第32卷第4期日用化學(xué)工業(yè)Vol 32 No. 4China Surfactant Detergent Cosmetics乙二醇葡萄糖苷的合成研究章亞?wèn)|,高曉蕾,王自健,蔣登高鄭州大學(xué)化工學(xué)院,河南鄭州45002)摘妾:研究了淀粉與乙二醇在酸性催化劑下合成乙二醇髓萄糖苷的工藝,考察了反應(yīng)溫度、糖醇摩爾比催化劑用量,反應(yīng)時(shí)問(wèn)和反應(yīng)壓力等因素對(duì)反應(yīng)和產(chǎn)品結(jié)果的影響,確立了較佳的工藝條件和參數(shù):反應(yīng)溫度為110℃,壓力為665kP,催化劑與經(jīng)折合的淀粉中葡萄糖單元摩爾比為003:1,醇糖元摩爾比為6:1,反應(yīng)時(shí)間為90min,中和劑為NaOH關(guān)詞:非離子表面活性劑;淀粉;乙二醇葡萄糖苷;合成中圖分類號(hào):TQ423.2文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):1001-1803(2002)04-0019-03烷基糖苷( Alkyl Polyglucoside,簡(jiǎn)稱APG)是糖河北承德實(shí)驗(yàn)機(jī)械廠。的半縮醛羥基與含有配質(zhì)或苷元的化合物進(jìn)行縮合反1.3合成及工藝流程應(yīng)得到的產(chǎn)物。烷基葡萄糖苷是糖苷中構(gòu)造最簡(jiǎn)單的1.3.1合成反應(yīng)式苷類化合物之一,通常用(G)nOR表示,式中G為葡萄糖單元,-OR為烷氧基,n為平均聚合度。)H +(m/n)HOCH CHAPG是20世紀(jì)90年代最新商品化的一類溫和型非離子表面活性劑,它不僅具有傳統(tǒng)表面活性劑的優(yōu)異性能,還具有其他獨(dú)特的性能:對(duì)人體(眼、皮CHCHOH +(m/n)H(膚)的刺激極微小,且配伍時(shí)可緩解其他物質(zhì)對(duì)人體的刺激,能迅速生物降解,對(duì)環(huán)境污染小;其毒性低,起泡力強(qiáng),泡沫穩(wěn)定,潤(rùn)濕性優(yōu)良,去污力強(qiáng),1.3.2合成工藝流程可在硬水中使用。它是以碳水化合物和天然脂肪醇流程圖見(jiàn)圖1。為合成原料的。因此開(kāi)展APG的合成研究,具有重要學(xué)術(shù)意義和應(yīng)用價(jià)值。催化劑淀份廣真空NaOH真本文在前期工作的基礎(chǔ)上2-6,開(kāi)展由淀粉為主要原料合成APG,為下一步合成高碳脂肪醇(Cs乙,一h一份圓-[k-hrC5)葡萄糖苷提供必要的基礎(chǔ)理論和基礎(chǔ)數(shù)據(jù)。圖1乙二醇葡萄糖苷合成工藝流程圖實(shí)驗(yàn)部分Fig. 1 Technological process diagram of synthesis APG1.1主要原料玉米淀粉,工業(yè)級(jí),黑龍江省牡丹江制藥廠;乙2合成反應(yīng)影響因素探討乙二醇與淀粉合成乙二醇葡萄糖苷,該反應(yīng)是液二醇,CP,鄭州市醫(yī)藥公司;催化劑及助催化劑,相反應(yīng)。淀粉常溫下不溶于乙二醇,溫度較高時(shí),發(fā)自制;NaOH,工業(yè)級(jí),河南開(kāi)普集團(tuán)公司。生溶脹,實(shí)驗(yàn)測(cè)得110℃時(shí),淀粉在乙二醇中的飽和12主要儀器溶解度為3.37×10-5molL0.5L不銹鋼反應(yīng)釜,威?；C(jī)械廠;ZG淀粉屬于天然的多糖高分子化合物,分子結(jié)構(gòu)是85A型旋蒸發(fā)器,上海醫(yī)療機(jī)械廠;GC-9C型色許多葡萄糖單元組成。根據(jù)組成不同,淀粉又分為直譜儀,中美合資上海全向電子有限公司;Ⅸ-2型旋鏈和支鏈淀粉兩種,常用(CHO3)m來(lái)表示淀粉的片真空泵,浙江黃巖化工機(jī)被廠;ND-79型旋轉(zhuǎn)式分子式。在研究中為便于與葡萄糖為原料的反應(yīng)比黏度計(jì),同濟(jì)大學(xué)機(jī)電廠;YZ-200型自動(dòng)張力儀,較中國(guó)煤化工析,扣除水分、溶解收稿日期:201-1-15;修回日期:200-03-25CNMHG基金項(xiàng)目:河南省自然科學(xué)基礎(chǔ)研究項(xiàng)目資助(作者簡(jiǎn)介:章亞?wèn)|(1965-),男,河南正陽(yáng)人,鄭州大學(xué)刪教授,博士生,聯(lián)系電話:(071)389317或3887303解究與開(kāi)譽(yù)日用化學(xué)工業(yè)第32卷物、蛋白質(zhì)、灰分和油脂等物質(zhì)后,按葡萄糖單元的相對(duì)分子質(zhì)量把淀粉折算成含葡萄糖摩爾量(簡(jiǎn)稱糖元摩爾量,以下同)。2.1醇糖元摩爾比對(duì)反應(yīng)組成的影響為使淀粉有高的轉(zhuǎn)化率,并保證反應(yīng)體系具適宜的黏度,有利于傳質(zhì)和傳熱,合成采用乙二醇過(guò)量。取反應(yīng)溫度110℃,壓力6.65kPa,n(催化劑)n(糖元)=0.03:1,反應(yīng)時(shí)間為1.5h,實(shí)驗(yàn)發(fā)現(xiàn)見(jiàn)圖2),醇糖元摩爾比由3:1增至6:1,單苷含量圖3反應(yīng)時(shí)間(1)與淀粉轉(zhuǎn)化率(n)的關(guān)系迅速增加,但由6:1增至8:1時(shí)、單苷含量增加緩Fig.3 Relationship between reaction time()and conversion慢。由此可見(jiàn),增加醇糖元摩爾比,可提高單苷產(chǎn)物rate of maize starch(110%.)的選擇性,但到達(dá)一定值后,作用大大降低。因此23催化劑用量對(duì)反應(yīng)速率的影響適宜的醇糖元摩爾比為6:1選取催化劑與糖元摩爾比分別為0.005:1,0.015:1,0.03:1,0,.045:1和0.06:1,在反應(yīng)溫度110℃,壓力6.65kPa下反應(yīng),分別測(cè)定反應(yīng)液變清所消耗時(shí)間t(min)(用碘滴定法檢測(cè)變色不明顯)為方便起見(jiàn),取反應(yīng)時(shí)間t的倒數(shù)簡(jiǎn)單表征該反應(yīng)速率,實(shí)驗(yàn)結(jié)果見(jiàn)圖4。隨著催化劑用量的增加,反應(yīng)速率快速增加、當(dāng)催化劑糖元摩爾比達(dá)0.03:1后,反應(yīng)速率加快不冉顯著,因此適宜的催化劑與糖元摩爾比為0.03:1。乙醅):n(糖單兒圖2醇糖元摩爾比對(duì)產(chǎn)品組成的影響ig. 2 FIect nMole ratin of glycol to glucose units on AP,products components(110 C)此外,實(shí)驗(yàn)測(cè)得(見(jiàn)表1)醇糖元摩爾比對(duì)反應(yīng)液黏度影響較大,隨著醇糖元摩爾比增大,由3:1至076:1黏度降幅較大,而從6:1增加到8:1時(shí),降幅不05L顯著,由此亦得到,從提高反應(yīng)體系傳質(zhì)、傳熱效果00.010020030405000出發(fā),適宜的醇糖元摩爾比亦可選6:1。n(化劑):n(糖單元)圖4催化劑糖元摩爾比對(duì)反應(yīng)速率的影響表1醇糖元摩爾比與反應(yīng)液黏度的關(guān)系Fig. 4 Effect of catalyst content on reaction rate(I" )(110(Tab. 1 Relationship between mole ratio of plycol to24溫度對(duì)淀粉轉(zhuǎn)化率及產(chǎn)品分布影響glucose and liquid viscosity取醇、糖元及催化劑摩爾比為6:1:0.03,反應(yīng)壓實(shí)驗(yàn)數(shù)據(jù)力665kPa下,實(shí)驗(yàn)測(cè)得在100℃、105℃、110℃5:16115℃下淀粉轉(zhuǎn)化率與反應(yīng)時(shí)間的關(guān)系(見(jiàn)圖5)及上述溫度卜產(chǎn)品組成分布的關(guān)系(見(jiàn)表2)黏度/mPa·s←一每2.2反應(yīng)時(shí)間對(duì)反應(yīng)的影響a.115(b.110C為合成出收率較高、顏色較好的產(chǎn)品,適宜的反c.105Cd.10C應(yīng)時(shí)間是非常重要的。實(shí)驗(yàn)得到在反應(yīng)溫度10℃壓力6.65kPa,糖元催化劑摩爾比1:0.03時(shí),不同反時(shí)間對(duì)淀粉轉(zhuǎn)化率(n)的影響見(jiàn)圖3。中國(guó)煤化工41010m由圖3看到,當(dāng)反應(yīng)時(shí)間小于90min區(qū)間,淀粉轉(zhuǎn)CNMHG反應(yīng)時(shí)間的關(guān)系化率呈快速線性上升。隨著反應(yīng)時(shí)間的延長(zhǎng),淀粉轉(zhuǎn)化率(η)提高微小,因此適宜的反應(yīng)時(shí)間為90mmFig. 5 Relationship between conversion rate of maizestarch(n)and reaction time(1)20第4期章亞?wèn)|等:乙二醇葡萄糖苷的合成研究新究與開(kāi)表2溫度對(duì)產(chǎn)品分布的影響不同攪拌速率下產(chǎn)品組成情況見(jiàn)表3Tab. 2 Effect of reaction temperature on experiment results表3攪拌速率對(duì)反應(yīng)結(jié)果的影響項(xiàng)目t/℃Tab. 3 Effect of stiring rale on reaction results轉(zhuǎn)速/rminn(單苷)/%67.269871.570.8項(xiàng)日150(多苷)/%21.823.90(單苷)/%50.2654715723v(聚糖等)/%11.0k(多苷)/%18.42124收率/%0(聚糖等)/%31.413.0由圖5看出,反應(yīng)溫度對(duì)反應(yīng)影響很大。反應(yīng)溫收率/%度為100℃時(shí),反應(yīng)180min,淀粉轉(zhuǎn)化率只有45%,由表3看出,當(dāng)攪拌速率達(dá)810r/min時(shí),多糖及而15℃時(shí),90min,轉(zhuǎn)化率已經(jīng)達(dá)到95%其他副產(chǎn)物僅3.6%,而且單苷和多苷含量也明顯增由表2得出,溫度雖對(duì)反應(yīng)影響很大,但對(duì)反應(yīng)加。但此后直到攪拌速率達(dá)1150m/min,產(chǎn)品組成變的選擇性和收率影響不大。然而溫度過(guò)高,產(chǎn)物的顏化不大,說(shuō)明此時(shí)已達(dá)臨界速率。實(shí)驗(yàn)發(fā)現(xiàn),在低色會(huì)加深,一定程度上會(huì)降低收率。速攪拌下,反應(yīng)液色澤較深,產(chǎn)品組成中主產(chǎn)物含量25系統(tǒng)壓力對(duì)反應(yīng)的影響低,這主要是低速率攪拌下,系統(tǒng)內(nèi)傳質(zhì)、傳熱和反由于玉米淀粉中含有11%~13%的水分,水的應(yīng)效果均差,生成了一些焦化產(chǎn)物所致存在將導(dǎo)致淀粉的糊化,加熱含水淀粉,將導(dǎo)致淀粉2.7中和劑對(duì)反應(yīng)的影響微晶熔融,同時(shí)發(fā)生不可逆溶脹,反應(yīng)體系將變得非乙二醇葡萄糖苷是縮醛。實(shí)驗(yàn)發(fā)現(xiàn),在不加中和常黏稠。本合成采用升溫時(shí),通過(guò)真空使玉米淀粉中劑的情況下反應(yīng)結(jié)束后,單苷含量明顯偏低,多苷的水分及反應(yīng)生成的水分迅速抽出反應(yīng)體系,以保證含量則較高,且產(chǎn)物色澤很深。這是由于縮醛在酸性體系內(nèi)良好的傳質(zhì)、傳熱和反應(yīng)要求。介質(zhì)不穩(wěn)定,在加熱脫醇時(shí),縮醛會(huì)發(fā)生分解,得到實(shí)驗(yàn)在反應(yīng)溫度110℃,醇、糖元及催化劑摩爾的葡萄糖會(huì)縮聚成多聚糖產(chǎn)生有色物質(zhì)。由于縮醛在比6:1:0.03時(shí),壓力分別在3.99kPa,5.32kPa,堿性介質(zhì)中穩(wěn)定,故反應(yīng)后應(yīng)加入適量堿或堿性氧化665kPa,7.89kPa和10.64kPa條件下,得到壓力對(duì)中和介質(zhì)酸性催化劑,保持反應(yīng)液呈弱堿性,使產(chǎn)反應(yīng)速率的影響(見(jiàn)圖6)。取反應(yīng)液變清(經(jīng)碘檢相對(duì)穩(wěn)定。本合成選用NaOH為中和劑。測(cè)無(wú)明顯變色)所需時(shí)間的倒數(shù)簡(jiǎn)單表征反應(yīng)速率。3結(jié)論6421)考察了反應(yīng)溫度、反應(yīng)壓力、醇糖元摩爾比、催化劑用量、攪拌速率和反應(yīng)時(shí)間等對(duì)由淀粉和乙二醇合成乙二醇葡萄糖苷反應(yīng)的影響。(2)得出∫合成乙二醇葡萄糖苷的適宜反應(yīng)條件,即:反應(yīng)溫度:110℃,壓力6.65kPa,醇、糖元和催化劑摩爾比6:1:0.03,反應(yīng)時(shí)間為90min參考文獻(xiàn)I」末啟埠,精細(xì)化工:「藝學(xué)[M!.北京:化學(xué)工業(yè)出版社,19%.圖6反應(yīng)壓力(p)對(duì)反應(yīng)速率(t1)的影響Fig.6 fert of reaction pressure(p) on reacton rate(t-1)(21章亞?wèn)|,王自健,黃恩才,正」基葡萄糖詩(shī)的合成J,華東琿從圖6可以看到,降低系統(tǒng)壓力對(duì)提高反應(yīng)速率大學(xué)學(xué)報(bào),199(6):578-580有明顯的影響,減低系統(tǒng)壓力對(duì)于去除反應(yīng)生成的水3]章亞?wèn)|、劉詩(shī)飛,黃恩才.正丁基葡萄糖苷合戰(zhàn)反應(yīng)動(dòng)力學(xué).華東理工大學(xué)學(xué)報(bào),1∞1(6):581-583有利,從而使可逆反應(yīng)加速向正反應(yīng)方向進(jìn)行。但壓41業(yè)東,將登高,和平,等、正十二烷基能的糖多首的合成力過(guò)低,反應(yīng)溫度下乙二醇亦會(huì)蒸出,對(duì)反應(yīng)不利,⊥藝研究!J.高?；瘜W(xué)工程學(xué)報(bào).3001,15(5):46-467.因而適宜的壓力應(yīng)選6.65kPa5】章業(yè)東,將登高,劉志偉,等.白接法合成正十:烷基葡萄糖2.6攪拌對(duì)反應(yīng)結(jié)果的影響苷的研究[].精細(xì)化T.200,18(9):50-512乙二醇和淀粉反應(yīng)屬非均相反應(yīng),攪拌速率直接16中國(guó)煤化工!學(xué)傳論文:D,那影響淀粉在乙二醇中溶解速率CNMHG].北京:化學(xué)工業(yè)出版社取醇、糖元和催化劑摩爾比6:1:0.03,反應(yīng)溫度110℃,壓力665kPa,反應(yīng)時(shí)間90min,實(shí)驗(yàn)測(cè)得在下轉(zhuǎn)第39頁(yè))21.第4期戚渭新等應(yīng)用于洗滌劑工業(yè)的高穩(wěn)定過(guò)碳酸鈉研究進(jìn)展康論與繃唱for prepare same LP]. U.S: 5366655,1994-11-22L 15 Bertsch-Frank, Birgit, Bewers. Coated solium percarbonate parti[9] Cuiliano, Basil A, Hills. Process for mecles, a process for their preparation and their use [P].U.S:5902682perhydrate particles and coating them with sodium borosilicate I P]1999-05-11U.S:5328721,194-07-12F 16] Chapple, Andrew P. Sodium percartk ne stabilized with a uting o anI 101 Klasen, Clasws-Juergen, Bertsch- Frank. Method for the preparationalkalimctal citrate [P]. U. S: 5258133, 1993of stabilized solium percarbonate [P]. U.S: 5632965, 1997-05[171 Suto. Kanji, Korbo, et al. Stabilized sodium percarbonate composition27P].U.S:5340×6,194-08-2311IBernch-Frark, Birgit, Klasen, el al. Coted sodian percarbonate [18] lagnenw, Hans, Jigtam. Bleaching agent[PI.U.S: 584692particles, a process for their production and bleaching compositions cun.1998-12-08ning then[P].C,S:56883,19×6-m7-1719] Iagnenw, Hans, Jigstam. Bleaching agent[ Pl. U. s: 5929015I 121 Mat unDO, Tadao, Koizawa, et al. Pruess for stabilization of sodiumpercarbonate[P.U.S:4325933,1982-04-20120]Roesler, Richanl, Mathes, et al. Solid peroxo comounds and peroxy[13] Kokubu, Jun, Hiro, Stabilized particle o sodium percarbonate [PTpounds stabilized by ooating [P]. U. S: 6086785,. 2000-07-111].S:5462804,1995-10-31[21]Lapmemo, Hans Sparks, et al. Bleaching agent [P.U.S:5.3364331994-08-09141 Dtsch, Wermer, Mathe. Detergent cmposition containing alkali metal [22] Beanjean, Hans-Joeef Caninck. Storage-stable encapeaulaled sodiumpemxysalt stabilized with alkali metal sulfate and chloride [P].U.S:percarbonate and process fox its production IP]. U. S: 5505875, 19965478488,1995-12-26Advances in studies of stable sodium percarbonate applied in detergentsQI Wei-zin, I SongResearth Institute of Jinling Petrochemical Corporation, Nanjing 210046, China)Abstract: Many kinds of methods which are used abroad in raising the stability of sodium percarbonate are introducedcoating materials include inorganic salts, organic salts and waler soluble polymers etc, Here, the pruduct multi-layere with inorganic salts and polymers is given with the solubility suitable for application, and its stability active oxygen leftrate)after two week ' s storage at 40 C, 80 relative humidity is above 90 % without detergent powter)and abov80%(with standard detergent powder)Key words: detergent auxiliary; sodiurm percarbonate; bleaching agent; detergent powder; coat: stahility2急急》】》》》》》D》》》當(dāng)》》》》}》》》游》》》》身身2》》衛(wèi)》2方》》當(dāng)》》》方》》2233》》}多》》》》》》》》》》》》》(上接第21頁(yè))Study of synthesis of glycol polyglucoside by maize starchZHANG Ya-dong, GAO Xiao-lei, WANG Zi-jian, JIANG /keng(College of Chemical Engineering, Zhenghou Universengzhou 450002, China)Abstract: In the presence of acid catalyst, synthesis process of glycol polyglucoside has been sludied with starch and glycolthe influences ofglycol to glucose units in maize starch, amounts of catalyst, reaction pressure and so on, have also been investigated. Betterocess conditions and parameters have been founded. The resultspressure is 6.65 kPa, the male ratio of catalyst, glycol to glucostion time is about 90 min and neutralization agent is NaOHH中國(guó)煤化工about 110℃CNMHG(mol: mol: mol ), reacKey words: nonionic surfactant; maize starch; glycol polyglucoside; synthesis