过Grignard反应合成单体正己基三苯乙炔基硅烷（NTPES）,其结构经¹H NMR,¹³C NMR, ²⁹Si NMR和FT-IR表征,采用非等温差热扫描量热法（DSC）研究了其热固化行为。通过热聚合合成了聚正己基三苯乙炔基硅烷树脂（PNTPES）,运用热重分析（TG）技术研究了固化树脂的热稳定性。结果表明：树脂在氮气气氛中质量损失5%的温度高于445 ℃, 800 ℃残存率大于60%,具有较好的热稳定性。     

马来酸酐和丙烯酸改性环氧大豆油基泡沫塑料

利用马来酸酐(MA)和丙烯酸(AA)对环氧大豆油进行双重改性,制得马来酸酐-丙烯酸改性环氧大豆油树脂(MA-AESO),从而在大豆油分子上引入更多的双键和极性基团.MA-AESO与苯乙烯(St)通过自由基共聚合可制得环境友好型泡沫塑料,其机械性能比单独用丙烯酸改性环氧大豆油树脂(AESO)基泡沫塑料有明显的提高,归因于分子链中较大量的双键和极性基团提高了泡沫塑料的交联密度,故而在含有较多植物油成分的情况下达到与传统石油基硬质不饱和聚酯泡沫塑料机械性能相当的目的.实验室模拟土埋实验证明,MA-AESO树脂基泡沫塑料因含有更多的可降解基团,其生物降解性优于AESO树脂基泡沫塑料.     

一种含氟丙烯酸树脂的制备及其表面疏水性

在聚合反应的后期阶段,向体系中引入含氟丙烯酸酯单体全氟辛基-(N-乙基-N-丙烯酸乙酯基)磺酰胺(QG-F814)共聚改性的方法制备了一种含氟丙烯酸树脂.接触角测定表明,该树脂具有良好的疏水性能.热重分析表明,该树脂在改性前后的耐热稳定性差别不大.     

含巯基MTQ树脂的合成及对丙烯酸酯体系光固化性能的影响

以六甲基二硅氧烷、γ-巯丙基三乙氧基硅烷（KH-580）和正硅酸乙酯为原料，在酸性条件下通过水解共聚反应合成了含巯基MTQ树脂（SH-MTQ）。通过傅里叶红外光谱、核磁共振氢谱（¹HNMR）、凝胶渗透色谱和热重，对所合成的树脂进行了表征和分析。以1-羟基环己基苯基甲酮（184）为光引发剂，考察了含巯基MTQ树脂对三丙二醇二丙烯酸酯（TPGDA）光固化过程和材料性能的影响，发现含巯基MTQ树脂的加入使得TPGDA的光固化速率和双键转化率有所提高，并且固化膜硬度、热稳定性、透过率和接触角等材料性能也有所提高。     

乙酸基和羟基对固化的环氧树脂吸水性能的影响

应用称重法、差示扫描量热法和腐蚀测试法研究固化的环树脂的吸水行为,实验结果表明,该树脂中的羟基改为乙酸基后可和低树脂的饱和吸水率,并增大水在 脂中的扩散能力,邻甲酚环氧树脂用乙酸线型酚醛互树脂固化后所得的树脂（ＥＰＡ）在３０℃时饱和吸水率为０．８４％（质量分数）,而用线型酚醛树脂固化所得的树脂（ＥＰ）则为１．９７％,水在ＥＰＡ和ＥＰ中的扩散活化能分别为４０和４８ｋＪ．ｍｏｌ＾－１,这可归因于乙酸基     

茜素红S螯合树脂分离富集测定地质样品中的痕量金、铂和钯

用螯合树脂对金属进行分离富集及测定，前人已做了许多有意义的研究［１～４］．曾用含键合Ｓ双硫腙（Ｐ－Ｄ）和脱氢双硫腙（Ｐ－ＤＴ）功能团的离子交换树脂和螯合树脂分离金和铂族金属［５］，用双硫腙负载树脂分离富集Ｃｕ（Ⅱ）［６］，用磺基二硫腙负载树脂分离富集...     

3—聚苯乙烯磺酰基环氧丙烷作为活性中间体制备聚合物试剂

本文讨论了聚苯乙烯亚磺酸钠树脂（１）在相转移催化剂存在下与环氧氯丙烷反应制备含环氧功能基的树脂（２），后者进一步与含氨基的化合物在碱性条件下通过亲核反应制备了数种含胺功能基的树脂（３）。     

双酚A型环氧磺酸酯的合成与表征

用双酚A型环氧树脂(E-51)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)合成了可用于紫外光固化的双酚A型环氧磺酸酯(AMPS-EP).研究了影响反应的多种因素,优化的合成条件为:以N,N-二甲基甲酰胺(DMF)为溶剂,AMPS与E-51的摩尔投料比为1:0.5,对苯二酚为阻聚剂,用量为环氧树脂质量的0.2％,反应时间...     

基于儿茶酚交替共聚物的干湿态双高效胶黏剂材料

以多巴胺(DA)和双酚A型环氧树脂(BAER)进行氨基-环氧点击化学反应, 合成了儿茶酚功能化交替共聚物聚(多巴胺-alt-双酚A型环氧)[P(DA-a-BAER)]. 以FeCl₃为交联剂, 研究了交联剂用量对聚合物在干态及水下环境中黏接性能的影响. 结果表明, 该聚合物可以在干态及水下环境中对多种基材进行黏接. 以不锈钢基材为例, 在干态条件下, 当Fe³⁺与儿茶酚基团的摩尔比为1:3 时, 黏接强度最高, 为(3.03±0.68) MPa; 在水下环境中, 当Fe³⁺与儿茶酚基团的摩尔比为1:6 时, 黏接强度最高, 为(0.65±0.10) MPa. 拉曼光谱(Raman)和紫外-可见光吸收光谱(UV-Vis)分析结果表明, Fe³⁺与儿茶酚基团可通过配位交联和氧化交联的方式增大胶体强度, 从而提高黏接强度.     

Surface modification of epoxy resin by amphiphilic fluoroorganosiloxane copolymers

Russian Chemical Bulletin - An amphiphilic fluoroorganosiloxane copolymer designed for a surface modification of epoxy resin by fluorine-containing fragments has been synthesized. The copolymer...     

Studies on the synthesis and curing of epoxidized novolac vinyl ester resin from renewable resource material

Cardanol-based epoxidized novolac vinyl ester resin (CNEVER) was synthesized by reacting cardanol-based epoxidized novolac (CNE) resin and methacrylic acid (MA) (CNE:MA molar ratio 1:0.9) in presence of triphenylphosphine as catalyst at 90 °C. The CNE resin was prepared by the reaction of cardanol-based novolac-type phenolic (CFN) resin and epichlorohydrin, in basic medium, at 120 °C. The CFN resin was synthesized by reacting cardanol (C) and formaldehyde (F) (C/F ratio = 1:0.7) with p-toluene sulphonic acid (PTSA) as catalyst (0.5 wt.%) at 120 °C for 7 h. The resin products were analyzed by Fourier-transform infra-red (FTIR) and nuclear magnetic resonance (NMR) spectroscopic analysis. The number-average molecular weight of the prepared CNEVER was found to be 859 gmol⁻¹ as determined by gel permeation chromatographic (GPC) analysis. The resin was cured by using the mixture of resin, benzoyl peroxide, and styrene at 120 °C. The CNEVER resin was found to be cured in 60 min at 120 °C. Differential scanning calorimetric (DSC) technique was used to investigate the curing behaviour. Single step mass loss in dynamic thermogravimetric (TG) trace of CNEVER was observed. Thermal stability of the vinyl ester sample containing 40 wt.% styrene was the highest amongst all other prepared systems.     

Synthesis of fluorine-containing organosilicon copolymers and their use for the preparation of stable hydrophobic coatings based on the epoxy binder

A series of novel fluorine-containing organosilicon copolymers was synthesized in an excess of acetic acid. The efficiency of their use as hydrophobic agents for epoxy film-forming materials was shown.     

Investigation on the Structure and Curing Performances of Secondary Amine Terminated Hyperbranched Poly（ester-amine）s

<正>Three secondary amine terminated hyperbranched poly(ester-amine)s(defined as HPEA1,HPEA2 and HPEA3)were synthesized from piperazine(A_2)and trimethylolpropane triacrylate(TMPTA,B_3)at their molar ratios of 2.5:1,2.25:1 and 2.0:1,respectively.The polymers were analyzed by ~1H NMR,GPC,DSC and TGA.The results indicated that the ratio of secondary amine to tertiary amine and the content of secondary amine decreased,while the molecular weight, molecular weight distribution and glass transition temperature(T_g)increased from HPEA1 to HPEA3.Due to their reactive terminal groups and flexible chains,these polymers further reacted with an epoxy resin(E51)to form cured films under ambient conditions.With increasing the ratio between secondary amine groups and epoxy groups from 1:2 to 2:1,the gel content,film hardness and onset decomposing temperature of the cured samples increased.The good film performances should make the polymers as the components of non-solvent coating materials.     

Efficient adsorption and desorption of Cu2+ by a novel acid-resistant magnetic weak acid resin

A novel magnetic weak acid resin NDMC-1 was prepared in the presence of methyl acrylate（MA）,divinylbenzene（DVB） and titanate coupling agent（TCA） coated 7-Fe₂O₃ particles.To evaluate the adsorption of Cu²⁺ on the obtained resin NDMC-1,another two magnetic resins NDMC-0（the precursor of NDMC-1 without hydrolyzation） and NDMO-l（the synthesized weak acid resin using oleic acid coatedγ-Fe₂O₃） were chosen for comparison.The results showed that the carboxyl groups were formed after hydrolyzation,and NDMC-1 exhibited a greater adsorption capacity to Cu²⁺.The desorption experiment demonstrated that the desorption ratio at pH 2（95.14%） was greatly higher than pH 3（25.97%）.Moreover,the magnetic resin NDMC-1 was proved to be stable at pH 2,extending the application of magnetic materials which were always considered to be acid-nonresistant.     

A Comparison of the Syntheses of High Molar Mass Epoxy Resins on the Basis of two Groups of Modified Vegetable Oils

Application of epoxidized and hydroxylated natural oils as a new group of environmentally friendly and renewable raw materials for the synthesis of high molar mass epoxy resins is described. Selected vegetable oils were first oxidized and next reacted with mono and diethylene glycols. Obtained epoxidized soybean, rapeseed, linseed and sunflower oils were used together with Bisphenol A in the fusion process. Analogously, hydroxylated soybean and rapeseed oils were reacted with commercial grade Bisphenol A-based low molar mass epoxy resin. The fusion process was carried out in the presence of selected catalysts (i.e., lithium chloride, 2-methylimidazole, triphenylphosphine and triethanolamine) giving high molar mass epoxies. The relationship between type of modified oil used in the synthesis and reaction conditions and properties of synthesized resins (e.g., value and distribution of average molar mass, contents of epoxy groups and colour) is discussed.     

A novel halogen‐free co‐curing agent with linear multi‐aromatic rigid structure as flame‐retardant modifier in epoxy resin

A novel halogen‐free 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐containing co‐curing agent, 6,6′‐(1,4‐phenylenebis(((4‐(phenylamino)phenyl)amino)methylene))bis(dibenzo[c,e][1,2]oxaphosphinine 6‐oxide) (DPN) was synthesized via a simple 1‐pot or 2‐step procedure with yield of 86.2% and 70.8%, respectively. The molecular structures of 4,4′‐((1,4‐phenylenebis(methanylylidene))bis(azanylylidene))bis(N‐phenylaniline) (DPN intermediate) and DPN are characterized by FTIR, NMR, and MS. TGA tests show that the char yield of DPN/EP composites raises to 30.9% when the molar ratio of DPN to 4,4‐diaminodiphenyl methane(DDM) is 20:80. T_g values of DPN/EP composites tested by DSC and DMA are similar to neat epoxy resin (EP), which is due to the secondary amine in DPN that participates in the cross‐linking reaction of epoxy resin. The storage modulus in the rubber stage (E′‐190 °C) of flame‐retardant epoxy resin is close to that of neat EP, while their tanδ's are lower, which indicates the similarity of samples' cross‐linking density due to the participation of DPN in the cross‐linking reaction. The results show that when the molar ratio of DPN and DDM is 5:95, the epoxy has a higher T_g value and better mechanical properties than other samples. The introduction of DPN efficiently improves the flame‐retardant properties of epoxy resin with V‐0 rating of UL‐94 vertical burning test, non‐dripping, 41% of limit oxygen index (LOI) value, low peak heat release rate (PHRR), and total heat release (THR).     

Preparation and thermomechanical properties of epoxy resins modified by octafunctional cubic silsesquioxane epoxides

The thermomechanical properties of octafunctional cubic silsesquioxane‐modified epoxy resins associated with dicycloaliphatic hardener (4,4′‐dimethyldiaminodicyclo hexyl methane) were studied using thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. The structures of epoxy resin containing cubic silsesquioxane epoxides were characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray scattering techniques. In this work, octa(dimethylsiloxybutylepoxide) octasilsesquioxane (OB), and octa(glycidyldimethyl‐siloxyepoxide) octasilsesquioxane (OG), were synthesized and used as additives to improve the properties of a commercial epoxy resin by exploring the effects of varying the ratio of OB or OG. The commercial Ciba epoxy resin (Araldite LY5210/HY2954) was used as a standard. It was found, by thermogravimetric analysis and dynamic mechanical analysis, that the highest thermal stability was observed at N = 0.5 (N = number of amine groups/number of epoxy rings). No glass transition temperature was observed by adding 20 mol % OB to the Ciba epoxy resin, indicating the reduction of chain motion in the presence of octafunctional cubic silsesquioxane epoxide. The storage modulus of the OB‐modified epoxy resin also increased, especially at higher temperatures, compared with the Ciba epoxy resin under identical curing conditions. Fourier transform infrared data elucidated the preservation of cubic silsesquioxane structure after curing at high temperature. In contrast, the OG/Araldite LY5210/HY2954 systems gave poorer thermomechanical properties. The low viscosity of OB at room temperature (～ 350 cPs) makes it suitable for composite processing and, when used in conjunction with the Ciba epoxy, lowers the viscosity of this system as well. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3490–3503, 2004