甲基双酚类单体共聚-溴化-羧化法制备羧基化聚醚醚酮
Preparation of Carboxylated Polyether Ether Ketone via Copolymerization of Methoxyphenol Monomer-Bromination-Carboxylation
陈俊俊 1段金汤 1张才亮 1顾雪萍 1冯连芳1
作者信息
- 1. 浙江大学化学工程与生物工程学院,化学工程联合国家重点实验室,浙江 杭州 310058;浙江大学衢州研究院,浙江 衢州 324000
- 折叠
摘要
针对2,5-二羟基甲苯、对苯二酚和4,4'-二氟二苯甲酮共聚反应进行研究.结果表明,随着固含量、反应温度以及碱金属碳酸盐中碳酸钾比例的增加,产物含甲基的聚醚醚酮(PEEK-CH3)的分子量分布先降低后增加,其最佳反应条件:固含量为25％,缩聚温度为200℃,碱金属碳酸盐与双酚单体物质的量比为 1.05:1,碱金属碳酸盐中碳酸钠与碳酸钾的物质的量比为19:1,反应时间为3.5 h.PEEK-CH3溴化反应中二溴取代产物(PEEK-CHBr2)最为重要,在液溴用量为—CH3摩尔当量的20倍、反应温度为160℃、365 nm长波紫外线光照下反应2 h后,PEEK-CHBr2占比达到95.8％.最后,通过次氯酸钠氧化PEEK-CHBr2,成功制备了数均分子量为4.6×104、特性黏度为1.5 dL/g的羧基化聚醚醚酮,其水接触角从未改性的PEEK的133.9°降至29.9°.
Abstract
The copolymerization reaction of 2,5-dihydroxytoluene,hydroquinone and 4,4'-difluorobenzophe was studied.The results showed that the molecular weight distribution of the PEEK-CH3 initially decreased and then increased with an elevation in solid content,reaction temperature,and the ratio of potassium carbonate to phenolic monomers in alkali metal carbonate.The optimal reaction conditions were identified as follows:a solid content of 25％,condensation temperature of 200℃,molar ratio of alkali metal carbonate to phenolic monomer was 1.05:1,molar ratio of sodium carbonate to potassium carbonate in alkali metal carbonate was 19:1,and reaction time was 3.5 h.In the PEEK-CH3 bromination reaction,the proportion of the crucial dibromide substitution product(PEEK-CHBr2)was critical.With a liquid bromine dosage 20 times that of the—CH3 molar equivalent,a reaction temperature of 160℃,UV light conditions at 365 nm,and reaction time 2 h,the PEEK-CHBr2 proportion reached 95.8％.Finally,through the oxidation of PEEK-CHBr2 with sodium hypochlorite,carboxyl-functionalized polyether ether ketone(PEEK-COOH)was successfully synthesized with an average molecular weight of 4.6×104 and a characteristic viscosity of 1.5 dL/g.The water contact angle decreased from 133.9° of unmodified PEEK to 29.9°.
关键词
聚醚醚酮/甲基/溴化/羧基化Key words
poly(ether-ether-ketone)/methyl/bromination/carboxylation引用本文复制引用
基金项目
国家重点研发计划(2020YFC1107100)
浙江大学衢州研究院科技计划(IZQ2020KJ2005)
出版年
2024
NETL
NSTL
万方数据