I3S8403 2011/10/27 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種以異丁烯及二乙二醇合成二 乙二醇第三丁基醚之方法，尤指一種利用異丁烯（IB=) 與二乙二醇（deg)，在固態酸觸媒作用下，於適當反 應條件中，經兩階段減壓蒸餾，即可有效合成產物得到 尚選擇性及咼純度之一乙二醇第三丁基謎（) .之合成方法。 【先前技術】 近年來由於芳香系溶劑具有高度光化學活性，因此 逐漸欠到環保法規限制，而改用較不具光化學活性之石 蠟烴、環烷烴及含氧系溶劑，並以含氧溶劑之使用比例 逐年增加，其中用途較廣之含氧溶劑係為醇醚類 (Glycol Ether)化合物。該醇醚類化合物係具有兩個 強溶解力之官能基，一為醚基，另一為羥基，前者具有 親油|±，後者具有親水性，因此成為性能優良之通用性 二劑。如乙二醇甲醚係為良好之表面塗料溶劑及飛機燃 料抗凍添加劑；乙二醇乙醚係用作塗料、染料、樹脂及 皮革等工業用溶劑，亦可作為金屬與玻璃清潔劑；及乙 二醇丁醚在水中具有良好分散性，被廣泛應用於水性塗 =中，另外，乙二醇醚類亦可應用於化粧品、香料及醫 藥工業等方面^而丙二醇醚類在塗料工業中，係可作為 醇酸樹脂及環氧樹脂等之溶劑，並且可使用於油墨使其 成為水溶性，藉以改善操作環境而提高印刷品質，此 5 1358403 2011/10/27 外’其亦可調配成各種清潔劑。 目前醇醚類溶劑中尤以乙二醇（EG)型醇醚用量 最大，其次為丙二醇（PG)型醇醚，包括曱基、乙基、 丙基及丁基醚等。雖然乙二醇醚價格較便宜，然而卻有 環保上之疑慮，並對人體健康有害，因此近年來丙二醇 喊之用量有逐漸增加之趨勢。除了可用丙二醇型取代乙 二醇型醇醚外，亦可用二乙二醇型醚類取代。目前乙二 醇醚全世界生產量約146萬噸/年，Dow Chemical在馬 藝來西亞設廠生產6萬嘴/年高純度乙二醇醚（99.9%)， 並在液晶平面顯示器製程中’作為洗淨液及正型光阻剝 離劑’且在半導體製程中之洗淨液需求量亦逐漸成長 中，尤其係二乙二醇丁醚之應用亦為將來發展之重點。 一般醇醚類化合物之合成方法有三種，首先第一種 • 為傳統之方法，係利用環氧化物與醇類反應合成，如第 7圖所示。由於此種合成方法可合成各種醇醚產品，因 此目前商用製程主要都係使用該方法製造醇醚。然而， _ 該方法之缺點係原料較貴，而且會產生很多副產物，以 乙二醇型產物為例，產物中乙二醇丁基醚約85%、二乙 二醇丁基醚約10%、以及其他多乙二醇丁基醚約5%， 另外，此合成方法亦不易提高二乙二醇丁基醚之產量， 因為若提高二·乙二醇丁基醚反應選擇性，則無法避免亦 會提高其他多乙二醇丁基醚等副產物之產量。 第二種合成方法係利用二醇與烯類進行醚化反 應，如第8圖所示。此方法之優點係副產物雙醚化合物 1358403 2011/10/27 螫 經分餾後’可回收進反應槽進行轉醚化反應（如美國專 利第4,345,102號）’同時可提高異丁烯溶解量，有助反 應活性並抑制雙丁基喊之生成（如美國專利第4,299,997 號）。然而’其缺點係受限於反應物係需要高活性之烯 類’.但活性太向之稀類又容易產生聚合副產物，因此醇 醚產品種類較少，而目前主要之產品係利用異丁烯合成 之第三丁基醚醇。另外醇醚產品與副產品雙醚化合物在 蒸餾時會產生共沸，較不易分離，亦係另一缺點。I3S8403 2011/10/27 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for synthesizing diethylene glycol tert-butyl ether from isobutylene and diethylene glycol, and more particularly to using isobutylene ( IB=) and diethylene glycol (deg), under the action of solid acid catalyst, under two-stage vacuum distillation under appropriate reaction conditions, can effectively synthesize the product to obtain one of the selective and oxime purity ethylene glycol. The third butyl mystery (). [Prior Art] In recent years, since aromatic solvents have high photochemical activity, they are gradually owed to environmental regulations, and are replaced with less photochemically active paraffin hydrocarbons, naphthenes and oxygen-containing solvents, and oxygen-containing solvents. The proportion of use is increasing year by year, and the most widely used oxygen-containing solvent is an alcohol ether (Glycol Ether) compound. The alcohol ether compound is a functional group having two strong dissolving powers, one being an ether group and the other being a hydroxyl group. The former has a lipophilic |±, and the latter has hydrophilicity, and thus is a versatile two agent having excellent performance. For example, ethylene glycol methyl ether is a good surface coating solvent and aircraft fuel antifreeze additive; ethylene glycol ether is used as an industrial solvent for coatings, dyes, resins and leather, and as a metal and glass cleaner; Glycol butyl ether has good dispersibility in water and is widely used in waterborne coatings. In addition, glycol ethers can also be used in cosmetics, perfumery and pharmaceutical industries. And propylene glycol ethers are used in the coatings industry. It can be used as a solvent for alkyd resins and epoxy resins, and can be used as an ink to make it water-soluble, thereby improving the operating environment and improving the printing quality. This can also be formulated into various cleanings. Agent. At present, the alcohol ether solvent has the largest amount of ethylene glycol (EG) type alcohol ether, followed by propylene glycol (PG) type alcohol ether, including mercapto, ethyl, propyl and butyl ether. Although the price of glycol ether is relatively cheap, it has environmental concerns and is harmful to human health. Therefore, the use of propylene glycol has gradually increased in recent years. In addition to the propylene glycol type substituted ethylene glycol type alcohol ether, it may be substituted with a diethylene glycol type ether. At present, the production of glycol ether is about 1.46 million tons per year. Dow Chemical has set up a factory in Ma Yilai to produce 60,000 mouth/year high purity glycol ether (99.9%), and in the process of liquid crystal flat panel display. As a cleaning solution and a positive photoresist stripping agent', the demand for cleaning liquid in the semiconductor process is also growing, especially the application of diethylene glycol butyl ether is also the focus of future development. There are three general methods for the synthesis of alcohol ether compounds. First, the first one is a conventional method, which is synthesized by reacting an epoxide with an alcohol, as shown in Fig. 7. Since this synthesis method can synthesize various alcohol ether products, the current commercial processes mainly use this method to produce alcohol ethers. However, the disadvantage of this method is that the raw materials are relatively expensive, and many by-products are produced. Taking the ethylene glycol type product as an example, the product has about 85% ethylene glycol butyl ether and about 10% diethylene glycol butyl ether. And other polyglycol butyl ether about 5%. In addition, this synthesis method is not easy to increase the yield of diethylene glycol butyl ether, because if the selectivity of diethylene glycol butyl ether is increased, it cannot be avoided. It will also increase the production of other by-products such as polyglycol butyl ether. The second synthesis method utilizes an etherification reaction of a diol with an olefin, as shown in Fig. 8. The advantage of this method is the by-product diether compound 1354403 2011/10/27 After fractionation, it can be recycled into the reaction tank for transetherification (such as U.S. Patent No. 4,345,102), which can increase the amount of isobutylene dissolved and help the reaction. Activity and inhibition of the formation of dibutyl shim (e.g., U.S. Patent No. 4,299,997). However, 'the disadvantage is limited by the fact that the reactants require highly active olefins'. However, the activity is too dilute and it is easy to produce polymerization by-products. Therefore, there are fewer types of alcohol ether products, and the current main products are synthesized by isobutylene. Third butyl ether alcohol. In addition, the alcohol ether product and the by-product diether compound are azeotropic when distilled, and are less likely to be separated, which is another disadvantage.
第三種合成醇醚方法係利用二醇類與醇類化合物 脫水合成，如第9圖所示。此方法需使用強酸性觸媒 (H2S〇4)於140〜18〇γ下反應。然而，由於反應條件 較嚴苛，W訂強酸對設備腐純亦高，因此較為少 2故，综域述可知…㈣料係無法符合使用者 於實際使用時之所需。 【發明内容】 上if 主要目的係在於’克服習知技藝所遭遇4 =喊並提供一種利用異丁婦與二乙二醇，在固態越 觸媒作用下，於適當反靡鉻杜 即可右兮人η此應條件中，經兩階段減壓蒸餾 产了有效合成產物得到高選 第三丁基社合成方法難及1"純度之二乙二萌 本發明之次要目的係在於，· - 醇雙第三丁㈣係可回收再反廡反”中之二乙二 量之同時，亦可與二乙-二可於提尚異丁烯溶解 制該項副產物之生成。°進仃轉醚化反應，並有效抑 7 1358403 為達以上之目的，太路日日你 2011/10/27 … ' 係—種以異丁烯及二乙二The third method of synthesizing an alcohol ether is carried out by dehydration of a glycol with an alcohol compound, as shown in Fig. 9. This method requires a strong acid catalyst (H2S〇4) to react at 140 to 18 〇 γ. However, due to the harsh reaction conditions, the strong acid content of the W is relatively high, so it is relatively low. Therefore, the comprehensive theory can be known... (4) The material system cannot meet the needs of the user in actual use. [Summary of the Invention] The main purpose of the above is to 'overcome the experience of the art. 4 = shout and provide a kind of use of Isopropyl and diethylene glycol, in the solid state of the catalyst, in the appropriate anti-靡 靡 即可 即可 right In this condition, the two-stage vacuum distillation produces an effective synthesis product to obtain a high-selection third-butyl synthesis method. 1" Purity of diethyl bismuth. The secondary purpose of the invention is that - Alcohol double third (4) can be recycled and then reversed, and the second and second amounts can be combined with the second to the second to dissolve the isobutylene to produce the by-product. Reaction, and effective inhibition 7 1358403 For the purpose of the above, Tai Road, you are 2011/10/27 ... ' Department - kind of isobutylene and two
知口成二乙二醇第三丁㈣之方法，係使用生產乙二醇 讀且副產物二乙二醇，與τ二烯萃餘油中之異丁婦進 灯喊化反應，即可有效合成產物得到高選擇性及高純度 之—乙二醇第三丁基，首先，係利用適當比例之二乙 =酵與異丁缔作為進料，在—酸性陽離子型㈣樹脂作 )、觸媒之作用下’於反應溫度為3G〜丨5代與反應壓力 為15〜500psi，且該觸媒酸量與該異丁烯（[Η+]ΓΙΒ=) 之莫耳比料moo,以及該二乙二醇與該異丁稀 (DEG/IB )之莫耳比值為〇 5〜1〇 〇之反應條件中， 混合得-_混合物；將此反應後所得之賴混合物進 行兩階段錢壓_分離純化，並以第—階段為低真空 水萃取蒸館’分離副產物二乙二醇雙第三丁基醚（ DEGDtBE)及辛烯（〇ctene)，再以第二階段為高真空 蒸餾，分離未反應之二乙二醇及產物_二乙二醇第三丁 基醚；以及將上述第一階段低真空蒸餾分離之副產物二 乙一醇雙第二丁基醚，迴流打入上述反應系統中，可於 提咼異丁烯溶解量之同時，亦可與該二乙二醇進行轉醚 化反應，並有效抑制該項副產物之生成。 另外，本發明醚化反應之進行亦可使用連續式固定 床反應設備操作，經兩階段減壓蒸餾，同樣可以有效分 離辛烯、二乙二醇雙第三丁基醚及二乙二醇，藉此得到 高純度之二乙二醇第三丁基醚。 【實施方式】 1358403 2011/10/27 凊參閱『第1圖』所示，係本發明之製作流程示意 圖。如圖所不：本發明係一種以異丁浠及二乙二醇合成 二乙二醇第三丁基醚之方法，係進料該異丁烯（IB=) 及該一乙二醇（DEG)，並在一酸性陽離子型交換樹脂 作為觸媒之作用T，.進行_化反應，該合成方法係至少 包含下列步驟： (Α)醇醚混合物製備11:將該二乙二醇及該異 丁烯與該酸性陽離子型交換樹脂之觸媒置於一反應槽 中，並將該反應槽控制於反應溫度介於3〇〜l5〇c>c之 間’及反應壓力介於15〜500psi之間進行混合得一醇醚 混合物，其中該觸媒酸量與該異丁烯（[h+]/ib=)之莫 耳比值係介於G.G1〜1.GG，且該二乙二醇與該異丁婦 (DEG/IB )之莫耳比值係介於〇5〜1〇〇; (B )兩階段式減壓蒸餾分離純化i 2 :將上述步 驟（A )反應後所得之醇醚混合物進行兩階段式 餾分離純化，並以第一階段為低真空水萃取蒸餾，控制 壓力介於50〜500托耳（Torr)，且溫度度介於5〇〜i5〇〇c 下，分離副產物二乙二醇雙蓆三丁基醚（DEGmBE)& 辛稀（Octene)，再以第二階段為高真空蒸館，控制壓 力介於0.1〜10托耳，且溫度度介於50〜150〇c下分 離未反應之二乙二醇及產物_上_乙二醇第三丁.基二 (DEGtBE)，其中該第-階段加人之水相對於該賴混 合物之重量比值係介於0.1〜5.0;以及 (C ) δ1】產物迴流1 3 :將上述步驟（B )第一階 Γ358403 2011/10/27 段低真空水萃取蒸餾分離之副產物二乙二醇雙第三丁_ 基鰱’迴流打入該反應槽中，與該二乙二醇進行轉醚化 反應’其中該二乙二醇雙第三丁基醚與該二乙二醇之重 量比值係介於0.002〜1.0。The method of knowing the diethylene glycol tributyl (4) is effective in the production of ethylene glycol and the by-product diethylene glycol, which is effective in reacting with the dibutyl cation lamp in the tau diene residue. The synthesized product obtains a highly selective and high-purity ethylene glycol tert-butyl group. First, it uses a suitable ratio of di-b = yeast and isobutylene as a feed, in an acid-cationic (four) resin, and a catalyst. Under the action of 'the reaction temperature is 3G ~ 丨 5 generations and the reaction pressure is 15~500 psi, and the amount of the catalyst acid and the isobutene ([Η+]ΓΙΒ=) molar ratio moo, and the diethylene The molar ratio of the alcohol to the isobutylene (DEG/IB) is 〇5~1〇〇, and the mixture is mixed, and the mixture obtained after the reaction is subjected to two-stage pressure-separation purification. In the first stage, the low-vacuum water extraction steaming plant 'separation by-product diethylene glycol di-tert-butyl ether (DEGDtBE) and octene (〇ctene), and then the second stage for high vacuum distillation, separation unreacted Diethylene glycol and product _ diethylene glycol tert-butyl ether; and separation of the above first stage of low vacuum distillation The product diethylene glycol double second butyl ether is refluxed into the above reaction system, and the deuteration of the isobutylene can be carried out, and the ethylene glycol can be subjected to transesterification reaction, and the by-product is effectively inhibited. The generation. In addition, the etherification reaction of the present invention can also be carried out by using a continuous fixed bed reaction apparatus, and the two-stage vacuum distillation can also effectively separate octene, diethylene glycol bis-tert-butyl ether and diethylene glycol. Thereby, high-purity diethylene glycol tert-butyl ether is obtained. [Embodiment] 1358403 2011/10/27 凊 Refer to the "Fig. 1", which is a schematic diagram of the production flow of the present invention. As shown in the figure: the present invention is a method for synthesizing diethylene glycol tert-butyl ether with isobutyl hydrazine and diethylene glycol, and feeding the isobutylene (IB=) and the monoethylene glycol (DEG), And performing an oxidation reaction on the acidic T-type exchange resin as a catalyst T, the synthesis method comprises at least the following steps: (Α) alcohol ether mixture preparation 11: the diethylene glycol and the isobutylene and the The catalyst of the acidic cationic exchange resin is placed in a reaction tank, and the reaction tank is controlled to be mixed between the reaction temperature of 3〇~l5〇c>c and the reaction pressure is between 15~500 psi. a mixture of alcohol ethers wherein the amount of the catalyzed acid and the molar ratio of the isobutylene ([h+]/ib=) are between G.G1 and 1.GG, and the diethylene glycol and the dibutyl woman (DEG) / IB ) The molar ratio is between 〇5 and 1 〇〇; (B) Two-stage vacuum distillation separation and purification of i 2 : the two-stage distillation of the alcohol ether mixture obtained after the above step (A) Purification, and the first stage is low vacuum water extraction distillation, the control pressure is between 50~500 Torr, and the temperature is between 5〇~i Under 5〇〇c, the by-product diethylene glycol double-span tributyl ether (DEGmBE) & Octene is separated, and the second stage is high vacuum steaming, and the control pressure is between 0.1 and 10 Torr. And separating the unreacted diethylene glycol and the product _upper_ethylene glycol tert-butyl 2 (DEGtBE) at a temperature of 50 to 150 〇c, wherein the first stage added water relative to the The weight ratio of the mixture is between 0.1 and 5.0; and (C) δ1] product reflux 1 3 : the by-product of the first step Γ 358403 2011/10/27 of the above step (B) is separated by low vacuum water extraction and distillation. The diol bis-tertiary dimethyl hydrazine is refluxed into the reaction tank to carry out transesterification reaction with the diethylene glycol, wherein the weight of the diethylene glycol bis-tert-butyl ether and the diethylene glycol The ratio is between 0.002 and 1.0.
上述步驟（A )反應之進行亦可.使用連續式固定床 反應設備操作，打入該二乙二醇及該異丁烯與該為酸性 陽離子型交換樹脂之觸媒’並控制反應溫度介於3〇〜 150°C之間，及反應壓力介於15〜500psi之間，其中該 二乙二醇與該異丁烯之莫耳比值係介於0.5〜1〇.〇，且 該 乙二醇與該異丁烯混合進料之重量小時空間流速 (WHSV)係介於（U〜1〇 〇h-i。 藉此，本發明係使用生產乙二醇（EG)之便宜副 產物二乙二醇，與丁二稀萃餘油中之異丁稀反應，並在 ，態酸觸媒作用下，於適當反應條件中，經兩階段減壓 蒸餾，即可有效合成產物得到高選擇性及高純度之二乙 二醇第三丁基_’而反應副產物中之二乙二醇雙第三丁 基鱗則可回收再反應，可於提高異丁_解量之同時， 二醇進行轉㈣反應，並有效抑制該項副產 人^㈣於利時，該異了叙關係 此合物’如丁婦混合物，且於其·中異丁稀之 工 = Wt% ’而該二乙二醇之進料中二乙二醇之2 係為10〜_ wt% ’並在—經酸化處理之 (-S03H)陽離子型交換樹脂作為觸媒之作用下「進ς 1358403 2011/10/27 越化反應，該合成方法係至少包含下列步驟： (A 1 )將該二乙二醇及該異丁烯與上述經酸化之 陽離子型交換樹脂之觸媒置於—反應槽中，並將該反應 槽控制於反應溫度介於5G〜6G。之間，及反應I力介於 50 200pSi之間進行混合得一醇醚混合物其中該觸媒 酸量與該異丁烯之莫耳比值係介於0.04〜〇.〇6,且該二 乙二醇與該異丁烯之莫耳比值係介於2 〇〜3 〇 ; (B1)將上述步驟（A1)反應後所得之醇醚混 合物進行兩階段式減壓蒸餾分離純化，並以第一階段之 低真空水萃取蒸餾，控制壓力介於100〜200牦耳，且 溫度度介於65〜1〇50C下，分離副產物_二乙二醇雙第 三I基醚及辛烯，再以第二階段之高真空蒸餾，控制壓 力介於0.3〜1·〇托耳，且溫度度介於8〇〜u〇〇c下分 離未反應之二乙二醇及產物-二乙二醇第三丁基醚，其 中該第一階段加入之水相對於該醇醚混合物之重量比 值係介於0.25〜1.0 ;以及 * ( C 1 )將上述步驟（B 1 )第一階段低真空水萃 取蒸餾分離之副產物二乙二醇雙第三丁基醚，迴流打入 該反應槽中，與該二乙二醇進行轉醚化反應，其中該二 乙二醇雙第三丁基醚與該二乙二醇之重量比值係介於 〇.〇1〜0.1 ’並且，迴流打入之二乙丄醇雙第三丁基醚中 係含有二乙二醇第三丁基醚或二乙二醇，且該二乙二醇 雙第三丁基醚之含量係為1〜lOOwt%。 上述步驟（A 1 )反應之進行亦可使用連續式固定 1358403 2011/10/27 -床反應設備操作，打入該二乙二醇及該異丁烯與該經酸 化之陽離子型交換樹脂之觸媒，並控制反應溫度介於 45〜55°C之間，及反應壓力介於50〜200psi之間，其 中該二乙二醇與該異丁烯之莫耳比值係介於1.5〜2.5， 且該二乙二醇與該異丁烯混合進料之WHSV係介於.1.2 〜2.01Γ1。 請參閱『第2 A〜2 C圖』所示，係分別為本發明 一較佳實施例之反應溫度對反應活性與選擇性影響示 • 意圖、本發明一較佳實施例之觸媒酸量對反應活性與選 擇性影響示意圖及本發明一較佳實施例之反應物 DEG/IB=比值對反應活性與選擇性影響示意圖。如圖所 示：依據上述第1圖所述之醚化反應，於一較佳實施例 中，本發明係使用高壓蚤（Autoclave )進行活性測定。 首先，取106克（g)乙二醇及11克經酸性處理後酸度 為4.5 meq[H+]/g之陽離子型交換樹脂（Amberlyst 15) 作為觸媒，將其置於600毫升（ml)之高壓釜中，之後 # 通入31克丁烯混合物，其中該丁烯混合物係内含90% 之異丁烯（約28克）。在DEG/IB=之莫耳比值為2.0， 且[H+]/IB=之莫耳比值為0.05，將此加壓密閉之高壓釜 置於油浴中，控制油浴溫度在50〜110°C之反應溫度 後，以氮氣加壓至200psi，開始攪拌進行反應6小時， 並定時以每次0.5ml取樣分析產物成份，計算不同時間 之異丁烯轉化率及DEGtBE、DEGDtBE與Octene之選 擇性。由第2 A圖顯示之結果可知，於60°C反應具有 12 1358403 2011/10/27 最高之異丁烯轉化率，但在50°C則有較高之DEGtBE 選擇性，因此，反應溫度對異丁烯轉化率與產物選擇性 之表現係以50〜60°C為較佳之反應條件。 依據上述第2A圖所設定之參數，反應物DEG/IB= .用量不變，僅改變上述酸性觸媒之用量為6.6克及15.4 克，因此其[H+]/IB=之莫耳比值係分別為0_03及0.07。 將其分別於60°C下反應6小時後，結果如第2 B圖所 示，當酸性觸媒用量提高時，係可提高異丁烯轉化率， • 其中並以[H+]/IB=莫耳比值對異丁烯轉化率與產物選擇 性之表現以0.04〜0.06為較佳之反應條件。 依據上述第2A圖所設定之參數，固定[H+]/IB=之 莫耳比值為0.05不變，改變反應物中DEG/IB=之莫耳比 值為1.5〜3.5。將其分別於60°C下反應6小時後，結 果如第2C圖所示，當DEG/IB=之莫耳比值提高時，係 可提高異丁烯轉化率及DEGtBE選擇性，其中並以反應 物DEG/IB=莫耳比值對異丁烯轉化率與產物選擇性之 • 表現以2.0〜3.0為較佳之反應條件。 請參閱『第3 A〜3 C圖』所示，係分別為本發明 •另一較佳實施例之反應溫度對反應活性與選擇性影響 • 示意圖、本發明另一較佳實施例之反應物DEG/IB=比值 對反應活性與選擇性影響示意圖及本發明另一較佳實 施例之WHSV對反應活性與選擇性影響示意圖。如圖 所示：依據上述第1圖所述之醚化反應，除了使用高壓 釜進行活性測定外，於另一較佳實施例中，本發明亦可 13 1358403 2011/10/27 使用連續式固定床反應設備進行測試。首先，於200psi 壓力下，分別利甩一液相層析幫浦（LC pump )以上向 流（Up-Flow )方式打入二乙二醇及丁烯混合物當進料， . 其中該丁烯混合物進料之組成分中係含有50%之異丁 .烯。利用循環熱.水浴加熱其反應管，且在該内徑為1/2 忖及管長50公分之反應管内係裝有55.5克Amberlyst 15之酸性陽離子型交換樹脂作為觸媒，控制反應溫度 在45〜80°C，於DEG/IB=進料莫耳比值為2.0以及 • WHSV為1.201Γ1，每小時取樣分析產物成份，計算不同 時間之異丁烯轉化率及產物選擇性。由第3 A圖顯示之 結果可知，於55°C反應具有最高之異丁烯轉化率，但 在45°C則有較高之DEGtBE選擇性，因此，反應溫度 對異丁烯轉化率與產物選擇性之表現係以45〜55°C為 較佳之反應條件。 依據上述第3A圖所設定之參數，WHSV不變，改 變上述反應物中DEG/IB=之莫耳比值為1.5〜4.0。將其 • 分別於55°C下進行反應，結果如第3 B圖所示，當 DEG/IB=之莫耳比值提高時，係可提高異丁烯轉化率及 DEGtBE選擇性，其中並以反應物DEG/IB=莫耳比值對 . 異丁烯轉化率與產物選擇性之表現以1.5〜2.5為較佳 之反應條件。The reaction of the above step (A) may also be carried out by using a continuous fixed bed reaction apparatus, driving the diethylene glycol and the catalyst of the isobutylene and the acidic cationic exchange resin and controlling the reaction temperature to be 3 〇. Between 150 ° C and a reaction pressure of between 15 and 500 psi, wherein the molar ratio of the diethylene glycol to the isobutylene is between 0.5 and 1 Torr., and the ethylene glycol is mixed with the isobutylene. The weight hourly space velocity (WHSV) of the feed is between (U~1〇〇hi. Thus, the present invention uses a cheap by-product of the production of ethylene glycol (EG), diethylene glycol, and distillate The isobutylene reaction in the oil, and under the action of the acid catalyst, under two-stage vacuum distillation under appropriate reaction conditions, the product can be effectively synthesized to obtain a highly selective and high-purity diethylene glycol third. Butyl-' and the diethylene glycol di-tert-butyl scale in the by-product of the reaction can be recovered and re-reacted, and the diol can be subjected to the trans (four) reaction while suppressing the amount of isobutylation, and the reaction is effectively inhibited. Producer ^ (4) Yu Li Shi, the difference between the relationship of this compound 'such as Dingfu mixture, and In the medium of isobutadiene = Wt% 'and the diethylene glycol in the feed of diethylene glycol is 10~_ wt% 'and in the acidified (-S03H) cationic type The exchange resin is used as a catalyst. The synthesis method comprises at least the following steps: (A 1 ) the diethylene glycol and the isobutylene and the acidified cationic type described above. The catalyst for exchange resin is placed in a reaction tank, and the reaction tank is controlled to have a reaction temperature between 5G and 6G, and a reaction I force is between 50 and 200 pSi to obtain an alcohol ether mixture. The molar ratio of the amount of the acid to the isobutene is between 0.04 and 〇.6, and the molar ratio of the diethylene glycol to the isobutylene is between 2 〇 and 3 〇; (B1) the above step (A1) The alcohol ether mixture obtained after the reaction is separated and purified by two-stage vacuum distillation, and is subjected to the first stage of low vacuum water extraction and distillation, the control pressure is between 100 and 200 牦, and the temperature is between 65 and 1 〇 50C. Next, separating the by-product _ diethylene glycol bis third I base ether and octene, and then using the second stage of high vacuum distillation, Controlling the pressure between 0.3~1·〇托耳, and separating the unreacted diethylene glycol and the product-diethylene glycol tert-butyl ether at a temperature of 8〇~u〇〇c, wherein the first The weight ratio of the water added in the stage to the mixture of the alcohol ethers is between 0.25 and 1.0; and * (C 1 ) the by-product diethylene glycol double of the first stage low vacuum water extraction and distillation separation of the above step (B 1 ) a third butyl ether, refluxed into the reaction tank, and subjected to a transetherification reaction with the diethylene glycol, wherein the weight ratio of the diethylene glycol di-tert-butyl ether to the diethylene glycol is between 〇.〇1~0.1 'and, the refluxed ethylene glycol di-tert-butyl ether contains diethylene glycol tert-butyl ether or diethylene glycol, and the diethylene glycol double third The content of the butyl ether is from 1 to 100% by weight. The above step (A 1 ) reaction can also be carried out by using a continuous fixed 1538403 2011/10/27 - bed reaction apparatus to drive the diethylene glycol and the catalyst of the isobutylene and the acidified cationic exchange resin. And controlling the reaction temperature is between 45 and 55 ° C, and the reaction pressure is between 50 and 200 psi, wherein the molar ratio of the diethylene glycol to the isobutylene is between 1.5 and 2.5, and the diethylene The WHSV system in which the alcohol is mixed with the isobutylene is between 1.2 and 2.01 Γ1. Please refer to the "2A~2C" diagram for the effect of reaction temperature on reactivity and selectivity, respectively, in accordance with a preferred embodiment of the present invention, and the amount of catalyst acid in a preferred embodiment of the present invention. A schematic diagram of the effect of reactivity and selectivity on the reaction activity and selectivity of the reactant DEG/IB= ratio of a preferred embodiment of the invention. As shown in the figure: According to the etherification reaction described in the above first embodiment, in a preferred embodiment, the present invention uses a high pressure enthalpy (Autoclave) for activity measurement. First, 106 g (g) of ethylene glycol and 11 g of a cationic exchange resin (Amberlyst 15) having an acidity of 4.5 meq [H+]/g after acid treatment were used as a catalyst, and placed in 600 ml (ml). In the autoclave, 31 g of a butene mixture was introduced, wherein the butene mixture contained 90% of isobutylene (about 28 g). The molar ratio of DEG/IB= is 2.0, and the molar ratio of [H+]/IB= is 0.05. The pressure-sealed autoclave is placed in an oil bath, and the temperature of the oil bath is controlled at 50 to 110 ° C. After the reaction temperature, the pressure was raised to 200 psi with nitrogen, stirring was started for 6 hours, and the product components were sampled at 0.5 ml each time to calculate the isobutene conversion at different times and the selectivity of DEGtBE, DEGDtBE and Octene. From the results shown in Figure 2A, it is known that the reaction at 60 ° C has the highest isobutene conversion of 12 1358403 2011/10/27, but has a higher DEGtBE selectivity at 50 ° C, therefore, the reaction temperature is converted to isobutylene. The ratio of product selectivity to product selectivity is preferably from 50 to 60 °C. According to the parameters set in Figure 2A above, the reactants DEG/IB=. The dosage is unchanged, only the amount of the above acidic catalyst is changed to 6.6 g and 15.4 g, so the molar ratio of [H+]/IB= is It is 0_03 and 0.07. After reacting at 60 ° C for 6 hours, the results are as shown in Fig. 2B. When the amount of the acidic catalyst is increased, the conversion of isobutylene can be increased, and wherein [H+] / IB = molar ratio The performance of isobutene conversion and product selectivity is preferably from 0.04 to 0.06. According to the parameters set in Fig. 2A above, the molar ratio of [H+]/IB= is fixed to 0.05, and the molar ratio of DEG/IB= in the reactant is changed to 1.5 to 3.5. After reacting at 60 ° C for 6 hours, the results are as shown in Fig. 2C. When the molar ratio of DEG/IB = is increased, the conversion of isobutylene and the selectivity of DEGtBE can be improved, wherein the reactant DEG is used. /IB = molar ratio to isobutene conversion and product selectivity. The performance is preferably 2.0 to 3.0. Please refer to "3A to 3C" for the reaction temperature and reactivity and selectivity of another preferred embodiment of the present invention. DEG/IB = Schematic diagram of the effect of ratio on reactivity and selectivity and the effect of WHSV on reactivity and selectivity in another preferred embodiment of the invention. As shown in the figure: in accordance with the etherification reaction described in the above first embodiment, in addition to the use of an autoclave for activity measurement, in another preferred embodiment, the invention may also be used for continuous fixation using 13 1358403 2011/10/27. Bed reaction equipment was tested. First, a mixture of diethylene glycol and butene is fed into the upper stream of the LC pump at a pressure of 200 psi, respectively. The composition of the feed contains 50% isobutylene. The reaction tube was heated by a circulating heat and water bath, and 55.5 g of Amberlyst 15 acidic cationic exchange resin was used as a catalyst in the reaction tube having an inner diameter of 1/2 忖 and a tube length of 50 cm, and the reaction temperature was controlled at 45 °. At 80 ° C, the DEG/IB = feed molar ratio of 2.0 and • WHSV of 1.201 Γ 1, the product components were sampled every hour, and the isobutene conversion and product selectivity were calculated at different times. From the results shown in Figure 3A, it is known that the reaction at 55 ° C has the highest isobutene conversion, but at 45 ° C there is a higher DEGtBE selectivity, therefore, the reaction temperature versus isobutene conversion and product selectivity The reaction conditions are preferably 45 to 55 ° C. According to the parameters set in the above Fig. 3A, the WHSV is constant, and the molar ratio of DEG/IB = in the above reactant is changed to 1.5 to 4.0. The reaction was carried out at 55 ° C, respectively. As shown in Fig. 3B, when the molar ratio of DEG/IB = increased, the conversion of isobutylene and the selectivity of DEGtBE were improved, and the reactant DEG was used. /IB = molar ratio. The performance of isobutene conversion and product selectivity is preferably from 1.5 to 2.5.
依據上述第3A圖所設定之參數，反應物DEG/IB= 用量不變，改變上述WHSV為0.6〜2.4，將其分別於 55°C下進行反應後，結果如第3 C圖所示，當WHSV 14 1358403 2011/10/27 提高時，係可提高異丁烯轉化率及DEGtBE選擇性，其 中並以WHSV對異丁烯轉化率與產物選擇性之表現以 - 1.2〜2.0 ΙΓ1為較佳之反應條件。 請參閱『第4圖』所示，係本發明產物之分離與純 .化示意圖。如圖所示：本發明採用減壓蒸餾，於第一階 段低真空蒸餾可在共沸現象時於蒸餾液中加入適量 水，利用水在減壓情況下，將DEGDtBE帶出來，殘餘 蒸餾液中之DEGDtBE逐漸減少，而蒸餾出之液體可自 φ 動分離成兩層，上層為DEBDtBE，下層為水，並將下 層之水迴流至底部蒸餾液中，如此循環蒸德，即可有效 分離副產物DEGDtBE。而殘留蒸餾液中含有之DEGtBE 及二乙二醇，可再利用第二階段高真空蒸餾分離 DEGtBE產物與二乙二醇反應物。 請參閱『第5圖』所示，係本發明反應溫度對 DEGDtBE轉醚化反應活性影響示意圖。如圖所示：為 進一步證實轉醚化反應之進行，於二乙二醇進料中不加 • 異丁烯成份，而加入10 wt% DEGDtBE，依上述第2 A 圖之反應條件進行反應，改變反應溫度，分別計算其 • DEGDtBE之轉化率及每莫耳DEGDtBE作為反應物生 \ 成DEGtBE之莫耳數，待反應6小時後，由其結果顯示 可知，反應溫度愈高，DEGDtBE轉化率愈高，DEGtBE 生成量亦隨之增加。在反應過程中，DEGDtBE除了可 與二乙二醇進行轉醚化反應，生成2分子DEGtBE外， 同時亦可能於較高溫時斷裂成1分子DEGtBE及1分子 15 1358403 2011/10/27 C4,或斷裂成1分子二乙二醇及2分子C4。如在含有 二乙二醇及C4反應物系統中添加DEGDtBE，（意即副 - 產物-DEGDtBE經第一階段分離後再迴流至反應槽）， 則此時裂解反應可減少，因此可在進行主要之轉醚化反 應同.時，亦可抑制DEGDtBE之生成。. 請參閱『第6圖』所示，係本發明反應溫度對 DEGDtBE裂解反應活性影響示意圖。如圖所示：為進 一步區別轉醚化反應及裂解反應，本發明乃進行另一實 φ 驗。以含10 wt% DEGDtBE之甲苯為進料，測試 DEGDtBE之裂解反應，依上述第2A圖之反應條件進 - 行反應，改變反應溫度，待反應6小時後，由其實驗結 果顯示可知，DEGDtBE轉化率隨反應溫度提高而增 加，50°C以下幾乎沒有裂解反應發生，90°C以下只生 成DEGtBE，而沒有二乙二醇生成，足以顯示DEGDtBE 在此條件下只斷裂1分子C4。 綜上所述，本發明係一種以異丁烯及二乙二醇合成 • 二乙二醇第三丁基醚之方法，可有效改善習用之種種缺 點，利用異丁烯與二乙二醇，在固態酸觸媒作用下，於 適當反應條件中，經兩階段減壓蒸餾，即可有效合成產 . 物得到高選擇性及高純度之二乙二醇第三丁基醚，而反 應副產物中之二乙二醇雙第三丁基醚則可回收再反: 應，可於提高異丁烯溶解量之同時，亦可與二乙二醇進 行轉醚化反應，並有效抑制該項副產物之生成，進而使 本發明之産生能更進步、更實用、更符合使用者之所 16 2011/10/27 .須，確已符合發明專利申請之要件，爰依法提出專利申 請。 惟以上所述者，僅為本發明之較佳實施例而已，當 不能以此限定本發明實施之範圍；故，凡依本發明申請 專利範圍.及發明說明書内容所作之簡單的等效變化與 修飾，皆應仍屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 第1圖，係本發明之製作流程示意圖。 第2 A圖，係本發明一較佳實施例之反應溫度對反應 活性與選擇性影響示意圖。 第2 B圖，係本發明一較佳實施例之觸媒酸量對反應 活性與選擇性影響示意圖。 第2 C圖，係本發明一較佳實施例之反應物DEG/IB= 比值對反應活性與選擇性影響示意圖。 第3 A圖，係本發明另一較佳實施例之反應溫度對反 應活性與選擇性影響示意圖。 第3 B圖，係本發明另一較佳實施例之反應物 DEG/IB:比值對反應活性與選擇性影響示意 圖。 第3 C圖，係本發明另一較佳實施例之WHSV對反 應活性與選擇性影響示意圖。 第4圖，係本發明產物之分離與純化示意圖。 第5圖，係本發明反應溫度對DEGDtBE轉醚化反應 活性影響示意圖。 17 第7圖， 第6圓’係本發明反應溫度對DEGDtBE裂解— iSl? 性影響示意圖。 ^習知利用環氧化合物與醇類合成_之示 第8圖圖係f知利用二醇類與異丁歸合成_之示意 醇類與醇類化合物脱水合成醇 第9圖，係習知利用 _之示意圖。 【主要元件符號說明】 1 1〜1 3步驟According to the parameters set in Figure 3A above, the amount of reactant DEG/IB= is unchanged, and the above WHSV is changed to 0.6 to 2.4, and the reaction is carried out at 55 ° C, respectively. The result is shown in Figure 3 C. WHSV 14 1358403 2011/10/27 When increasing, it can improve the conversion of isobutylene and the selectivity of DEGtBE. Among them, the performance of WHSV to isobutene conversion and product selectivity is -1.2~2.0 ΙΓ1 is the preferred reaction condition. Please refer to Fig. 4 for the separation and purification of the product of the present invention. As shown in the figure: the present invention uses vacuum distillation, in the first stage of low vacuum distillation, an appropriate amount of water can be added to the distillate during azeotropy, and DEGDtBE is taken out under reduced pressure with water, and the residual distillate is The DEGDtBE is gradually reduced, and the distilled liquid can be separated into two layers from φ, the upper layer is DEBDtBE, the lower layer is water, and the lower layer of water is returned to the bottom distillate, so that the steam can be recycled to effectively separate by-products. DEGDtBE. The DEGtBE and diethylene glycol contained in the residual distillate can be used to separate the DEGtBE product from the diethylene glycol reactant by the second stage high vacuum distillation. Please refer to Fig. 5, which is a schematic diagram showing the effect of the reaction temperature of the present invention on the activity of DEGDtBE to etherification reaction. As shown in the figure: In order to further confirm the progress of the etherification reaction, the isobutylene component is not added to the diethylene glycol feed, and 10 wt% DEGDtBE is added, and the reaction is carried out according to the reaction conditions of the above FIG. 2A, and the reaction is changed. The conversion rate of DEGDtBE and the molar amount of DEGtBE per mole of DEGDtBE were calculated. After 6 hours of reaction, the results showed that the higher the reaction temperature, the higher the conversion of DEGDtBE. The amount of DEGtBE produced also increases. During the reaction, DEGDtBE can be depolymerized with diethylene glycol to form 2 molecules of DEGtBE, and it may also be broken into 1 molecule of DEGtBE and 1 molecule at a higher temperature. 15 1358403 2011/10/27 C4, or It is broken into 1 molecule of diethylene glycol and 2 molecules of C4. If DEGDtBE is added to the system containing diethylene glycol and C4 reactants (meaning that the by-product-DEGDtBE is separated into the reaction tank after the first stage separation), the cracking reaction can be reduced at this time, so that the main reaction can be carried out. When the etherification reaction is the same, the formation of DEGDtBE can also be inhibited. Please refer to Figure 6 for the effect of the reaction temperature of the present invention on the activity of DEGDtBE cracking reaction. As shown in the figure: In order to further distinguish the etherification reaction from the cleavage reaction, the present invention is subjected to another actual test. The toluene reaction of DEGDtBE was tested with 10 wt% of DEGDtBE as feed. The reaction was carried out according to the reaction conditions of Figure 2A above, and the reaction temperature was changed. After 6 hours of reaction, the results of the experiment showed that DEGDtBE was converted. The rate increases with the increase of the reaction temperature, and almost no cracking reaction occurs below 50 °C. Only DEGtBE is formed below 90 °C, and no diethylene glycol is formed, which is sufficient to show that DEGDtBE only breaks one molecule of C4 under this condition. In summary, the present invention is a method for synthesizing diethylene glycol tert-butyl ether by isobutylene and diethylene glycol, which can effectively improve various disadvantages of the conventional use, using isobutylene and diethylene glycol, in solid acid contact Under the action of the medium, under the appropriate reaction conditions, the two-stage vacuum distillation can effectively synthesize the product to obtain the highly selective and high-purity diethylene glycol tert-butyl ether, and the reaction by-product The diol di-tertiary butyl ether can be recovered and reversed: It can increase the amount of isobutylene dissolved, and can also carry out transesterification reaction with diethylene glycol, and effectively inhibit the formation of the by-product, thereby The invention can produce more advanced, more practical and more suitable users. 2011 2011.27. It must have met the requirements of the invention patent application, and filed a patent application according to law. However, the above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto; therefore, the simple equivalent changes made by the scope of the invention and the contents of the invention are Modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the production process of the present invention. Figure 2A is a schematic illustration of the effect of reaction temperature on reactivity and selectivity in a preferred embodiment of the invention. Fig. 2B is a schematic view showing the effect of the amount of catalyzed acid on the reactivity and selectivity of a preferred embodiment of the present invention. Figure 2C is a graphical representation of the effect of reactant DEG/IB= ratio on reactivity and selectivity in a preferred embodiment of the invention. Fig. 3A is a schematic view showing the effect of reaction temperature on reaction activity and selectivity in another preferred embodiment of the present invention. Figure 3B is a schematic representation of the effect of the ratio DEG/IB on the reactivity and selectivity of another preferred embodiment of the invention. Fig. 3C is a schematic view showing the effect of WHSV on the reaction activity and selectivity in another preferred embodiment of the present invention. Figure 4 is a schematic diagram showing the separation and purification of the product of the present invention. Fig. 5 is a schematic view showing the effect of the reaction temperature of the present invention on the activity of DEGDtBE to etherification reaction. 17 Fig. 7, the sixth circle is a schematic diagram of the effect of the reaction temperature of the present invention on the DEGDtBE cracking-iSl? property. ^Synthesis of the use of epoxy compounds and alcohol synthesis _ Figure 8 is a diagram of the use of glycols and isobutyl amide synthesis _ Illustrated alcohols and alcohols dehydration to synthesize alcohol Figure 9, is a customary use Schematic diagram of _. [Main component symbol description] 1 1~1 3 steps