2005年1月SPECIALITY PETROCHEMICALS第1期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CH2C1與二乙二醇單乙醚單鈉鹽進行 Williamson反應(yīng)合成了二乙二醇甲乙醚( DEGMEE)。研究了反應(yīng)溫度、反應(yīng)時間及CH3Cl/C6H14O3(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(jié)構(gòu)。結(jié)果表明:在反應(yīng)溫度80℃,CH2Cl通入時間4.0h,n(CH3Cl):n(C6H4O3)=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(yīng)二乙二醇甲乙醚中圖分類號: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醚化反良的高沸點有機溶劑,廣泛用于生產(chǎn)染料、樹脂、應(yīng)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(shù)法中存在的缺點,而且合成方法簡捷,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重要作1實驗用6。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行直接醚化;②以C6H1O3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(yīng)生成醇司。鈉,然后再與CH3Br反應(yīng)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;NaOH,分析純,合肥工業(yè)大學(xué)化學(xué)試劑廠;酸作催化劑而嚴重腐蝕設(shè)備,同時生成的產(chǎn)物復(fù)氯甲烷,工業(yè)品,w≥99.5%,丹陽市雙陽化工雜,原料利用率低;②法用的硫酸二甲酯有劇毒,廠;苯,分析純,宜興市第二化學(xué)試劑廠;甲醇,分而碳酸二甲酯價格又較高,增大成本;③法使用析純,宜興市亞盛化工廠金屬鈉作原料成本較高,同時反應(yīng)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。作者簡介:許琦(1965-),江蘇阜寧人,副教授,博士,主要從筆者采用在過量的NaOH與CnH1O2反應(yīng)事工北水處理和應(yīng)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, extracti中國煤化工 once again. Underthese optimal conditions, the extraction rate is 96. 8%CNMHG8%, 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(yīng)原理由表2可見,CHCl的通入速度會影響DEGMEE的合成反應(yīng)式如下CH3C在反應(yīng)體系中的分散情況,以較低速度通CH: OCH: CHs NaOH CH2 OCH: CH3 CH3 CI入CH3Cl時,有利于它充分與醇鈉反應(yīng),提高H2 OCH, CH2 OH CH2 OCH2,ONaDEGMEE收率;但是CH3Cl通入速度過慢時,會使反應(yīng)時間過長。綜合考慮,通入時間選擇4.0CH, OCH: CH3h為宜。CH, OCH2 CH OCH3表2CH2C通入時間與產(chǎn)物收率的關(guān)系1.3 DEGMEE的合成將100mLC4H14O3和80mL苯加入到四口通人時間/h收率,%通入時間/h收率,%燒瓶中,安裝好回流和攪拌裝置,開動攪拌,分批71.21加入44.1 g NaOh,加完后水浴升溫至50℃并2.5保溫至NaOH完全溶解;然后升溫至60℃反應(yīng)1h,再加熱至65℃,蒸出苯水混合物直至餾出液注:n(CH3Cl):n(CH14O3)=1.40:1,反應(yīng)溫度為80℃2.3CH3C與C5H14O3摩爾比滴澄清;將物料溫度調(diào)至反應(yīng)溫度后開始通入CH3Cl與C6H14O3摩爾比對產(chǎn)物收率的影CHCl,控制氣體流量使計量的CHC在所需的響見表3。時間內(nèi)通完,再繼續(xù)在對應(yīng)的反應(yīng)溫度下反應(yīng)1.0表3n(CHCI)/n(CH4O3)對收率的影響h后對物料進行冷卻、抽濾,所得濾渣用100mL甲醇分兩次浸泡,洗滌抽濾以回收濾渣中的產(chǎn)CH1O3)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,%74.3983.5188.22得 DEGMEEn(CH, CI):n(Cs H1 O3)1.4:11.5:11.4產(chǎn)物含量及結(jié)構(gòu)分析用島津GC-14B氣相色譜儀分析含量,測定DEGMEE收率,%90.4191.68條件為:色譜柱30m×0.25mm(ID.)×0.5ym注:CH3Cl通入時間為4.0h,反應(yīng)溫度為80℃SE-52毛細管柱,柱溫90℃,汽化室溫度250℃,由表3可見,在合成中使CH2Cl過量,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(yīng),也可以降低因CH3Cl受熱逸28mL/min,分流比1:60,進樣量1.0μL,標樣出而造成的不利影響,但n(CH2CD)/n(CH14O3)法定量。用FT-IR(液膜法)和HNMR方法大于1.40:1以后,收率增長緩慢,所以選用n(CD3Cl為溶劑)進行表征(CH3C1)/nC6H14O3)=1.40:1。2結(jié)果和討論2.4 DEGMEE的含量分析2.1反應(yīng)溫度將 DEGMEE產(chǎn)物用氣相色譜法進行分析,提高反應(yīng)溫度有利于提高醚化反應(yīng)速率,但結(jié)果表明 DEGMEE含量大于99.5%也會增加CH3Cl的逸出速度,降低CH3Cl的利2,5 DEGMEE的結(jié)構(gòu)表征結(jié)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(yīng)溫度的影響見表1。征譜圖分別見圖1、圖2。表1反應(yīng)溫度對 DEGMEE收率的影響反應(yīng)溫度/℃收率,%‖反應(yīng)溫度/℃收率,%89注:n(CH3Cl)/n(CH14O3)=1.40/1,CH3Cl通入時間4h。中國煤化工由表1可見,適宜的反應(yīng)溫度為80℃CN MHG100O 8002.2CH3Cl通入時間圖1 DEGMEE及C5H14O3的紅外譜圖CH3Cl通入時間對產(chǎn)物收率的影響見表21- DEG MEE;2—CH14O3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(3400,1648.87,1068.39,參考文獻650cm-1)I Fujioka Norio, Sayama Tetsuya, Tokune Takashi. Detergentimpositions for screen 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. Cleaning403.5302.5201510agents for glass molds for plastic lenses [P]. JP08224740A2.199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 forδ=1.1828~1.2109對應(yīng)于乙氧基中一CH3上mation of color filter[P]. JP 11 281 815 A2. 1999的H,=3.3690對應(yīng)于一OCH3中的H,進Soijima Toshiaki. Separation of polyolefins from waste plastic步說明生成的產(chǎn)物為 DEGMEE2000327828A2.20003結(jié)論6章思規(guī)精細有機化學(xué)品技術(shù)手冊[M].北京:科學(xué)出版社,先用C6H14O3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7楊樹良,王新榮,陳志榮等雙烷基封端聚醚的合成方法[PCN1276391A.2000二乙二醇單乙醚單鈉鹽與CH3Cl通過 william-8陳志柴,尹紅,王偉松等甲基或乙基封端聚醚的合成方法son反應(yīng)合成出 DEGMEE,合成條件為:反應(yīng)溫[P].CN1311265A.200度80℃,CH3Cl通入時間4.0h,n(CH3Cl):n9 Ono Kyoko, Watabe Yasuyoshi. Preparation of(poly) ethane(CH14O3)=1.4:1,在此條件下, DEGMEE收glycol diethers from the corresponding monoethers and ca率可達90%以上。bonate esters[P]. JP 09 227435 A21997SYNTHESIS OF DIETHYLENE GLYCOL METHYL ETHYL ETHERXu Qi, Cai Zhaosheng, Yang Chunsheng and Yan JinlongDepartment of Chemical and Biological EngineeringYancheng Institute of Technology, Yancheng 224003, Jiangsu, 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(C Hu O3)=1.5:1.0. Then diethylene glycol methyl ethyl ether (DEGMEE) was synthesizedthrough Williamson reaction from CH3 Cl and CH3 CH2 O(CH2 CH2 O)2 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(CH3 CD)/n(C Hu O3)=1.4: 1. The yield of dEgmee could be more than 90%Key words: diethylene glycol mono-ethyl ether; diethyleneWilliamson reaction; diethylene glycol methyl ethyl etherHH中國煤化工CNMHno-sodium salt: