过氧乙酸水相悬浮法合成环氧化反式-1,4-聚异戊二烯

采用过氧乙酸水相悬浮法合成了环氧化反式-1,4-聚异戊二烯(ETPI),通过红外光谱(IR)和1H-核磁共振表征了ETPI的微观结构和环氧度,并考察了环氧化反应的影响因素。结果表明,通过IR谱图可间接求得ETPI的环氧度;在过氧乙酸浓度不大于2.0 mol/L、过氧乙酸与TPI双键摩尔比为0.6、温度为27℃、反应时间为0.5~1.0 h的条件下可制得环氧度约为10%的ETPI。     

预处理法合成环氧化反式-1,4-聚异戊二烯及其结构与性能

采用预处理法对反式-1,4-聚异戊二烯(TPI)进行环氧化改性,合成了具有不同环氧度的环氧化TPI( ETPI),考察了预处理剂/水(体积比,下同)、投料比[过氧乙酸/TPI(摩尔比,下同)]对ETPI环氧度的影响,并对ETPI的结构及性能进行了表征.结果表明,预处理法合成的ETPI其环氧度显著提高,当预处理剂/水为7...     

环氧化反式- 1,4-聚异戊二烯的合成

以负载钛催化异戊二烯本体沉淀聚合所合成的粉状反式-1,4-聚异戊二烯(TPI)为原料,过氧乙酸水溶液为介质,研究了水相悬浮法合成环氧化TPI(ETPI)的合成条件及动力学特性,并考察了ETPI的环氧度测定方法和反应残液的回收利用问题.结果表明,用该法合成ETPI适宜的反应条件为体系pH值等于4.5,且于约20℃反应1～3 h,可获得环氧度小于50%的ETPI;聚合动力学特性为过氧乙酸参与了环氧化反应,过氧乙酸的生成反应可忽略不计,反应的活化能为(72±5)KJ/mol,ETPI的环氧度可由反应前后过氧乙酸浓度的变化求得,与核磁共振法测得的环氧度相比,误差为±10%,有利于环氧度的控制.     

用溶液法环氧化改性反式-1,4-聚异戊二烯及产物表征

以过氧乙酸为环氧化剂,在反式-1,4-聚异戊二烯(TPI)的氯仿溶液中进行环氧化反应,获得了具有不同环氧度的环氧化反式异戊橡胶(ETPI),用红外光谱和核磁共振氢谱对其进行了表征,并通过差示扫描量热分析研究了其热性能.结果表明,用溶液法能够合成出环氧度较高(最高可达80%)的ETPI,合适的反应温度为30 ℃;环氧化反...     

环氧化反式-1，4-聚异戊二烯的环氧度表征

采用过氧乙酸水相悬浮法制备环氧化反式-1,4-聚异戊二烯（ETPI）,通过过酸浓度差法、称重法、红外光谱法、核磁共振法对ETPI环氧度进行表征。结果表明,以核磁共振法测定的环氧度为基准。采用过酸浓度差法、称重法测定的ETPI环氧度误差大于20％;ETPI的红外谱图中A1250／A1383值与环氧度具有很好的线性关系．可以通过核磁共振法和红外谱图校正曲线来校正红外法测定的环氧度。     

ETPI改性PVC性能的研究

研究了反式-1,4-聚异戊二烯(TPI)及环氧化反式-1,4-聚异戊二烯(ETPI)对聚氯乙烯(PVC)性能的影响,并与丁腈橡胶、粉末丁腈橡胶、氯化聚乙烯改性PVC做了比较。结果表明:不同环氧度的ETPI均对PVC有明显的增韧作用;与丁腈橡胶、粉末丁腈橡胶、氯化聚乙烯相比,环氧基摩尔分数为25%的ETPI对PVC的增韧效果最显著。     

用过氧甲酸水相悬浮法制备环氧化反式-1,4-聚异戊二烯

研究了用过氧甲酸体系水相悬浮法制备环氧化反式-1,4-聚异戊二烯(ETPI)的合成条件,并用红外光谱和核磁共振氢谱对ETPI及其环氧基团含量进行了表征和计算。结果表明,用过氧化氢与甲酸合成ETPI较适宜的条件为反应温度40℃、甲酸/过氧化氢/反式-1,4-聚异戊二烯(摩尔比)0.50/1.00/0.50及反应时间1～2h。在此条件下可以制备环氧度10%左右的疏松粉末状ETPI。     

环氧化反式-1,4-聚异戊二烯的毛细管流变行为

采用毛细管流变仪研究了不同环氧度的环氧化反式-1,4-聚异戊二烯(ETPI)的流变行为。结果表明,ETPI的非牛顿指数小于1.00,熔体为假塑性流体;随着ETPI环氧度的增大,非牛顿指数略有降低。环氧度为30%的ETPI在剪切速率较低时,其熔体的黏流活化能较大,说明对温度的敏感性较大;随着剪切速率的增大,黏流活化能降低,ETPI对温度的敏感性降低。随着剪切速率的增大,ETPI熔体在入口区的弹性形变增大;在相同剪切速率下,ETPI的环氧度越大,入口区的弹性形变越大。     

反式-1,4-聚异戊二烯橡胶的制备及其在轮胎胶料中的应用(一)

介绍反式-1,4-聚异戊二烯橡胶(TPI)的结构与性能、负载钛系催化本体沉淀聚合法制备TPI的工艺、TPI在半钢子午线轮胎和全钢子午线轮胎中的应用,以及环氧化TPI(ETPI)和反式丁二烯-异戊二烯(TBIR)-TPI复合胶等TPI改性材料的性能。TPI的负载钛系催化本体沉淀聚合工艺的生产成本较低,且在生产过程中无三废排放;用TPI制备的轮胎耐屈挠性能、耐磨性能较好,每100 km油耗降低约2.5%,行驶里程延长约20%。     

环氧化反式1，4-聚异戊二烯塑炼行为的研究

采用转矩流变仪研究环氧化反式1,4-聚异戊二烯(ETPI)的塑炼行为及其在塑炼过程中的老化降解行为。结果表明:随着环氧度的提高,ETPI达到塑化点的时间缩短,较高环氧度的ETPI的塑炼行为对温度更为敏感。ET-PI在塑炼过程中发生明显的副反应,生成醇及呋喃环结构,且环氧度越高,副反应越严重。ETPI在塑炼前期,首先发生交联反应,进而发生交联键的断裂引起凝胶质量分数减小。     

对甲苯胺改性双氰胺衍生物潜伏性固化剂的合成及性能

合成了一种新型的环氧树脂潜伏性固化剂——对甲苯胺改性的双氰胺衍生物，讨论了反应条件对合成的影响，并通过熔点测定、IR、^1H NMR对其结构进行了表征。初步固化实验结果表明，这种环氧树脂潜伏性固化剂具有较好的固化性能。     

Novel nitrogen‐containing epoxy resin. I. Synthetic kinetics

A novel nitrogen‐containing epoxy resin was synthesized by two steps: (1) condensation reaction between xyleneformaldehyde resin and phenol, to obtain thermoplastic xylenephenolformaldehyde (XPF) resin; and (2) addition reaction between XPF resin and triglycidyl isocryanurate (TGIC). The synthetic kinetics of XPF resin were intensively investigated by gel permeation chromatography (GPC). The results showed that XPF resin, with different molecular weights and low content of free phenol, could be obtained by changing the reaction conditions. The kinetics of reaction between XPF resin and TGIC was monitored by GPC and epoxy value titration. The results showed that the percentage conversion of TGIC was >85% within 60 min at 140°C and the epoxy value, about 0.3–0.4 mol/100 g, varied with the reaction conditions. This novel epoxy resin exhibited good stability of storage and could be used as a basic resin for making prepreg and laminate. The structures of XPF and XT resins were characterized by IR and ¹H‐NMR spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96:723–731, 2005     

二甲基硅烷芴基环氧树脂的合成、表征及非等温固化动力学分析

以双酚芴、二甲基二氯硅烷、环氧氯丙烷为原料,合成了二甲基硅烷芴基环氧树脂（BMEBF）,并利用FT IR、^1H NMR确认了产物结构,盐酸-丙酮法测定其环氧值为0.22。热重分析表明,BMEBF的初始分解温度达347.66℃,较环氧树脂E-51高89℃;在600℃时的残余质量分数也高出21个百分点。对二氨基二苯甲烷（DDM）-BMEBF固化体系的非等温固化动力学研究发现,根据Kissinger法及Ozawa法得到的该固化反应活化能分别为53.616 kJ/mol和57.980 kJ/mol,反应级数都接近1;BMEBF-DDM体系的固化温度为140-150℃,后固化温度为180-190℃。     

紫外光固化环氧丙烯酸酯涂料的制备及耐蚀性能研究

以E-51环氧树脂和丙烯酸为原料合成出光敏性环氧丙烯酸酯低聚物,制备了不同组成的紫外光固化涂料.合成产物的红外光谱分析结果表明,光敏性碳碳双键基团被引入到环氧树脂结构中;固化后涂层的红外表征结果表明,碳碳双键C=C的特征吸收峰消失,涂层固化较完全.在无水乙醇、5%NaOH和5%H2SO4溶液中的浸泡实验以及在3.5%NaCl溶液中的电化学阻抗谱测量结果表明,涂层具有较好的耐蚀性,其耐蚀性随着涂料中环氧丙烯酸酯含量的增加,呈先提高后下降的趋势.当环氧丙烯酸酯含量为40%,二缩三丙二醇双丙烯酸酯含量为50%时,所得涂层的耐蚀性最佳.     

Synthesis,thermal behavior,and cone calorimetry of organophosphorus epoxy materials

An organophosphorus epoxy resin with diglycidyl ether of bisphenol A (DGEBA), which has improved fire performance, was synthesized from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and DGEBA. The epoxy resin was then cured with an isomeric mixture of 3,5‐diethyltoluene‐2,4‐diamine and 3,5‐diethyltoluene‐2,6‐diamine. The reaction kinetics were measured by Fourier transform IR, ¹H‐NMR, and differential scanning calorimetry. The effect of the incorporation of a phosphorus species into the epoxy network structures was also measured using thermogravimetric, thermal conductivity, and dynamic mechanical thermal analyses. The fire performance was measured using cone calorimetry, which showed that a significant improvement was achieved by the addition of only 1–4% phosphorus into the epoxy backbone. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3696–3707, 2003     

Spectral,thermal, and photoreactivity studies on epoxy resin containing benzylidene units in the main chain

A photosensitive epoxy resin was synthesized from bis(4‐hydroxy ‐3‐methoxy benzylidene) acetone and epichlorohydrin using solution polycondensation method. The prepared epoxy resin was characterized by UV, IR, ¹H NMR, and ¹³C NMR spectroscopy. The thermal stability of the epoxy resin was assessed by thermogravimetric analysis. The glass transition temperature of the polymer was determined by differential scanning calorimetry. The photocrosslinking property and photopolymerizing ability of the epoxy resin were studied in film and solution state using UV spectroscopy. The effect of photo acid generator and sensitizer on photosensitivity of the resin was also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

丙环唑的合成

采用溴化法对环菌唑类杀菌剂丙环唑的合成进行了研究,总反应分三步进行。结果表明,第一步2,4-二氯苯乙酮的α单溴代反应较适宜的反应温度为5℃,较适宜的反应介质为四氯化碳,在此反应条件下,单溴代产物α-溴-2,4-二氯苯乙酮的收率为93%。丙环唑的总收率为69.5%(以2,4-二氯苯乙酮计),产品含量95.0%。产物结构经IR、1HNMR和MS表征。     

A simple imide compound as a curing agent for epoxy resin. I. Synthesis and properties

A simple imide compound, 4‐amino‐phthalimide (APH), was synthesized as a curing agent for epoxy resin. APH was prepared from the hydration of 4‐nitro‐phthalimide, which was prepared from the nitration of phthalimide. The chemical structure of APH was verified by IR and ¹H‐NMR spectra. The thermal properties and dielectric constant (ε) of a phosphorus‐containing novolac epoxy resin cured by APH were determined and compared with those of epoxy resins cured by either 4,4′‐diamino diphenyl methane (DDM) or 4,4′‐diamino diphenyl sulfone (DDS). The results indicate that the epoxy resin cured by APH showed better thermal stability and a lower ε than the polymer cured by either DDM or DDS. This was due to the introduction of the imide group of APH into the polymer structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

季铵化嵌段聚醚氨基聚硅氧烷的合成与表征

以二元聚醚胺(D230)、苄基氯及环氧基聚醚封端聚二甲基硅氧烷(α,ω-PESO)为原料,合成了季铵化嵌段聚醚氨基聚硅氧烷(QBPEAS);并制成乳液,用于织物的整理。利用红外光谱、核磁共振氢谱对其结构进行了表征,并对合成条件及应用试验进行了探讨。IR、1H NMR分析表明,聚硅氧烷主链成功引入了聚醚、羟基、苄基等基团;较佳工艺为:n(CC)∶n(Si—H)=1.10∶1、α,ω-PESO与D230的反应时间3～4 h,在较佳条件下制得的QBPEAS的残留Si—H键的摩尔质量浓度为1.0×10-4mol/g,黏度为2.3 Pa.s;乳化剂选择1350与1390的质量比为1∶1的复配型脂肪醇聚氧乙烯醚且用量为QBPEAS质量的20%、整理棉织物的定形温度为150℃时整理的织物,与空白棉织物和用PESO整理的织物相比,柔软性分别提高25.5%和16.1%;白度分别是几乎不变和提高0.4%。