【作者】 黄志强；

【导师】 宋才生；

【作者基本信息】 江西师范大学 ， 有机化学， 2011， 硕士

【摘要】 聚芳醚砜酮是分子主链上带有芳香族环和醚键、砜基、酮键的耐高温特种工程塑料。它具有优异的机械物理性能、阻燃、耐化学品腐蚀、耐剥离、耐辐射、耐水解、抗冲击、抗蠕变、绝缘稳定、和易加工等性能,近年来在高技术、民用及航空工业领域得到了广泛的应用和发展。本论文主要包括以下部分：1.利用自制的4,4’-二苯氧基二苯砜(DPODPS)、二苯醚(DPE)与对苯二甲酰氯(TPC)在无水AICl3和N,N-二甲基甲酰胺(DMF)的存在下,与1,2-二氯乙烷(DCE)一锅法进行低温溶液三元无规共缩聚,制得聚芳醚酮酮／聚芳醚砜醚酮酮(PEKK/PESEKK)树脂,并用1H-NMR, IR、DSC、TGA和耐溶剂性对其进行了表征分析。结果表明：聚合物具有预期的结构；对数比浓黏度(ηinh)均在0.65以上；随着PESEKK结构单元的增加,聚合物的Tg提高,结晶熔融峰在343℃并随着PEKK结构单元的比例的增加而提高：5%热失重在481℃以上,具有较高的耐热性能。聚合物只溶解于二氯乙酸、四氯乙烷等少数几种溶液,不溶解于常见溶剂,表现出较好的耐溶剂性能。2.以DPODPS和偏苯三酸酐酰氯(TMAC)为单体,在无水AICl3和N-甲基吡咯烷酮(NMP)的存在下,以1,2-二氯乙烷(DCE)为溶剂进行二元共缩聚,制得含羧基侧基的聚芳醚砜醚酮酮(PESEKK-A)树脂。用1H-NMR, FT-IR, TGA, DSC进行了表征分析。结果表明：聚合物具有预期的结构；且TMAC主要是以对位的链接方式为主；聚合物5%热失重为324.6℃；树脂具有优良的耐溶剂性和耐腐蚀性能。为树脂作为离子交换和吸附剂的基底材料提供了条件。PESEKK-A及其钠盐具有吸附金属离子的作用,是一种结构新颖的弱酸性阳离子交换树脂和吸附剂。3.以PESEKK-A的钠盐,环氧氯丙烷为原料,在四氯乙烷为溶剂和催化剂的条件下合成了含环氧侧基的聚芳醚砜醚酮酮(PESEKK-E)树脂,测出其环氧值在0.04-0.12之间,用4,4’-二氨基二苯砜(DDS)做固化剂,在一定温度下进行固化,用FT-IR, TGA, DSC对固化后的环氧树脂进行了表征分析。结果表明：聚合物具有预期的结构,固化后的各个主要峰的特征显示150℃/2h+180℃/2h+200℃/1h进行固化较好。由TG和DSC谱图分析得知,该树脂固化后分解温度在240～250℃范围内,通过环氧固化剂固化,树脂未出现玻璃化转变温度,可能是树脂的热分解温度低于其Tg的缘故。4.用自制的1,1’-二(4-羟基苯基)环己烷(环己基双酚)、过量的环氧氯丙烷在一定温度,和催化剂下作用生成表卤醇,再加入适量的氢氧化钠(NaOH)进行环化反应,制得了环己基双酚型环氧树脂,树脂为无色透明。采用FT-IR、1H-NMR对其结构进行了表征,并对其环氧值进行了滴定。用DDS做固化剂,在一定温度下进行固化,用FT-IR, TGA, DSC对固化后的环氧树脂进行了表征分析。结果表明：环氧树脂具有预期的结构。用盐酸-丙酮法滴定不同条件下合成的环氧树脂,环氧值最高为0.463.对合成的环氧树脂进行溶解性实验表明,树脂能溶于丙酮,卤代烃等常见的低沸点有机溶剂中,工艺性能良好。用DDS固化环己基双酚环氧树脂后,5%热失重在315℃以上,在220℃以前未出现玻璃化转变,可能是Tg高于初始热分解温度的缘故,耐热性能优良。更多还原

【Abstract】 Ether sulfone ketone with the molecular main chain aromatic rings and ether, sulfone, ketone key special high temperature engineering plastics.It has excellent mechanical and physical properties, fire resistance, chemical corrosion resistance, peel resistance, radiation, hydrolysis, impact resistance, creep resistance, insulation and stability, easy processing properties, in recent years in high technology, civil and aviation Industry has been widely applied and developedThe paper includes the following sections:1. Poly ether ketone ketone / poly ether sulfone ether ketone (PEKK/PESEKK) copolymer were synthesized from 4,4’-diphenoxy diphenylsulfone(DPODPS), diphenyl ether (DPE) and terephthaloyl chloride (TPC) in the presence of anhydrous aluminum trichloride(AlCl3), N,N-dimethylformamide(DMF) and 1,2-dichloroethane (DCE) by low temperature polycondensation. Copolymers were characterized by 1H-NMR, FT-IR, DSC and TGA. Their solubilities were also tested. The results showed that copolymers are expected, have high glass transition temperature and thermal stability. The inherent viscosity of the copolymers is more than 0.65 dL/g which conducted by Ubbelodhe viscometer and calculated by the One-Point Method. Copolymers have good chemical resistance only soluble in dichloroacetic acid, tetrachloroethane in room temperature even by heating.2 Poly ether sulfone ether ketone ketone with pendent carboxyl groups prepared from DPODPS and trimellitic anhydride chloride (TMAC) in the mixture solvent of N-methyl pyrrolidone (NMP) 1,2-dichloroethane (DCE), for anhydrous aluminum trichloride(AlCl3) as catalyst.’H-NMR and FT-IR characterized the chemical structures. The result carried on TGA show that the 5% weight loss was 324.6℃. Polymer has excellent solvent resistance. resistance for the ion exchange and adsorbent resin as base material of the conditions provided. PESEKK-A and its sodium salt with adsorption of metal ions, is a novel structure of the weak acid cation exchange resins and adsorbents.3. Poly ether sulfone ether ketone ketone containing epoxy groups (PESEKK-E) were obtained from PESEKK-A and epichlorohydrin, in the presence of tetrachloroethane and sodium hydroxide as catalyst. The values of epoxy are in the range 0.04 to 0.12 by titration. The heat curing strategy were investigated for 4,4’-diaminodiphenyl sulfone (DDS) as curing agent. The PESEKK-E was characterized by FT-IR, TGA and DSC. The results showed that:the polymer with the desired structure, curing characteristics of each of the major peaks showed 150℃/ 2h + 180℃/ 2h +200℃/ 1h for a better cure. Spectrum from the TG and DSC analysis showed that the decomposition temperature of the resin cured in the range of 240～250℃, through the epoxy curing agent, resin, glass transition temperature does not appear, may be the resin of the thermal decomposition temperature lower than Tg Reasons.4. 1,1-bis-(4-hydroxyphenyl)-cyclohexane was synthesized from cyclohexanone and phenol in the presence of HCl and mercaptoacetic acid as mixture catalysts. Then a novel transparent or light yellow epoxy resin was obtained from 1,1-bis-(4-hydroxyphenyl)-cyclohexane and epichlorohydrin for sodium hydroxide (NaOH) as catalyst. The chemical structure of the resulting Epoxy resin was characterized by FT-IR and 1H-NMR. The epoxy value of the titled resin was determined by the method of titration. The epoxy resin was cured by thermal curing, DDS as curing agent. The chemical structure of the cured Epoxy resin was characterized by FT-IR, thermal properties obtained from TGA and DSC. The results showed that epoxy resin was expected. With hydrochloric acid - acetone titration under different conditions, the synthesis of epoxy resin, epoxy value of up to 0.463. The solubility of the resulting polymers was also tested and it show that the epoxy resin can be dissolved in acetone, halogenated hydrocarbons and other common organic solvents. The process performance is good. DDS cured with double-cyclohexyl Phenol epoxy resin, the 5% weight loss at 315℃,220℃not previously appeared in the glass transition, Tg may be higher than the initial thermal decomposition temperature of the reason, over heat resistance.更多还原