季铵盐催化合成丙烯酸四溴双酚-A二缩甘油酯的反应动力学

本文讨论了用季铵盐催化剂合成丙烯酸四溴双酚-A二缩甘油酯的合成反应动力学及催化反应动力学.     

阻燃环氧树脂的合成与性能的研究

木文研究了在季铵盐、聚乙二醇等相转移催化剂存在下,以四溴双酚-A和环氧氯丙烷为原料,用适当的溶剂合成阻燃性环氧树脂的方法,并讨论了其阻燃性以及在工业上应用的可能性。     

阻燃剂四溴双酚S双烯丙基醚的制备研究

在NaOH水溶液中,以四溴双酚S(TBS)为原料,通过滴加的方式加入醚化剂烯丙基氯,用季铵盐催化醚化法和其他表面活性剂醚化法成功地合成了收率、纯度均较高的阻燃剂四溴双酚S双烯丙基醚(ATBS)。研究了催化剂用量、反应时间、烯丙基氯用量及其他因素对ATBS收率及纯度的影响情况,找到了反应的最优化条件。季铵盐催化醚化法和其他表面活性剂醚化法的最佳收率分别为97·55%和95·21%,相应纯度为95·57%和93·96%。     

离子液体中制备壳聚糖季铵盐及其絮凝效果研究

采用一步合成法制备了离子液体甘氨酸盐酸盐,以其水溶液为反应介质,壳聚糖与2,3-环氧丙基三甲基氯化铵进行季铵化反应,得到壳聚糖季铵盐,并将其用于中药废水的絮凝处理.考察了温度、时间、反应物配比及离子液体浓度对季铵盐取代度的影响,以及季铵盐加入量、pH、搅拌时间对絮凝效果的影响.实验结果表明,在离子液体中进行的季铵化反应效率及产品取代度均高于常规的非均相反应,壳聚糖季铵盐能够有效去除中药废水的浊度和COD.     

两步法合成环氧树脂的反应动力学

论述了两步法合成环氧树脂的反应动力学。结果表明,在季铵盐存在下,双酚A与环氧氯丙烷的开环反应为二级反应,而第二步的闭环反应为一级反应。计算了各步反应的活化能,探讨了闭环反应的机理。     

合成环氧树脂的反应动力学

本文研究了由双酚—A和环氧氯丙烷合成环氧树脂的反应动力学,测定了表观反应速率常数和活化能,研究了闭环反应速率和相转移催化条件下季铵盐催化效果时温度的依赖性。     

紫外光固化抗静电涂膜的制备及性能研究

用丙烯酸与环氧氯丙烷反应生成的丙烯酸酯与N,N-二甲基乙醇胺反应得到单丙烯酸酯取代季铵盐;用马来酸酐、三乙醇胺反应生成的分子内季铵盐二元醇与IPDI、聚乙二醇400、甲基丙烯酸-2-羟乙酯反应制得端丙烯酸酯聚氨酯季铵盐;用三乙醇胺、IPDI、甲基丙烯酸-2-羟乙酯反应生成的三端丙烯酸酯氨基甲酸酯与氟硼酸及盐酸反应制备了三官能团季铵盐。用1H-NMR和FT-IR对合成的季铵盐进行分析表征。所得季铵盐经复配后光固化速度较快,固化膜抗静电性及耐水洗性较好。     

丙烯酸双酚—S环氧酯的合成

本文用季铵盐,叔胺为催化剂合成了丙烯酸双酚-S环氧酯。讨论了反应温度、酸和双酚的分子结为、催化剂的种类对反应速率的影响。结果表明,反应转化率对温度的依赖性很大,在89℃反应2小时,其转化率不足30%,而在113℃反应2小时,转化率可达65%左右。甲基丙烯酸的反应速率比丙烯酸高,在89℃时,其反应速率常数分别为4.91×10~(-5)s~(-1)和8.66×10~(-5)s~(-1)。双酚S的反应速率比双酚A高,在99℃的反应速率常数分别为1.32×10~(-4)s~(-1)。叔胺的催化效果不及季胺盐。用N,N’-二甲基甲酰胺代替二氧六环作溶剂,虽同样用季胺盐作催化剂,但反应速率可增加,这是由于溶剂参与反应所致。     

阻燃剂双酚-A双(磷酸二苯酯)的合成

以双酚A、三氯氧磷、苯酚等廉价原料,通过两步反应合成双酚-A双(磷酸二苯酯)阻燃剂,总收率95%。采用红外光谱、核磁共振氢谱、质谱、元素分析等对产物结构进行表征。研究反应原料配比、催化剂用量、反应温度、反应时间等因素对收率的影响。适宜反应条件为:以氯化镁为催化剂,n(双酚A)∶n(催化剂)∶n(三氯氧磷)∶n(苯酚)=1∶0.01∶4.0∶5.0,第一步反应温度控制在65℃,反应时间3h;第二步反应温度控制在120℃,反应时间12h;热失重分析(TGA)表明:合成的双酚-A双(磷酸二苯酯)阻燃剂起始分解温度为299.16℃,在299.16～386.66℃和386.66～439.16℃温区迅速炭化;阻燃剂在330℃失重1%,阻燃剂被加热到427.50℃时,炭残余量为46.26%,已经达到了塑料的加工温度要求;合成的双酚-A双(磷酸二苯酯)阻燃剂阻燃性能达到UL94V-0级。     

季铵盐催化合成7,7-二氯双环[4.1.0]庚烷

研究了季铵盐A-1催化二氯卡宾与环己烯的加成反应,考察了不同相转移催化剂的催化活性、反应温度、催化剂用量、反应时间对产物7,7-二氯双环[4.1.0]庚烷收率的影响.在优化反应条件(即反应温度为50C,反应时间为5 h)下,以季铵盐A-1为相转移催化剂,产率可达94.0%.实验证明,季铵盐A-1的催化活性要优于其他短碳链的季铵盐和聚乙二醇,并且在分离过程中不乳化,使产物易于分离纯化.     

Study of photopolymers. IX. Synthesis and rates of photocrosslinking of epoxy acrylates

Epoxy acrylates such as bisphenol type (I-A), propylene glycol type (II-A), and phthalic acid ester type (III-A) were prepared from addition reaction between each epoxy resin and acrylic acid. These reactions were carried out in the absence of solvent and in the presence of quaternary ammonium salt. The rate of addition reaction between glycidyl ether-type epoxide and acrylic acid obeyed first order. The rates of addition reaction between glycidyl ester-type epoxide and acrylic acid obeyed first order at 80°C, but obeyed second order rather than first order at 90°C and above. The rates of photocrosslinking of epoxy acrylates were measured by IR spectrophotometry. Epoxy acrylates with benzoin ethyl ether (1 wt-%) were irradiated with a high-pressure mercury lamp in oxygen-free atmosphere. The rates of photocrosslinking of epoxy acrylates II-A, III-A, and I-A decrease in that order.     

季铵盐对酸酐/环氧树脂体系固化反应和性能影响的研究

本文研究了季铵盐对酸酐/环氧树脂体系的促进作用.结果表明,这种季铵盐与叔胺一样可作为酸酐/环氧树脂固化体系的促进剂,且具有一定的潜伏性.在室温下,该体系的贮存期是通常叔胺促进剂的6～8倍.整个固化反应过程遵循准一级的力学方程.两固化体系的机电热性能略有差异.     

改进感光性能的水溶性季铵盐酚醛树脂的合成

用丙烯酰氯对新型水溶性丙烯酸酯季铵盐酚醛树脂的羟基进行了反应,羟基是由丙烯酸及叔胺盐与环氧酚醛树脂开环反应生成的.讨论了反应时间、反应温度、丙烯酰氯用量对羟基转化率的影响,并比较了丙烯酰化前后树脂在光交联时凝胶含量的变化.结果表明,最佳反应条件为：丙烯酰氯/羟基摩尔比为1.5,温度40～50 ℃,时间1～2 h.羟基转化率可达75%以上.产物在紫外光交联时凝胶含量比未反应前高1倍.     

季铵盐类荧光增白剂的合成及性能

三聚氯氰与4,4′-二氨基二苯乙烯-2,2′-二磺酸和两种氨基化合物经过三步缩合反应得到三嗪基氨基二苯乙烯型荧光增白剂,用三乙醇胺和三乙胺分别替代二乙醇胺和二乙胺,合成新型两性季铵盐类荧光增白剂,研究其与对比的非季铵盐类荧光增白剂的应用性能和在水溶液中的紫外吸收性能、光致异构化现象、荧光发射性能及其应用性能.结果表明：该季铵盐类增白剂耐酸碱性能明显提高,使用范围扩大,但其紫外吸收和荧光发射性能下降,且同样存在较为明显的光致异构化现象,耐光性也较差.     

Selection of quaternary ammonium groups for optimizing properties of water‐soluble,photosensitive phenolic resins and study of their postcuring mechanism

This article deals with the selection of quaternary ammonium groups for synthesis of water‐soluble, photosensitive phenolic resins, containing acrylate and different quaternary ammonium salt groups (AQSPRs), via ring‐opening reactions of epoxy phenolic resin (EPR) with acrylic acid and with different tertiary amine‐protonic acid salts. Conversion of epoxy groups, solubility, photosensitive properties, and thermal decomposition of the different AQSPRs were compared. Modification of AQSPR with methanol solution of KOH to form phenolic resin containing both quaternary ammonium hydroxide groups and acrylate groups (AQHPR) was also studied. Characterization by IR spectrum, DSC, and thermal gravimetric analysis was carried out. The results showed that in the synthesis of AQSPRs containing different quaternary ammonium salt groups, the efficiency of ring‐opening reaction of epoxy phenolic resin with tertiary amine salt in terms of conversion of epoxy groups decreases in the following order: for the tertiary amine, N,N‐dimethyl benzylamine (DMBA) > triethylamine (TEA) > trimethylamine (TMA) > N,N‐dimethyl aniline (DMA) > triethanolamine (TENA) > tri(n‐butylamine) (TBA); for the protonic acid, HCl > HBr > HCOOH > HI > NaHSO₃ > Cl₃CCOOH > HClO₄ > HBF₄. All the AQSPRs except that from HClO₄ can be dissolved in water, methanol, DMF, or DMSO. The gel content formed during UV exposure decreases in the following order of acids used in forming quaternary ammonium salt groups: HCl > HCOOH > NaHSO₃ > Cl₃CCOOH; or decreases in the following order of tertiary amines or hydrohalic acids used in forming the quaternary ammonium groups: TMA. > TEA > DBMA; HCl > HBr > HI. During thermal decomposition of EPR with about half epoxy groups of EPR ring‐opened with tertiary amine salt at 160°C for 0.5 h, water‐insoluble product was formed. The insoluble content and the % decrease of epoxy groups or halide ions increase in the following order: TMA < TEA < DMBA; HCl < HBr < HI. The % decrease of epoxy groups for the insoluble residue is nearly equal to the % decrease of halide ions. A crosslinking reaction mechanism occurred in the thermal decomposition was thus proposed. During the modification of AQSPR with KOH, conversion of quaternary ammonium chloride groups can reach above 90%. The decomposition temperature of the quaternary ammonium groups was lowered from 204 to 120°C after modification of AQSPR with KOH. The photosensitive properties of the resin after modification became lower. It is better to react DMBA · HCl with EPR so as to obtain a product with higher conversion of epoxy groups, good water solubility, moderate photosensitivity, lower decomposition temperature, and better postcuring. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2914–2922, 2004     

乙酰丙酮铬(Ⅲ)催化合成己酸环氧酯的影响因素及其动力学研究

采用乙酰丙酮铬(Ⅲ)为催化剂,催化环氧树脂与己酸的加成酯化反应,探讨了反应温度和催化剂质量分数对酯化反应的影响,以及催化剂的活性,并研究了其动力学行为。实验结果表明,乙酰丙酮铬(Ⅲ)的催化能力高于叔胺和季铵盐催化剂,当其用量为原料总质量的0.4%时,于120℃反应200 min后酯化率可达86.2%。通过积分反应速率方程,对该反应的实验数据进行了动力学计算,确定乙酰丙酮铬(Ⅲ)催化环氧树脂与己酸的加成酯化反应级数为二级,反应表观活化能Ea为139.476 kJ/mol。用IR和1HNMR对产物进行了表征,证实合成了目标产物。     

环氧丙烯酸双酯树脂的合成与表征

探讨了季铵盐催化环氧树脂与丙烯酸的酯化反应过程中催化剂、反应温度、反应时间对反应过程的影响 ,对反应产物进行了化学分析和红外光谱表征。结果表明 ,反应过程中环氧基团和羧基基团的消耗速率是相当的 ,适当提高温度有利于酯化反应的进行     

咪唑啉季铵盐缓蚀剂改性蒙脱土/水性环氧纳米复合涂料

以油酸、二乙烯三胺和氯化苄为原料,合成了油酸基咪唑啉季铵盐缓蚀剂。通过FTIR、¹HNMR对其结构进行了表征,并离子交换至钠基蒙脱土(DK0)层间,制备了缓蚀剂改性蒙脱土(QACDK0)。通过XRD、TGA和UV-Vis对其结构、组成及层间缓蚀剂释放性能进行了表征。结果表明,咪唑啉季铵盐缓蚀剂约占QACDK0质量的38.96%,并将蒙脱土层间距由1.28 nm(DK0)扩大至3.98 nm(QACDK0)。利用DLS及Zeta电位对添加有QACDK0的水性环氧树脂进行了稳定性测试,其Zeta电位为–27.8 m V,具有较高的稳定性。电化学阻抗谱(EIS)测试表明,在腐蚀介质中浸泡30 d后,基于QACDK0制备的清漆漆膜仍具有2.29×10⁸?·cm²的高阻抗,表明涂层具有较好的耐腐蚀性。并且在耐中性盐雾测试中,QACDK0对应的防腐色漆耐盐雾时间最长,验证了该涂层具有良好的耐盐雾性能。     

The effect of different ammonium structure of quaternary ammonium resin on the electrochemical properties

The quaternary ammonium resin is synthesized by the ring-opening reaction of an epoxy resin with a tertiary amine in the presence of a proton donor in the solution. This kind of resin can be dispersed in the water phase to form a conductible milky dispersion. In this study, different kinds of tertiary amines including the full-alkyl group and the ester group-containing or urethane group containing tertiary amine are reacted with DGEBA-type epoxy resin to synthesize the quaternary ammonium resins. The resin characteristics and the electrochemical properties of its emulsion are investigated. In addition, properties of the emulsion prepared from tertiary amine salt resin are also measured for comparison. It is found that if the substituted groups of the ammonium structure of the quaternary ammonium resin are all alkyl groups, rupture voltage of the emulsion is very low. But when one of the substituted group contains an ester group or an urethane group, rupture voltage increases remarkably and the resin can be used for electrodeposition. Meanwhile, the electrodeposition theory of quaternary ammonium resin and its thermal cross-linking reaction and the electrochemical properties of coemulsion prepared by mixing the quaternary ammonium resin and the tertiary amine salt resin are also discussed. © 1993 John Wiley & Sons, Inc.     

甲基丙烯酸缩水甘油酯的合成

在季铵盐催化作用下 ,甲基丙烯酸与环氧氯丙烷反应生成甲基丙烯酸缩水甘油酯。实验结果表明 ,二步法可获得较高的产率