5-磺酸鈉間苯二酸二甲酯的製程研究

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Title:	5-磺酸鈉間苯二酸二甲酯的製程研究
Other Titles:	Research of Dimethyl 5-sulfoisophthalate sodium salt
Authors:	鄭智惠
Contributors:	楊怡寬 Yang, I-Kuan 東海大學化學工程與材料工程學系
Keywords:	磺化;酯化;發煙硫酸;5-磺酸鈉間苯二酸二甲酯;間苯二酸 sulfonation;esterification;oleum;Dimethyl 5-sulfoisophthalate sodium salt;isophthalate acid
Date:	1999
Issue Date:	2011-06-15T02:44:07Z (UTC)
Abstract:	摘要在紡織工業上，5-磺酸鈉間苯二酸二甲酯是一種重要的染整助劑。但是目前此種化學品必須仰賴進口，造成成本上的負擔。有鑑於此，為提昇國內自製化學品的研發能力以及節省生產成本，本研究針對這助劑的製程進行探討以當作工業上大量生產之參考。本項研究主要在規劃5-磺酸鈉間苯二酸二甲酯的製程；以成本較低廉的間苯二酸作為原料，並採取三階段合成5-磺酸鈉間苯二酸二甲酯；先是磺化再皂化接著進行酯化反應。並且分別求出反應的反應速率定律式和反應活化能，與產物分離所需的資料。在磺化方面：磺化反應為串列式反應，中間產物為一元磺化物，最終產物為二元磺化物，但二元磺化物的產量很低（低於1％）。況且當中間產物- 5-磺酸鈉間苯二酸的產量達到最大時，二元磺化物的產量更是極少，因此可將二元磺化物的反應速率忽略不計。最後得到一元磺化反應的活化能因反應組成的不同約為20kcal/gmole ( 反應物間苯二酸與發煙硫酸莫耳比1：4 & 1：3)及28 kcal/gmole ( 反應物間苯二酸與發煙硫酸莫耳比1：5 & 1：6)。若以較少量的發煙硫酸反應（1：3 & 1：4）則反應速率亦較低，反應所需的活化能相對的亦小；反之，在發煙硫酸量較多時，會有較大的反應速率與活化能。而在本研究中所得到的最大反應速率常數值是在1：5中的200℃下得到0.204（1/ gmole‧hr），最大的產量發生在反應後2小時。在酯化方面：本試驗的酯化反應也是串列式(in series)的二元酯化反應，所以會有兩個反應速率常數：k1 & k2。本實驗所求得之k1值約為0.022 ~ 0.032（1/ gmole‧hr）；k2值約為0.022 ~ 0.031（1/ gmole‧hr）。其中在莫耳比為1：300的編號第15組可得到最大的k1=0.032（1/ gmole‧hr）與次多的k2=0.026（1/ gmole‧hr）；綜合本研究所得，若要獲得較大的經濟利益，則反應時間應控制在4小時左右，建議的反應物C8H5O7SNa與甲醇的莫耳比為1：300。綜合前述：在所做的試驗中，磺化反應的最佳反應速率發生在反應物C8H6O4：oleum之莫耳比為1：5、反應溫度200℃。k=0.20（1/ gmole‧hr）、E=2.80×104 cal/gmole；酯化反應則最佳反應速率發生在反應物（C8H5O7SNa：MeOH）莫耳比為1：300、k1=0.03（1/ gmole‧hr）、k2=0.03（1/ gmole‧hr）。 61 Abstract Dimethyl 5-sulfoisophthalate sodium salt, MS, is a dyeing assistant in the textile industry. At present this chemical must rely on import, and causes cost on bears. In view of this, to promote local R&D ability and to reduce production cost are the aims of this research. Hopefully, this research can help to develop the manufacture process of this dyeing assistant and to offer useful information to the mass production. The main object of this research is to establish the processes for producing MS with isophthalic acid as a raw material that is cheap in these markets. There needs three steps in synthesizing MS：first, sulfonation, second saponification, and then esterification. This research aims to obtain the rate equations of the reactions and their corresponding energy of activation and the appropriate separation process for the products. Sulfonation is a series reaction. The intermediate product is mono-sulfonates while the final is di-sulfonates. Only trace amount of di-sulfonates was observed（less than 1﹪）. When the amount of the intermediate reaches the maximum, which is the optimal timing to stop the reaction, the amount of di-sulfonates is even less, so the reaction rate of di-sulfonates is ignored in this research. The energy of activation of mono-sulfonates is different for various feeding ratios. They are about 20 kcal/gmole（the mole ratio of isophthalic acid and oleum are 1：4 & 1：3）and 28 kcal/gmole（the mole ratio of isophthalic acid and oleum are 1：5 &1：6）respectively. Less oleum in this reaction will induce slower the reaction rate and the energy of activation will be less, too. On the other hand, when more oleum is used, faster rate and higher energy of activation are observed. The maximal value of reaction rate constant is 0.204（1/ gmole‧hr）at the mole ratio of 1：5 and 200℃. The maximal amount of products was obtained at 2 hr after the reaction starts. The esterification is also a series reaction. So there are two reaction rate constants , k1 & k2 . The k1 from this study is about 0.022 ~ 0.032（1/ gmole‧hr）and k2 is about 0.022 ~ 0.031（1/ gmole‧hr）. For the reaction of the mole ratio 1：300 , k1 =0.032 and k2 ＝0.026（1/ gmole‧hr）. To sum up, for gaining more economical benefits, the time of the action should be controlled within about 4 hr and the mole ratio of 5-sulfoisophthalate sodium salt and methanol should be 1：300 .
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