201204464 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種酯化及聚酯化反應之催化劑改良，更詳而言之， 指一種用於酯化及聚酯化反應中作為觸媒之錯合物，及使用此錯合物 於酯化及聚酯化反應中作為觸媒之方法及產物。 【先前技術】 酯化反應一般為可逆反應’傳統上實驗室及工業界採行之酯化反應 φ 為用酸與醇於過量強酸，如無水鹽酸（HC1)、硫酸（H2S04)催化下進 行加熱迴流反應，前述反應為一平衡反應，為使平衡向產物方向進行， 必須使用過量之無水鹽酸或濃硫酸作為催化劑及除水劑，然而強酸之 毒性及危險性較高，並強酸脫出之水分若與過量之強酸再接觸可能因 大量放熱而產生起火爆炸之情形，在使用安全性上為一大顧慮；另， 必須添加過量強酸始可讓酯化反應向產物方向進行，使得成本大為提 升，並有環境污染等問題；且因強酸會導致許多有機化合物之官能基 • 分解，使得上述方法僅能使用於簡單院基酸之醋化反應，無法應用在 許多工業特用分子、官能化高分子與精密化學分子之醋化反應；此外， 催化劑之選擇會影_化產物的顏色，於製備綠(例如，聚對苯二甲 酸乙二醋)之有效觸媒，在s旨化產物上會產生令人難以接受的黃化現 象，耗費時間及成本將產物漂㈣為製程上之浪費與不便。 此後發展出較成功之催化系統，區分為（一）路易士酸型，如有機 錫化合物’以及如錄，鈦，鐘等化合物，録，欽，链等化合物作為催 化劑雖為商業上之產品，然而因其具高度空氣敏感性導致使用於催 201204464 化酯化反應時，需配合嚴格之無水溶劑，且上述化合物皆具稀有金屬， 使成本提高並降低操作實用性，另一方面，有機錫化合物之毒性極高， 具強烈致癌性，反應完成後易殘留於酯化產物上且分離不易，可能對 人體致生危害，造成產物性質不佳，且以有機錫化合物作為催化劑需 於高溫（120。〇150。(：）下進行反應，亦增加成本上之消耗。（二）路易 士鹼類型，如醇基鈉、醇基鋁等烷氧金屬錯合物作為催化劑，雖然其 價格較低且具高度空氣穩定性，然而因烷氧金屬錯合物之強驗性，使 其無法運用在含有驗敏感性之工業用分子、官能化高分子上，因此降響 低其可應用性。 再者’傳統酯化反應為使用苯或甲苯作為反應溶劑，然甲苯毒性極 強，暴露於其中將會對人體產生傷害，亦會對環境造成污染壓力，且 傳統酯化反應之催化劑也難以回收再利用，上述種種之缺點都顯示傳 統酯化反應過程有需改進之處。 【發明内容】 傳統酯化反應所使用之強酸催化劑可能有造成產品泛黃、操作上具鲁 危險性與不環保等缺點，後改良之催化劑則具毒性、易殘留與成本過 高之缺點’因此需提供一種新的催化劑用以解決傳統之問題。 本發明提供一種酯化及聚酯化反應之觸媒，該觸媒係由乙醯丙酮鐵 錯合物所組成，該乙醯丙酮鐵錯合物具有通式：Fe (RC〇CH2C〇R) 3， 其中’ R為曱基或其他取代基。 本發明又提供一種酯化及聚酯化反應之方法，包括使用如前述之乙 醯丙酮鐵錯合物作為酯化及聚酯化反應之觸媒之方法，其方法為將待 4 201204464 反應之甲基或乙基酯類與醇類於一反應溶劑中混合，並將觸媒加入後 加熱至一反應溫度，使酯類與醇類經觸媒催化進行酯化反應，進而得 一酯化物’其特徵在於：該觸媒為一乙醯丙酮鐵錯合物，具有通式： Fe (RCOCHfOR) 3 ’其中R為甲基或其取代基，因此，乙醯丙酮鐵 錯合物之曱基被三氟曱基所取代’使觸媒成為三氟甲基乙醯丙酮鐵錯 合物；其曱基被苯基所取代，使觸媒成為雙苯醯基曱基乙醯丙酮鐵錯 合物；其甲基被正丁基所取代，使觸媒成為2,2,6,6-四甲基-3,5-雙酮庚 烷乙醯丙酮鐵錯合物。 以及一種酯化物，其特徵係藉由前述之乙醯丙酮鐵錯合物作為觸媒 使用於酯化及聚酯化反應所得之反應產物。 本發明之主要目的在於利用乙醯丙酮鐵錯合物作為酯化及聚酯化 反應之催化劑，乙醯丙酮鐵錯合物為一正三價鐵離子（Fe3+)與三乙醯 丙酮基（acetyl acetone)結合而成，因乙酿丙酮基具高度配位性，因此 穩定正三價鐵離子，使乙醯丙酮鐵錯合物具有活性高，易與反應物反 應之特性，並與空氣、水接觸均保有高度穩定性，室溫下不易被氧化， 不易變質’且乙酿丙酮鐵錯合物不具毒性，因此無需顧慮後續產品是 否殘留有毒物質，不具毒性之特點亦不會對環境造成負擔。 本發明之次要目的在於使用乙醯丙酮鐵錯合物作為酯化及聚酯化 反應之催化劑，藉此’不會使酯化及聚酯化反應下的產物產生泛黃之 現象，如此將可使產品具美觀性且節省後續需t漂白的成本與時間。 本發明之另一次要目的在於乙醯丙酮鐵錯合物與酯化產物係可離 析，藉由一矽膠吸附乙醯丙酮鐵錯合物，再將酯化產物以過濾方式與 201204464 吸附於矽膠之乙酿丙酮鐵錯合物分離，使乙醯丙酮鐵錯合物不會殘留 在酯化產物内，回收的乙酿丙酮鐵錯合物則可用1%乙醯丙酮基之乙醇 沖洗後再利用，使乙酿丙酮鐵錯合物得以回收再利用，對工業上使用 而言相當有利並可節省成本的。 本發明又一次要目的在於與目前所使用的觸媒相比時，本發明之觸 媒（乙醯丙酮鐵錯合物）能夠在反應溫度低於傳統的環境下（約8〇〇c 至100°c )進行酯化及聚酯化反應，能夠減少反應時所需要的能源。 本發明之再一次要目的在於反應過程中所使用之反應溶劑為烷類 溶劑，如較不具毒性之正庚烷’相較於傳統酯化反應所使用毒性較強 的苯、甲笨溶劑’本發明之反應溶劑將更為環保。 【實施方式】 為便於說明本發明於上述發明内容一欄中所表示的中心思想，茲以 具想實施例表達。實施例中各種不同物件係按適於說明之比例、尺寸、 變形量或位移量而描繪’而非按實際元件的比例予以繪製，合先敘明。 且以下的說明中，類似的元件是以相同的編號來表示。 請參閱第一圖至第二圖’本發明係提供一種酯化及聚酯化反應之觸 媒，該觸媒係由乙醯丙酮鐵錯合物所組成，將待反應之酯類與醇類加 入一反應溶劑，該反應溶劑為正庚烧，後添加一乙醯丙酮鐵錯合物作 為觸媒，該乙醯丙酮鐵錯合物具有通式：Fe (RC〇CH2C〇R) 3，其中， R為甲基或其他取代基。 以及一種酯化及聚酯化反應之方法，包括使用如前述之觸媒，其方 法為將待反應之酯類與醇類於一反應溶劑中混合，並將觸媒加入後加 201204464 熱至一反應溫度，該反應溫度約80°c至約100°c，使酯類與醇類經觸 媒催化進行反應，進而得一醋化物，且該反應溶劑中更可加入為邱莫 耳濃度之金屬碳酸鹽溶液（如碳酸鈉溶液）以增加反應速度，並於反 應後更可藉由一矽膠吸附該觸媒，使觸媒得以回收再利用，其特徵在 於： 該觸媒為一乙酿丙酮鐵錯合物，該乙醯丙酮鐵錯合物具通式：Fe (RCOCHKOR) 3，其中R為甲基或其取代基。 該酯化及聚酯化反應包括使官能化甲基或乙基酯類與官能化醇類 藉由該觸媒進行反應，以製備一酯化物，因此本發明更提供一種酯化 物，其特徵為係藉由前述之乙醯丙酮鐵錯合物作為觸媒使用於酯化及 聚酯化反應所得之反應產物。 明暸上述結構後，以下係針對本發明之動作及原理作一詳細說明： 請參閱第二圖，本發明利用正三價鐵乙醯丙酮基鐵金屬錯合物作為 酯化及聚酯化反應之觸媒，僅需5%莫耳量作為觸媒，即可催化各種不 同類型包括酸敏感性酯類、驗敏感性酯類、烷基酯類、芳香族之醋類、 含醚類之酯類、含酸基之酯類、含長鏈順式雙鍵之脂肪酸酯等酯基交 換反應，其反應條件為以5%莫耳比例之乙酿丙嗣鐵錯合物作為觸媒， 將參與反應之官能化甲基或乙基酯類與官能化曱基或乙基醇類於反應 瓶中混合，以無毒性之正庚烷作為溶劑，並可加入5%莫耳比例之金屬 碳酸鹽如碳酸納（NaKO3)、碳酸卸（K2C〇3)或碳酸絶（cS2c〇3)以 增加酯化及聚酯化反應之速度，後加熱至一反應溫度作為溶劑迴流溫 度，該反應溫度約80°C至約100°C，反應過程中並施予一除水手段除 201204464 去反應產生之多於水份，又反應過程中所產生甲醇或乙醇等副產物’ 則以索氏萃取法之分子篩作為醇類吸附劑，用以吸附甲醇或 乙醇等副產物使其不會殘留於後續之酯化物上，藉此得到一酯化物’ 而觸媒則可以矽膠吸附後回收，回收的觸媒則可用1%乙醯丙酮基之乙 醇沖洗後再利用。 請參閱第三圖至第五圖，以乙醯丙酮鐵錯合物作為觸媒，其通式 為：Fe (RCOCH2COR) 3，其中R為甲基或其取代基，前述實施態樣 中R係為甲基，然而酯化及聚酯化反應中之觸媒可為乙醯丙酮鐵錯合馨 物或其類似物之其中之一。因此在不同實施態樣中，乙醯丙酮鐵錯合 物之甲基可被三氟曱基所取代’使觸媒成為三氟甲基乙醯丙酮鐵錯合 物；其甲基亦可被苯基所取代，使觸媒成為雙苯醯基甲基乙醯丙酮鐵 錯合物；其甲基更可被正丁基所取代，使觸媒成為2,2,6,6-四曱基-3,5-雙酮庚烷乙醯丙酮鐵錯合物。 雖本發明是以一個最佳實施例作說明，但精於此技藝者能在不脫離 本發明精神與範疇下作各種不同形式的改變。以上所舉實施例僅用以鲁 說明本發_已，非用鎌制本發明之範圍^舉凡对本發明精神所 從事的種種修改或變化，俱屬本發明申請專利範圍。 8 201204464 【圖式簡單說明】 第一圖係本發明之觸媒化學結構示意圖。 第二圖係本發明之觸媒使用於酯化及聚酯化反應之流程示意圖。 第三圖係本發明之觸媒具不同取代基之化學結構示意圖（一）。 第四圖係本發明之觸媒具不同取代基之化學結構示意圖（二）。 第五圖係本發明之觸媒具不同取代基之化學結構示意圖（三）。 【主要元件符號說明】201204464 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst modification for esterification and polyesterification reactions, and more particularly to a catalyst for esterification and polyesterification reactions. The complex and the method and product used as a catalyst in the esterification and polyesterification reaction using the complex. [Prior Art] The esterification reaction is generally a reversible reaction. Traditionally, the esterification reaction in the laboratory and industry has been carried out by heating with an acid and an alcohol in excess of a strong acid such as anhydrous hydrochloric acid (HC1) or sulfuric acid (H2S04). In the reflux reaction, the above reaction is an equilibrium reaction. In order to carry out the equilibrium in the direction of the product, an excess of anhydrous hydrochloric acid or concentrated sulfuric acid must be used as a catalyst and a water removing agent. However, the toxicity and risk of the strong acid are high, and the moisture of the strong acid is removed. If re-contact with an excessive amount of strong acid may cause a fire and explosion due to a large amount of exothermic heat, it is a big concern in terms of safety in use; in addition, excessive acid must be added to allow the esterification reaction to proceed toward the product, which greatly increases the cost. And there are problems such as environmental pollution; and because of the strong acid, the functional groups of many organic compounds are decomposed, so that the above method can only be used for the vinegarization reaction of simple fenyl acids, and cannot be applied to many industrial special molecules, and has high functionalization. The acetalization of molecules with precision chemical molecules; in addition, the choice of catalyst will affect the color of the product, in the preparation of green (eg Poly effective catalyst terephthalic acid ethylene vinegar), the aimed product in s will produce unacceptable yellowing phenomenon, time-consuming and cost of the product (iv) rinsing the waste and inconvenient process. Since then, a more successful catalytic system has been developed, which is divided into (1) Lewis acid type, such as organotin compounds, and compounds such as ruthenium, titanium, bell, etc., as a catalyst, although it is a commercial product, However, due to its high air sensitivity, it is used in the esterification reaction of 201204464. It needs to be combined with a strict anhydrous solvent, and all of the above compounds have rare metals, which increases the cost and reduces the practicality of operation. On the other hand, the organotin compound It is extremely toxic and has strong carcinogenicity. It is easy to remain on the esterified product after the reaction is completed and is difficult to separate. It may cause harm to the human body, resulting in poor product properties, and the organotin compound is required as a catalyst at high temperature (120. 〇150. The reaction is carried out under (:), which also increases the cost. (2) The Lewis base type, such as an alkoxy metal complex such as an alcohol-based sodium or an alcohol-based aluminum, is used as a catalyst, although its price is low and High air stability, however, due to the strong nature of the alkoxy metal complex, it can not be used in industrial molecules with high sensitivity, functionalized high scores On the other hand, the low-reducing effect is low. In addition, the traditional esterification reaction uses benzene or toluene as the reaction solvent, but toluene is extremely toxic. Exposure to it will cause harm to the human body and also cause environmental pollution. Moreover, the catalyst of the conventional esterification reaction is also difficult to recycle and reuse, and all of the above disadvantages indicate that there is a need for improvement in the conventional esterification reaction process. SUMMARY OF THE INVENTION The strong acid catalyst used in the conventional esterification reaction may cause yellowing of the product. The operation has the disadvantages of being dangerous and not environmentally friendly, and the modified catalyst is toxic, easy to residue and costly. Therefore, it is necessary to provide a new catalyst to solve the conventional problem. The present invention provides an esterification. And a catalyst for the polyesterification reaction, the catalyst is composed of an iron acetal iron complex which has the general formula: Fe (RC〇CH2C〇R) 3, wherein 'R is Mercapto or other substituents. The invention further provides a method for esterification and polyesterification comprising the use of an ethylene acetonate iron complex as described above for esterification and polyesterification. The method of the medium is to mix the methyl or ethyl ester reacted with the alcohol to be reacted with the alcohol in a reaction solvent, and then add the catalyst to the reaction temperature to make the ester and the alcohol touch. The catalyst is subjected to an esterification reaction to obtain an esterified product, which is characterized in that the catalyst is an acetoacetate iron complex having the formula: Fe (RCOCHfOR) 3 ' wherein R is a methyl group or a substituent thereof, Therefore, the thiol group of the acetamidine iron complex is replaced by a trifluoromethyl group, which makes the catalyst a trifluoromethylacetamidine iron complex; its thiol group is replaced by a phenyl group, making the catalyst double Phenylhydrazinylacetoxime iron complex; its methyl group is substituted by n-butyl group to make the catalyst 2,2,6,6-tetramethyl-3,5-dione heptaneacetone acetone And an esterified product characterized by the use of the aforementioned ethyl acetonate iron complex as a catalyst for the reaction product obtained by esterification and polyesterification. The main object of the present invention is to use acetamidine iron complex as a catalyst for esterification and polyesterification reaction, and the acetonitrile iron complex is a positive ferric ion (Fe3+) and triacetyl acetonide (acetyl acetone). The combination of the acetone base has a high degree of coordination, so the stable trivalent iron ions are stabilized, so that the acetamyl iron complex is highly active, easily reacts with the reactants, and is in contact with air and water. It has high stability, is not easy to be oxidized at room temperature, and is not easy to be deteriorated'. The ethyl acetonide complex is not toxic, so there is no need to worry about whether the toxic substances remain in the subsequent products, and it is not toxic and does not burden the environment. A secondary object of the present invention is to use an acetamidine iron complex as a catalyst for esterification and polyesterification reaction, thereby 'not causing yellowing of the product under esterification and polyesterification, so It can make the product beautiful and save the cost and time of subsequent bleaching. Another secondary object of the present invention is that the acetamidine iron complex and the esterified product can be isolated, and the acetamidine iron complex is adsorbed by a bismuth gel, and the esterified product is adsorbed to the sulphur by filtration with 201204464. The separation of the acetone-iron complex is not allowed to remain in the esterification product, and the recovered ethylene-silk iron complex can be washed with 1% acetoacetone-based ethanol and then used. The recycling of the ethyl acetonide complex is economically advantageous and cost effective. The present invention is again intended to have a catalyst (acetamidine iron complex) capable of reacting at a lower temperature than conventional environments (about 8 〇〇 c to 100) when compared with the catalyst currently used. °c) The esterification and polyesterification reactions can reduce the energy required for the reaction. A further object of the present invention is that the reaction solvent used in the reaction process is an alkane solvent, such as a less toxic n-heptane, which is more toxic than a conventional esterification reaction. The reaction solvent of the invention will be more environmentally friendly. [Embodiment] For the convenience of description, the central idea expressed by the present invention in the column of the above-mentioned invention is expressed in the preferred embodiment. Various items in the embodiments are depicted in terms of ratios, dimensions, amounts of deformation or displacements that are suitable for the description, and are not drawn to the proportions of the actual elements, as set forth in the foregoing. In the following description, like elements are denoted by the same reference numerals. Please refer to the first to second figures. The present invention provides a catalyst for esterification and polyesterification, which is composed of an iron acetal iron complex, and the esters and alcohols to be reacted. A reaction solvent is added, the reaction solvent is n-gum, and then an acetamidine iron complex is added as a catalyst, and the acetonitrile iron complex has the formula: Fe (RC〇CH2C〇R) 3, wherein , R is a methyl group or other substituent. And a method for esterification and polyesterification reaction, comprising using a catalyst as described above by mixing the ester to be reacted with an alcohol in a reaction solvent, adding the catalyst, adding 201204464 heat to a The reaction temperature, the reaction temperature is about 80 ° C to about 100 ° C, the ester and the alcohol are reacted by a catalyst to obtain an acetate, and the reaction solvent can be added to a metal having a concentration of Qiu Moer. A carbonate solution (such as a sodium carbonate solution) is used to increase the reaction rate, and after the reaction, the catalyst is adsorbed by a ruthenium gel, and the catalyst is recovered and reused, wherein the catalyst is a acetylacetonate. The complex, the acetamidine iron complex is of the formula: Fe (RCOCHKOR) 3, wherein R is a methyl group or a substituent thereof. The esterification and polyesterification reaction comprises reacting a functionalized methyl or ethyl ester with a functionalized alcohol by the catalyst to prepare an esterified product. Therefore, the present invention further provides an esterified product characterized by The reaction product obtained by the esterification and polyesterification reaction by using the aforementioned acetamidine iron complex as a catalyst. After the above structure is clarified, the following is a detailed description of the operation and principle of the present invention: Referring to the second figure, the present invention utilizes a trivalent iron acetonitrile acetonyl iron metal complex as a touch of esterification and polyesterification reaction. The medium requires only 5% of the molar amount as a catalyst to catalyze various types including acid-sensitive esters, sensitive esters, alkyl esters, aromatic vinegars, ethers containing ethers, An ester group exchange reaction of an acid group-containing ester or a fatty acid ester having a long-chain cis double bond, and the reaction condition is that a 5% molar ratio of the styrene-iron-iron complex as a catalyst will participate in the reaction. The functionalized methyl or ethyl ester is mixed with the functionalized thiol or ethyl alcohol in a reaction flask, using non-toxic n-heptane as a solvent, and a metal carbonate such as carbonic acid in a 5% molar ratio can be added. Nano (NaKO3), carbonic acid unloading (K2C〇3) or carbonic acid (cS2c〇3) to increase the rate of esterification and polyesterification reaction, and then heated to a reaction temperature as the solvent reflux temperature, the reaction temperature is about 80 ° C Up to about 100 ° C, during the reaction and a water removal method in addition to 201204464 to react More than water, and by-products such as methanol or ethanol produced during the reaction process, the molecular sieve of Soxhlet extraction is used as an alcohol adsorbent to adsorb by-products such as methanol or ethanol so that it does not remain in the subsequent On the esterified product, an esterified product is obtained, and the catalyst can be recovered by adsorption of the ruthenium, and the recovered catalyst can be washed with 1% acetonacetone-based ethanol and then used. Referring to the third to fifth figures, the acetonitrile iron complex is used as a catalyst, and the general formula is: Fe (RCOCH2COR) 3, wherein R is a methyl group or a substituent thereof, and the R system in the foregoing embodiment. It is a methyl group, however, the catalyst in the esterification and polyesterification reaction may be one of acetamiprilon iron mis-synthesis or the like. Therefore, in different embodiments, the methyl group of the acetamidine iron complex can be substituted by a trifluoromethyl group to make the catalyst a trifluoromethylacetamidine iron complex; the methyl group can also be benzene. Substituting the base to make the catalyst a bisphenylhydrazinylmethylacetone iron complex; its methyl group can be replaced by n-butyl group, so that the catalyst becomes 2,2,6,6-tetradecyl- 3,5-diketoheptane acetamidine iron complex. While the invention has been described in terms of a preferred embodiment, the embodiments of the invention may The above-mentioned embodiments are only used to clarify the scope of the present invention, and all modifications and variations made to the spirit of the present invention are within the scope of the present invention. 8 201204464 [Simplified description of the drawings] The first figure is a schematic diagram of the chemical structure of the catalyst of the present invention. The second figure is a schematic flow diagram of the catalyst used in the esterification and polyesterification reaction of the present invention. The third figure is a schematic diagram of the chemical structure of the different substituents of the catalyst of the present invention (I). The fourth figure is a schematic diagram of the chemical structure of the different substituents of the catalyst of the present invention (2). The fifth figure is a schematic diagram of the chemical structure of the different substituents of the catalyst of the present invention (III). [Main component symbol description]