精細(xì)石油化工進(jìn)展第10卷第10期ADVANCES IN FINE PETROCHEMICAIS甲醇與甲醛合成乙二醇的研究徐安陽(yáng)杜蕾陳學(xué)璽(青島科技大學(xué)化工學(xué)院,青島266042摘要以甲醇與甲醛為原料,選擇二叔丁基過(guò)氧化物(DTBP)和過(guò)氧化二異丙苯(DCP)分別作為引發(fā)劑進(jìn)行縮合反應(yīng)制得乙二醇?？疾炝艘l(fā)劑用量、反應(yīng)溫度、反應(yīng)時(shí)間、甲醇與甲醛質(zhì)量比、引發(fā)劑加入速度對(duì)反應(yīng)產(chǎn)物的影響,優(yōu)化了合成線路,使過(guò)程簡(jiǎn)單可行,產(chǎn)率提高。同時(shí)對(duì)DTBP的合成進(jìn)行改進(jìn),達(dá)到了降低成本,清潔生產(chǎn)的目的。確定了以DCP為引發(fā)劑合成乙二醇的最佳工藝條件:DCP用量2%,甲醇與甲醛質(zhì)量比10:1,反應(yīng)溫度145℃,反應(yīng)時(shí)間3hDTBP為引發(fā)劑合成乙二醇的最佳工藝條件:反應(yīng)溫度145℃,反應(yīng)時(shí)間4h,甲醇與甲醛質(zhì)量8:1,DTBP用量25%,引發(fā)劑加入速度0.05ml/min,在此條件下產(chǎn)物中乙二醇含量可達(dá)9.65%。關(guān)鍵詞乙二醇甲醇甲醛引發(fā)劑乙二醇(EG)是一種重要的石油化工基礎(chǔ)原1.2儀器料,主要用于生產(chǎn)聚酯纖維產(chǎn)品、防凍液、非離子磁力攪拌反應(yīng)釜及控制儀,煙臺(tái)市招遠(yuǎn)松嶺表面活性劑、增塑劑、不飽和聚酯樹脂、潤(rùn)滑劑及儀器設(shè)備有限公司;低溫冷卻循環(huán)泵,鞏義市英峪炸藥等,用途十分廣泛12)予華儀器廠;高壓輸液泵,北京創(chuàng)新通恒科技有限環(huán)氧乙烷直接水合法是目前國(guó)內(nèi)外工業(yè)化生公司;氣相色譜儀,島津GC-14型氣相色譜議。產(chǎn)乙二醇的主要方法。我國(guó)乙二醇的生產(chǎn)幾1.3實(shí)驗(yàn)步驟乎完全采用環(huán)氧乙烷直接水合法,即加壓水合的1.3.1DCP為引發(fā)劑合成乙二醇工藝路線4),存在技術(shù)依賴進(jìn)口、原料單一、成本DCP不溶于甲醛、甲醇和水中,因此,合成乙較高、污染較重的缺點(diǎn)。美國(guó) Celanese公司在醇采用一鍋法,即將原料一次投入到反應(yīng)釜中1982年開發(fā)了以甲醇和甲醛為原料,縮合生成乙進(jìn)行反應(yīng)。將一定量的甲醇、甲醛溶液和DCP按二醇的生產(chǎn)工藝”)。該技術(shù)主要是用有機(jī)過(guò)氧比例投入到反應(yīng)釜中,總質(zhì)量為300g。為防止甲化物如二叔丁基過(guò)氧化物(DTBP)、過(guò)氧化二異醛縮合,加入質(zhì)量分?jǐn)?shù)為0.02%的碳酸氫鈉。升丙苯(DCP)作為引發(fā)劑6,具有明顯的經(jīng)濟(jì)優(yōu)溫至110-145℃,反應(yīng)時(shí)間1-4h。反應(yīng)結(jié)束后勢(shì)。但產(chǎn)物中乙二醇含量最高為771%,存在收用冷卻水強(qiáng)制冷卻,產(chǎn)品用氣相色譜進(jìn)行分析。率低、分離成本高的劣勢(shì),未實(shí)現(xiàn)工業(yè)化。我國(guó)具1.3.2DTBP為引發(fā)劑合成乙二醇有豐富的煤、天然氣資源煤化工行業(yè)發(fā)展迅速,DTBP的合成(7:按化學(xué)計(jì)量比量取298%甲醇、甲醛呈現(xiàn)過(guò)剩態(tài)勢(shì)。因此,找到一條經(jīng)濟(jì)合雙氧水2.2g、40%硫酸35.9g和叔丁醇197g理的利用甲醇、甲醛為原料合成乙二醇的清潔生將硫酸移至燒瓶中降溫到10℃,劇烈攪拌下,同產(chǎn)工藝路線,在我國(guó)很有必要。本實(shí)驗(yàn)以甲醇和時(shí)滴加雙氧水和叔丁醇,控制滴加速度為:雙氧水甲醛為原料,合成乙二醇。考察了各種因素對(duì)合0.5mL/min叔丁醇0.6mL/min,反應(yīng)溫度不超成反應(yīng)的影響,確定了最佳工藝條件,所獲產(chǎn)品中過(guò)15℃,滴加完畢自然升至室溫繼續(xù)攪拌2h。乙二醇含量提高。分離上層有機(jī)相,先用30%NaOH溶液洗滌,再用實(shí)驗(yàn)8mL水洗,用無(wú)水MgSO4干燥,得到有刺激性氣1.1試劑味的中國(guó)煤化工叔丁醇,天津市博迪化工有限公司;甲醇,上中加入一定量甲醇CNMHG海振興化工一廠;甲醛溶液(含量37.4%),煙臺(tái)三和化學(xué)試劑有限公司;碳酸氫鈉,上海虹光化工收稿日期:2009-07-28作者簡(jiǎn)介:徐安陽(yáng),在讀碩士研究生,研究方向?yàn)樘家换衔飶S。所用試劑均為分析純。合成乙二醇2009年10月徐安陽(yáng)等.甲醇與甲醛合成乙二醇的研究和甲醛溶液及微量碳酸氫鈉,將反應(yīng)釜密封好,表2DTBP為引發(fā)劑正交試驗(yàn)設(shè)計(jì)及結(jié)果分析加熱到指定溫度,用高壓輸液泵以一定流速將DTBP和部分甲醇的混合物輸入到高壓反應(yīng)釜"P甲醇與甲反應(yīng)溫反應(yīng)時(shí)”速度/乙三醉含序號(hào)量,%醛質(zhì)量比度/℃問(wèn)/h中,然后開始計(jì)時(shí),到指定反應(yīng)時(shí)間后停止加8.000.052.8590熱。將反應(yīng)產(chǎn)物用冷凝水進(jìn)行強(qiáng)制冷卻,取出21.010.25:114520.103.8319進(jìn)行分析。12.14:10.1541.015.00:117540.203.01332結(jié)果及討論8.00:30.202.715521DCP引發(fā)劑合成乙二醇最佳條件的確定62.010.25:11300.152.630472.012.14:117510.102.3502確定DCP用量(A)、甲醇與甲醛質(zhì)量比(B)、0.052.3094反應(yīng)溫度(C)反應(yīng)時(shí)間(D)4個(gè)因素,設(shè)計(jì)4因92.58.00:10.105.2487素3水平正交試驗(yàn),考察反應(yīng)條件對(duì)產(chǎn)物的影響,102.510.25:117530.054.7292112.512.14:113020.201.9075結(jié)果見表1。從表1可看出,各因素對(duì)產(chǎn)物中乙122.515.00:114510.158.0931二醇含量的影響程度為C>A>B>D,最佳組合1750.155.5017為A3B1C2D3。綜合考慮原料成本和能耗等因素,143.010.25:116010.204.1607153.012.14:1450.059.650確定最佳工藝條件為:DCP用量2%,甲醇與甲醛1302.5493質(zhì)量比10:1,反應(yīng)溫度145℃,反應(yīng)時(shí)間3h。k12.8874.0812.4874.3664.887k22,5013.8386.0733.3883.495表1DCP為引發(fā)劑正交試驗(yàn)設(shè)計(jì)及結(jié)果分析k4.9953.9383.3902.9594.517序號(hào)DCP用量,甲醇與甲醛反應(yīng)溫反應(yīng)時(shí)乙三醇含k45.4663.9913.8995.1362.949R2.9650.2433.5862.1771.9388.0:10.1511.5:13結(jié)論0.991)甲醇與甲醛縮合生成乙二醇要使用帶雙8.0:1氧鍵結(jié)構(gòu)的引發(fā)劑,本研究選擇了過(guò)氧化二異丙15.0:10.23苯(DCP)和二叔丁基過(guò)氧化物(DTBP)作為引2發(fā)劑lI.5:11.18(2)通過(guò)正交試驗(yàn)并綜合考慮原料成本等因15.0:1145素,確定了DCP作為引發(fā)劑合成乙二醇的最佳工0.7831.8430.520藝條件為:反應(yīng)溫度145℃,反應(yīng)時(shí)間3h,DCP用k31.8200.973l.657量2%,甲醇與甲醛質(zhì)量比10:1;DTBP作為引發(fā)0.8700.490劑合成乙二醇的最佳工藝條件為:反應(yīng)溫度145℃,反應(yīng)時(shí)間4h,DTBP用量2.5%,甲醇與甲22DTBP引發(fā)劑合成乙二醇最佳條件的確定醛質(zhì)量比8:1,引發(fā)劑加入速度005mL/min。在確定DTBP用量(A)、甲醇與甲醛質(zhì)量比此反應(yīng)條件下,產(chǎn)物中乙二醇含量可達(dá)9.65%。(B)、反應(yīng)溫度(C)、反應(yīng)時(shí)間(D)、DTBP滴加速度(E)5個(gè)因素,設(shè)計(jì)5因素4水平正交試驗(yàn),考參考文獻(xiàn)察反應(yīng)條件對(duì)產(chǎn)物的影響,結(jié)果見表2。從表21賀俊海,黃集鉞,石鳴彥等.乙二醇合成技術(shù).精細(xì)化工原料及中間體,2008,(11):28-31可看出,各因素對(duì)產(chǎn)物中乙二醇含量影響的大小2崔小明乙二醇生產(chǎn)技術(shù)及國(guó)內(nèi)外市場(chǎng)分析.化工科技市場(chǎng),順序?yàn)镃>A>D>E>B,最佳組合為A4B1C2DE1。綜合考慮原料成本等因素,確定最3沈中國(guó)煤化工現(xiàn)狀及技術(shù)進(jìn)展石油化佳工藝條件為:DTBP用量2.5%,甲醇與甲醛質(zhì)CNMHGm小區(qū)術(shù)進(jìn)展.化工文摘,2003量比為8:1,反應(yīng)溫度145℃,反應(yīng)時(shí)間4h,DTB滴加速度0.05mL/min。在此條件下,產(chǎn)物中乙5 Kollar John. Production of Ethylene Clycol by Reaction of Metha二醇含量達(dá)9.65%。nolan Organic Peroxide and Formaidehyde. US 4337371. 1982精細(xì)石油化工進(jìn)展第10卷第10期ADVANCES IN FINE PETROCHEMICALS6游賢德.有機(jī)過(guò)氧化物.精細(xì)石油化工進(jìn)展,2000,1(7):7陳炳志,王超杰,宋金勇等,過(guò)氧叔丁醇和叔丁基過(guò)氧化物合成方法的改進(jìn).化學(xué)試劑,2000,2(6):50~51Study on Synthesis of Ethylene Glycol UsingMethanol and FormaldehydeXu Anyang Du Lei Chen XuexiChemical Engineering College of Qingdao Science and Technology University, Qingdao 266042)Abstract Ethylene glycol was prepared by condensation reaction using methanol and formaldehyde as rawmaterials and di-tert-butyl peroxide( DTBP )and dicumyl peroxide( DCP )as initiators respectively. Theeffects of initiator amount, reaction temperature, reaction time, mass ratio of methanol to formaldehydedding speed of initiator on the reaction product were investigated. The synthetic routes were optimized so thatthe processes were simple and feasible and rates of production were raised. At the same time, the synthesis ofDTBP was modified. The producing cost was lowered and the productive process was clean. The optimalprocess conditions for synthesizing ethylene glycol using DCP as initiator were determined as follows: dosage ofDCP was 2%, the mass ratio of methanol to formaldehyde was 10: 1, reaction temperature was 145 C and re-action time was 3 h. The optimal process condition for synthesizing ethylene glycol using DTBP as initiator wasas follows reaction temperature was 145C, reaction time was 4 h, the mass ratio of methanol to formaldehydewas 8: 1, dosage of DTBP was 2. 5%, adding speed of initiator was 0. 05 mL min. Under this condition, theethylene glycol content in the product could reach 9. 65%Key Words ethylene glycol, methanol, formaldehyde, initiator(上接第17頁(yè))Synthesis and Properties Research of Acrylate modifiedWaterborne Polyurethane EmulsionWangCollege of Chemical Engineering and Environment, North University of China, Taiyuan 030051)Abstract A waterborne polyurethane emulsion with C=C double bond in the main chain was synthesizedfrom toluene diisocyanate, polyether glycol, dimethylol propionic acid, and N-Hydroxymethyl acrylamide andthen was modified with methyl methacrylate( MMA) to prepare polyurethane-polymethylmethacrylate(PUA)copolymer emulsion. The influences of amount of MMA on the properties of the emulsion and its film wereinvestigated. The results indicated that the PUA emulsion had the best dispersion stability, and the waterabsorption rate and the water-resistance property of its film were improved markedly when the amount of methylmethacrylate was 20%中國(guó)煤化工Key Words waterbome polyurethane, polyurethane-polymetCN MHGnulsion, modification