二乙二醇甲乙醚的合成

2005年1月精細石油化工SPECIALITY PETROCHEMICALS第1期二乙二醇甲乙醚的合成許琦蔡照勝楊春生嚴金龍(鹽城工學(xué)院化學(xué)與生物工程學(xué)院,江蘇鹽城224003)摘要:以二乙二醇單乙醚(CH14O3)和氫氧化鈉為原料在n(NaOH):n(CH14O3)=1.5:1.0,苯為帶水劑的條件下,先合成了二乙二醇單乙醚單鈉鹽,然后使CH3C1與二乙二醇單乙醚單鈉鹽進(jìn)行 Williamson反應合成了二乙二醇甲乙醚( DEGMEE)。研究了反應溫度、反應時(shí)間及CH3Cl/C4H14O(摩爾比)對 DEGMEE收率的影響。用氣相色譜法分析了產(chǎn)物的純度,用FTR和HNMR的方法表征了產(chǎn)物結構。結果表明:在反應溫度80℃,CHCl通入時(shí)間4.0h,n(CH3Cl):n(CH4O3)=1.40:1的條件下, DEGMEE的收率大于90%。關(guān)鍵詞:二乙二醇單乙醚二乙二醇單乙醚單鈉鹽威廉遜反應二乙二醇甲乙醚中圖分類(lèi)號:TQ223.249文獻標識碼:A二乙二醇甲乙醚( DEGMEE)是一種性能優(yōu)生成醇鈉后,再與氯甲烷發(fā)生 Williamson醚化反良的高沸點(diǎn)有機溶劑,廣泛用于生產(chǎn)染料、樹(shù)脂、應生成 DEGMEE,該法不但克服了前述三種方油漆、清洗劑、特種墨水等-5;因它能與大多數法中存在的缺點(diǎn),而且合成方法簡(jiǎn)捷,污染低,收醇、酮、醚、鹵代烴等混溶,對堿金屬氫氧化物有較率高,產(chǎn)物易提純好的溶解能力因此在有機合成中也起著(zhù)重要作1實(shí)驗用。目前 DEGMEE的合成方法有以下3種:1.1儀器與原料①以二乙二醇單乙醚(C6H14O3)、甲醇為原料,濃島津GC-14B氣相色譜儀,島津(香港)有限硫酸為催化劑進(jìn)行直接醚化;②以C6H14O3為原公司; NEXUS670型紅外光譜儀,美國 Nicolet料,硫酸二甲酯或碳酸二甲酯為烷基化劑進(jìn)行烷公司;DRX500型核磁共振儀,瑞士 BRUKER公基化;③首先用CH14O3與金屬鈉反應生成醇司鈉,然后再與CH3Br反應生成醚( WilliamsonC5H14O3,工業(yè)品,v≥99.0%,宜興市助劑化法)6。以上三種方法的不足是:①法使用濃硫工廠(chǎng);NaOH,分析純,合肥工業(yè)大學(xué)化學(xué)試劑廠(chǎng);酸作催化劑而嚴重腐蝕設備,同時(shí)生成的產(chǎn)物復氯甲烷,工業(yè)品,v≥99.5%,丹陽(yáng)市雙陽(yáng)化工雜,原料利用率低;②法用的硫酸二甲酯有劇毒,廠(chǎng);苯,分析純,宜興市第二化學(xué)試劑廠(chǎng);甲醇,分而碳酸二甲酯價(jià)格又較高,增大成本;③法使用析純,宜興市亞盛化工廠(chǎng)。金屬鈉作原料,成本較高,同時(shí)反應中生成H2,生收稿日期:2004-08-08;修改稿收到日期:2004-12-24產(chǎn)條件要求較高。作者簡(jiǎn)介:許琦(1965-,江蘇阜寧人,副教授,博士,主要從筆者采用在過(guò)量的NaOH與CH14O3反應事工業(yè)水處理和應用化學(xué)的教學(xué)及研究工作Hance were studied. The optimal extraction conditions were obtained as follows: the dosage of dryflower powder is 2 g, the extracting solvent is 60% alcohol( volume percent), the ratio of solvent topowder is 60 g/mL, microwave power is 648 W, extraction time is 200 s and repeat once again. Underthese optimal conditions, the extraction rate is 96. 8 %, the productive rate is 9. 98%, the colority(1%,526 nm)and ph value of the extractive are 10. 5 and 6. 5 respectively.Key words: begonia fimbristipula hance; microwave assisted extraction; food stain第1期許琦等.二乙二醇甲乙醚的合成1.2合成反應原理由表2可見(jiàn),CH3Cl的通入速度會(huì )影響DEGMEE的合成反應式如下:CH3Cl在反應體系中的分散情況,以較低速度通CH: OCH: CHs NaOH CH: OCH2 CH3入CH3C時(shí),有利于它充分與醇鈉反應,提高CH, OCH, CH: OH CH2 OCH,ONaDEGMEE收率;但是CH3Cl通入速度過(guò)慢時(shí),會(huì )使反應時(shí)間過(guò)長(cháng)。綜合考慮,通入時(shí)間選擇4.0CH: OCH, CHsh為宜。CH, OCH? CH2 OCH表2CHCl通入時(shí)間與產(chǎn)物收率的關(guān)系1.3 DEGMEE的合成將100mLC6H14O3和80mL苯加入到四口通人時(shí)間/h收率通入時(shí)間/h收率,%燒瓶中,安裝好回流和攪拌裝置,開(kāi)動(dòng)攪拌,分批加入44.1 g NaOh,加完后水浴升溫至50℃并2.584.784.5保溫至NaOH完全溶解;然后升溫至60℃反應191.36h,再加熱至65℃,蒸出苯-水混合物直至餾出液注:n(CH3Cl):n(C4H14O3)=1.40:1,反應溫度為80滴澄清;將物料溫度調至反應溫度后開(kāi)始通入2.3CHC1與CH1;O3摩爾比CH3Cl與CH14O3摩爾比對產(chǎn)物收率的影CH3Cl,控制氣體流量使計量的CH3Cl在所需的響見(jiàn)表3。時(shí)間內通完,再繼續在對應的反應溫度下反應1h后對物料進(jìn)行冷卻、抽濾,所得濾渣用100mL表3m(CHC)/n(CH4O3)對收率的影響甲醇分兩次浸泡,洗滌,抽濾以回收濾渣中的產(chǎn)n(C4H1O3)1.1:11.2:11.3:1物;合并濾液并分餾,收集168~171℃的餾分,即 DEGMEE收率,%74.39得 DEGMEE。n(C Hi O31.5:11.4產(chǎn)物含量及結構分析用島津GC14B氣相色譜儀分析含量,測定DEGMEE收率,%90.41條件為:色譜柱30m×0.25mm(.D.)×0.5pm注:CH3Cl通入時(shí)間為4.0h,反應溫度為80℃SE-52毛細管柱,柱溫90℃,汽化室溫度250℃,由表3可見(jiàn),在合成中使CH3Cl過(guò)量,可以檢測器溫度220℃,載氣N2流速(柱后總流速)保證醇鈉充分反應,也可以降低因CH3Cl受熱逸28mL/min,分流比1:60,進(jìn)樣量1.0μL,標樣出而造成的不利影響,但n(CH3C)/n(CH14O3)法定量。用FTIR(液膜法)和HNMR方法大于1.40:1以后,收率增長(cháng)緩慢,所以選用n(CD3Cl為溶劑)進(jìn)行表征。(CH3Cl)/n(C6H14O3)=1.40:1。2結果和討論2.4 DEGMEE的含量分析2.1反應溫度將 DEGMEE產(chǎn)物用氣相色譜法進(jìn)行分析,提高反應溫度有利于提高醚化反應速率,但結果表明 DEGMEE含量大于99.5%。也會(huì )增加CH3Cl的逸出速度,降低CH3Cl的利2.5 DEGMEE的結構表征結果用率,從而使 DEGMEE的收率降低。 DEGMEE用FTIR和HNMR得到的 DEGMEE表收率與反應溫度的影響見(jiàn)表1。征譜圖分別見(jiàn)圖1、圖2。表1反應溫度對 DEGMEE收率的影響反應溫度/C收率,%‖反應溫度/℃收率,7086.8978.93注:n(CH3C1)/n(CH14O3)=1.40/1,CH3Cl通入時(shí)間4h。由表1可見(jiàn),適宜的反應溫度為80℃000800波數cm12.2CH3Cl通入時(shí)間圖1 DEGMEE及C5H14O3的紅外譜圖CH3Cl通入時(shí)間對產(chǎn)物收率的影響見(jiàn)表2。1-DEGMEE: 2-C H14 O3精細石油化工2005年由圖1可以看出, DEGMEE的IR譜圖中已不再有羥基的吸收峰(3400,1648.87,1068.39,考文獻650cm-1)。I Fujioka Norio, Sayama Tetsuya, Tokune Takashi. Detergentimpositions for sereen printing plates[ P]. JP 10 077 426 A22 Shiino Toru, Nobuta Kenichi, Onishi Hiroshi. Method fortaking off part fixed on jig with hot-melt adhesive[P]. JP08283668A2.19963 Nabeshima Toshiichi, Kono Takeshi, Sato Hisami, Cleaning4035302.520151.0agents for glass molds for plastic lenses [P]. JP08224740A2.1996圖2 DEGMEE的HNMR譜圖4 Deshimaru Yuichi, Nakamura Toshio, Shimizu Yoshihiro, et由圖2可以看出,在得到的HNMR譜圖中al. Radiation-sensitive resin composition for the partition for6=1.1828~1.2109對應于乙氧基中一CH3上mation of color filter[P]. JP 11 281 815 A2, 1999的H,δ=3.3690對應于一OCH3中的H,進(jìn)5 Soijima Toshiaki. Separation of polyolefins from waste plasticmixtures and solvents for the methods [P3. JP步說(shuō)明生成的產(chǎn)物為 DEGMEE。00327828A2.20006章思規精細有機化學(xué)品技術(shù)手冊[M]北京:科學(xué)出版社先用C5H14O3和固體NaOH為原料,苯為帶1993.688~691水劑,合成出二乙二醇單乙醚單鈉鹽;再用生成的楊樹(shù)良,王新榮,陳志榮等,雙烷據封端醚的合成方法[PCNI276391A.2000乙二醇單乙醚單鈉鹽與CH3Cl通過(guò) William-8陳志榮,尹紅,王偉松等.甲基或乙基封端聚醚的合成方法son反應合成出 DEGMEE,合成條件為:反應溫[P].CN1311265A.2001度80℃,CH3Cl通入時(shí)間4.0h,n(CH3Cl):n9 Ono Kyoko, Watabe Yasuyoshi. Preparation of(poly) ethane(C6H14O3)=1.4:1,在此條件下, DEGMEE收glycol diethers from the corresponding monoethers and car率可達90%以上。bonate esters[P]. JP 09 227435 A2 1997SYNTHESIS OF DIETHYLENE GLYCOL METHYL ETHYL ETHERXu Qi, Cai Zhaosheng, Yang Chunsheng and Yan JinlongDepartment of Chemical and Biological EngineeringYancheng Institute of Technology, Yancheng 224003, Jiang su, China)Abstract: Diethylene glycol mono-ethyl ether monosodium salt was prepared from diethylene glycolmono-ethyl ether (C H1O3) and sodium hydroxide with benzene as water carrier under n(Naoh)/n(Cs Hu O3)=1.5:1.0. Then diethylene glycol methyl ethyl ether (DEGMEE) was synthesizedhrough Williamson reaction from CH, CI and CH3 CH2 O(CH2 CH, O) Na. The influence of temperature and time of reaction and mass ratio of CH3 ci to diethylene glycol mono-ethyl ether to the yield ofDEGMEE was studied. The quality of product was analyzed by gC and the structure of product wascharacterized by FT-IR and H NMR. The results indicated that the suitable Wiliamson reaction con-ditions were as follows: reaction temperature 80 C, reaction time 4.0 h, n(CHa CI)/n(C Hu O3)=1. 4:1. The yield of DEgMEe could be more than 90%.Williamson reaction; diethylene glycol methyl ethyl ether Jcol mono-ethyl ether mono-sodium saltKey words: diethylene glycol mono-ethyl ether; diethylene gl