200938570 九、發明說明： 【發明所屬之技術領域】 本發明有關一種自回收之聚酯廢料製備對苯二曱酸二萨 之方法，尤其有關一種自回收之聚酯廢料，以草酸鹽 ^ 媒，經醇解、酯交換反應等而製備高純度對笨二曱酸二二: 劑之方法。 【先前技術】 聚對苯二曱酸乙二酯(PET)之聚酯樹脂，由於擁有良好 塑化性與吹塑性而廣泛應用於飲料容器、包裝膜以及紡纖工 〇 f。然而經由加工之飲料容器、薄膜以及纖維使用後產生之大 量廢料，或是加工時產生副料皆會對地球環境帶來嚴重之衝 擊。所以以往有各種不同之回收方法如，副料的回收、物理的 回收以及化學的回收方法。 聚酯廢料的回收經由物理法可再生使用，如粉碎或押出造 粒或抽絲紡纖來做為加工品之掺混料；但經此路徑所回收再生 之產品對產業利用之附加價值並不高。雖然近年來對於聚酯廢 料化^回收技術之研究相當多，但多數應用在聚酯廢料與二元 醇經高溫醇解反應後，二次入料共聚合反應所得到之^酯樹 Q 脂二如圯2002-60474人中提到，PET廢料在鈦觸媒存在下，添 加二元醇進行醇解反應後’與順丁烯二酸酐共聚得到不飽和聚 酯樹脂。但該專利文獻中未提及PET中乙二醇保⑺之分離技 術，以致於所獲得之聚酯樹脂成份中因含有過量之EG而使得 實際應用上受到限制。JP2001-316327A則提到以PET廢料與 二元醇，在含鈦、錫或辞之化合物作為分解反應觸媒存在下， 經醇解反應獲得酯寡聚物。此反應中為了要將過剩之二元醇萃 =出，所以必須使用劇毒之三氯甲烷；且依該方法所製造之酯 寡聚物進而與二異氰酸酯反應所製得之聚胺基甲酸酯因材質 偏硬而在使用上受到限制。 上述聚酯廢料的回收技術皆涉及醇解反應後，系統中乙二 200938570 ΐ;、其共聚合反應所得到之共聚酯樹脂。文中皆未涉 法，以致於再生品在物性上仍然存有聚酯廢 ^之性質。故上述ΡΕΤ廢料再處理後之產業職上未令人滿 意。 據此’另提出將聚醋廢料經由醇解隨後添加脂肪族單元醇 與之反應再生而形絲苯m方法，該對苯二甲酸二 酯為具有赠價值之增_。但若由PET廢料於再生辦 ❹ Ο ΐΐϊ用方面產業時，麻臨系統中之乙二醇須從系^ 中移除’才祕到純度佳且能提供產業利用之增塑讎品。對 苯二曱酸二異辛g旨(DOTP)是—種用途廣泛之無毒增塑劑，由 =其電阻性歧好所以大量顧在㈣之電線與賴排線。此 ^由於DOTP之耐麟錄、加讀紐異，也#遍應用於 、vc押延加工之薄膜產品。經由聚酯廢料透過特殊製程所製 造之DOTP不失為低成本經濟價值高之方法。 故而CN113M79A公開-種由聚醋廢料與—元醇製備對 苯二甲酸二|旨增麵的方法。上料料在賴存在下，以一段 醇解、醋交換反應法，於反應系中連續不斷地定速加入乙二醇 捕捉劑，使乙二醇從反應系中很快分離開來。但實際上操作 時，由於PET的熔點相當高，若以沸點較低之一元醇在常壓 與PET進行酯交換反應，則反應時間冗長且效率差。此外， 反應中缺乏一種快速監測反應終點之方法而致使其粗製酯產 品酸價與色相偏高，乃致製程最後須進行中和、水洗、脫醇、 脫水、壓濾等繁瑣程序，效率差且產生大量廢水。 、再者’ CN1073164A公開一種以PET廢料製備D〇Tp的 方法與設備，PET與2-乙基己醇之醇解反應產生可與2_乙基 己醇相溶的乙二醇，經相移轉分離器將乙二醇分離出來。由於 乙二醇沸點(197。〇與2-乙基己醇沸點(185。〇差距不大，經實 際操作結果是乙二醇回收率不高，D0Tp之轉化率偏低；且反 應過程需使用鹼液中和、水洗、脫水，製程繁瑣而效率偏低。 200938570 JP2000_256274A Μ 公開一種以聚 ^ 塑劑之方法。PET廢料與過量的單元醇 予ί分離，上層液2·乙基己醇則持^回 ;;合液，藉由簡!之蒸鮮裝置並 致於少里之乙二醇隨上層液2_乙基己醇：流進入反 ϋ 應，導致反鱗間過長，對苯二甲酸二醋轉化率 Ο Ο usem28說明使用聚g旨廢料分 一 樹脂與單== k油水分離器巾贱置人水與單元 ^高成份之二_製品，但魏大油水分離 序;此專利文獻中未涉及製品之色相，所以商業i 【發明内容】 本發明有關一種回收聚酯原料再生膺用方法 舰與二元醇經二 ^脂更好，本發明中之聚醋原料為聚對苯二甲酸乙二醋师丁）200938570 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for preparing terephthalic acid disodium from self-recycling polyester waste, in particular to a self-recycling polyester waste, which is an oxalate medium A method of preparing a high-purity p-phthalic acid di-ordinary agent by alcoholysis, transesterification or the like. [Prior Art] A polyester resin of polyethylene terephthalate (PET) is widely used in beverage containers, packaging films, and spun fibers because of its good plasticity and blow plasticity. However, the processing of beverage containers, films, and the large amount of waste generated after the use of fibers, or the generation of by-products during processing, can have a serious impact on the global environment. Therefore, there have been various recovery methods such as recycling of secondary materials, physical recovery, and chemical recovery methods. The recycling of polyester waste can be regenerated by physical means, such as crushing or extruding granulation or spinning and spinning as a blend of processed products; however, the added value of the products recovered through this route is not used for industrial use. high. Although there have been quite a lot of researches on polyester waste recycling technology in recent years, most of them are used in the secondary feed copolymerization reaction of polyester waste and glycol after high temperature alcoholysis reaction. As mentioned in 2002-60474, PET waste is copolymerized with maleic anhydride to obtain an unsaturated polyester resin in the presence of a titanium catalyst by adding a glycol to carry out an alcoholysis reaction. However, the separation technique of the ethylene glycol (7) in PET is not mentioned in the patent document, so that the obtained polyester resin component is limited in practical use due to an excessive amount of EG. JP2001-316327A mentions the use of PET waste and glycol to obtain an ester oligomer by alcoholysis in the presence of a compound containing titanium, tin or a compound as a decomposition reaction catalyst. In this reaction, in order to extract excess diol, it is necessary to use highly toxic chloroform; and the urethane which is produced by the method and further reacted with diisocyanate to obtain a polyurethane Due to the hard material, it is limited in use. The above-mentioned polyester waste recycling technology involves a copolyester resin obtained by copolymerization reaction in the system after the alcoholysis reaction. There is no reference in the text, so that the recycled product still has the property of polyester waste. Therefore, the above-mentioned industrial wastes after reprocessing of the waste materials are not satisfactory. According to this, it is proposed to regenerate the polyester vinegar waste by alcoholysis followed by the addition of an aliphatic unit alcohol to form a benzene m method, and the terephthalic acid diester has an added value of _. However, if the PET waste is used in the recycling industry, the ethylene glycol in the Ma Lin system must be removed from the system to be a plasticized product with good purity and industrial utilization. The diisooctyl phthalate (DOTP) is a non-toxic plasticizer with a wide range of uses, and it has a large number of wires (resistances). This is due to the DOTP's resistance to Lin Lu, plus reading New Zealand, and also # applied to, vc entangled processing of film products. DOTP produced through special processes through polyester waste is a low-cost, economically valuable method. Therefore, CN113M79A discloses a method for preparing a terephthalic acid from a polyester waste and a monohydric alcohol. In the presence of the upper material, a glycolysis and vinegar exchange reaction method is used, and a glycol trapping agent is continuously added at a constant rate in the reaction system to rapidly separate the ethylene glycol from the reaction system. However, in practice, since the melting point of PET is relatively high, if a lower boiling point monohydric alcohol is transesterified with PET at normal pressure, the reaction time is long and inefficient. In addition, there is a lack of a method for rapidly monitoring the end point of the reaction, so that the acid value and the hue of the crude ester product are too high, so that the process must be subjected to cumbersome procedures such as neutralization, water washing, dealcoholization, dehydration, pressure filtration, etc., and the efficiency is poor. A large amount of wastewater is produced. Further, 'CN1073164A discloses a method and a device for preparing D〇Tp from PET waste. The alcoholysis reaction of PET with 2-ethylhexanol produces ethylene glycol which is compatible with 2-ethylhexanol, and undergoes phase shift. The separator separates the glycol. Due to the boiling point of ethylene glycol (197. 〇 and 2-ethylhexanol boiling point (185. 〇 不 不 , , , , , , , , , , , , , , , , , , , , , , , , , 乙二醇 乙二醇 乙二醇 乙二醇 乙二醇 乙二醇 乙二醇Neutralization, washing and dehydration of lye, the process is cumbersome and the efficiency is low. 200938570 JP2000_256274A Μ A method of using a plasticizer is disclosed. The PET waste is separated from the excess unit alcohol, and the upper liquid 2·ethylhexanol is held. ^回;; The liquid mixture, by the simple! The steaming device and the ethylene glycol of the Shaoli with the upper liquid 2_ethylhexanol: the flow into the anti-caries, resulting in the anti-scale is too long, the benzene The conversion rate of formic acid diacetate Ο Ο usem28 shows that the use of poly-g waste material is divided into a resin and a single == k oil-water separator towel to set up human water and unit ^ high-component two products, but Wei Da oil-water separation order; this patent document The hue of the product is not involved, so the commercial i [Summary] The present invention relates to a method for recycling recycled polyester raw materials. The ship and the glycol are better than the second ester. The raw material of the polyacetate in the present invention is polyparaphenylene. Ethyl formate
廢料本發明係有關—種自聚對苯二甲酸乙二醋师T) ίϋΐ備⑥純度對苯二甲酸二醋之方法，該方法包括使PET 雜购媒存在下，進行轉反應、 苯二苯;"甲酸乙二醋(PET)廢料製備高純度對 所產ΞΪί ’在進摘交換反應之後，又包括使反應 叮座生之乙一醇脫除以及純化之步驟。 本發明之自聚對苯二甲酸乙4(ΡΕΤ)廢料製備高純度對 7 200938570 護膜、纖維工，、包裝薄膜或面板之保 元醇為含6_101磁=1加工後產生之殘料。且脂肪族單 法中，PPT叙碳原子之直鏈或分歧鏈之烷醇。本發明之方 甲酸-賴與麟料猶反應，可制對苯二 方狄碰為在狀觸存在下，進 方法發明主要目的在於提供—種回收聚®旨廢料再生之 Ο ❹ ϊίΠ疋此聚酯樹脂是由對苯二甲酸與乙二醇為原料所製 k之簡稱為PET的聚對苯二甲酸乙二醋之聚g旨。 如莖2本之方法’該所用之觸媒可單獨使用草酸鹽，例 草祕、魏錫、草酸鋅、草轉、草魏等。本發明方法 所用之觸媒’除了草酸鹽以外，又可視情況併入其他辅觸 媒，例如醋酸鹽例如酷酸辞、醋酸錫、醋酸鎮、醋酸妈、醋= ,、，酸綈;錫化合物例如二乙酸二了基錫、月桂酸二丁基錫、 乳化二丁基錫、氧化單丁基錫等；鈦酸醋例如四異丙基鈦 酯、四丁基鈦酸酯等。 —依據本發明之方法，可得到高純度、低色相之工業產品即 對苯二:酸二酯增塑劑，尤其是對苯二甲酸二異辛酯增塑劑， 其純度高於94.0%，較好高於98 〇% ;且色相低於。 依據本發明之方法，藉由乙二醇脫除步驟，可解決習知 PET廢料回收製程中，乙二醇殘存量偏高的問題。此外，本發 明方法中，利用折射計檢測乙二醇回收溶液之折射率，得以快 速獲知反應是否完全，故而可以最經濟的反應時間，獲得高純 度的對苯二甲酸二酯。 ' 依據本發明之方法，由於不需進行洗滌，可藉由低污染製 程，經由聚酯廢料得到具經濟價值之工業產品，且因減少大量 洗滌廢水而可避免環境污染。且本發明之方法中，藉由更簡便 的乙二醇脫除方法，而可藉由更簡易、低能源的製程，降低產 8 200938570 業生產成本。 【實施方式】 本發明主要目的是由PET廢料製造純度高於94.0%且色 相低於APHA 25之對苯二甲酸二醋增麵的方法。進一步說 明^發明改良以往PET廢料生產對苯二甲酸二酯增塑劑，乙 二醇殘存在系統偏高的問題，簡化現有技術須進行中和、水 ，二脫水、過濾之問題。其解決方法是使pET廢料與脂肪族 早，醇在特稿媒存*下，断醇*反應、g旨雜反應、純化 程序。本發明方法於後述更詳細加以說明。 Ο Ο 树^發崎使狀起始稱PET廢料係指礦泉水或碳酸飲 丄在製造時產生的碎片或回收的寶特瓶、面板之包裝薄 =保護膜、纖維工業之紡紗、以及生產PET之規格外產品， ，中較佳為保舰碎⑽面板保賴。此pET廢料可不經洗 污程序即做為本方法之原料，雖然雜質會對製程與製品 卜觀產生影響，健由純絲序補償方式可驗此一問題。 ^本發明方法之設備可使用單一反應器、或串聯2個或 而成’若使用多個反應器之情況，此等反應器 。白〜、為同>1反應器’只要其中進行醇解之反應器可承受壓 = >5kg/cm之能力即可；該等反應器上設有冷凝器、 加水速率之開關裝置、油水分離器；該油上分 上層液回流進入反應器繼續反應，經收集下 蒸ίϋ、乙—醇溶液、祕水分離器的下層流收集於儲槽再 分歧應ί麟料元醇可為直鏈或 J、正辛醇、異辛醇、壬醇、異壬醇、正癸 J ,Waste The present invention relates to a method for self-polymerizing ethylene terephthalate T) 6 6 6 purity terephthalic acid diacetate, which comprises reacting benzene diphenylbenzene in the presence of a PET miscible medium. ; " Formic acid ethane vinegar (PET) waste preparation of high purity for the production of ΞΪ 在 ' After the exchange reaction, it also includes the step of removing and purifying the reaction of the reaction of the ethanol. The self-polyethylene terephthalate (4) waste material of the invention is prepared into a high-purity pair of 7 200938570 film, fiber, packaging film or panel, and the residual alcohol is processed after 6_101 magnetic=1. In the aliphatic mono-method, PPT is a linear or divalent alkanol of a carbon atom. The formic acid-lysine of the present invention reacts with the sap, and can be made into a bismuth diene. The main purpose of the invention is to provide a recycling granule for recycling. 聚酯 Π疋 Π疋 Π疋 聚酯It is a polyethylene terephthalate condensed by PET, which is made of terephthalic acid and ethylene glycol. For example, the method of the stem 2 can use oxalate alone, such as grass secret, Wei Xi, zinc oxalate, grass turn, grass Wei and the like. The catalyst used in the method of the present invention, in addition to oxalate, may be incorporated into other auxiliary catalysts, such as acetates such as sulphuric acid, tin acetate, acetic acid, acetic acid, vinegar =, acid strontium; tin The compound is, for example, a nonyltin diacetate, dibutyltin laurate, dibutyltin emulsified, monobutyltin oxide or the like; a titanic acid vinegar such as tetraisopropyltitanate, tetrabutyl titanate or the like. - according to the method of the present invention, an industrial product of high purity and low hue, that is, a terephthalic acid: acid diester plasticizer, especially a diisooctyl terephthalate plasticizer, having a purity higher than 94.0%, can be obtained. It is preferably higher than 98 〇%; and the hue is lower than. According to the method of the present invention, the ethylene glycol removal step can solve the problem that the residual amount of ethylene glycol is high in the conventional PET waste recycling process. Further, in the method of the present invention, by using a refractometer to detect the refractive index of the ethylene glycol recovery solution, it is possible to quickly know whether or not the reaction is complete, so that a highly pure terephthalic acid diester can be obtained with the most economical reaction time. According to the method of the present invention, since no washing is required, an economical industrial product can be obtained via polyester waste by a low-pollution process, and environmental pollution can be avoided by reducing a large amount of washing wastewater. Moreover, in the method of the present invention, the production cost of the production industry can be reduced by the simpler and lower energy process by the simpler method of removing the ethylene glycol. [Embodiment] The main object of the present invention is to produce a method of producing a terephthalic acid diacetate having a purity higher than 94.0% and a hue lower than that of APHA 25 from PET waste. Further, the invention improves the production of terephthalic acid diester plasticizer from PET waste, and the problem of high residual system of ethylene glycol remains, simplifying the problems of neutralization, water, dehydration and filtration in the prior art. The solution is to make the pET waste as early as the aliphatic, and the alcohol in the special medium*, the alcohol reaction, the heterogeneous reaction, and the purification procedure. The method of the present invention will be described in more detail later. Ο Ο ^ ^ 发 ^ ^ ^ PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET PET For the specification of PET, it is better to protect the ship from the (10) panel. This pET waste can be used as the raw material of the method without the washing process. Although the impurities will affect the process and the product, the pure wire order compensation method can be used to check this problem. The apparatus of the process of the present invention may use a single reactor, or two or in series, if such multiple reactors are used, such reactors. White ~, is the same > 1 reactor 'as long as the reactor in which the alcoholysis is carried out can withstand the pressure = > 5 kg / cm capacity; the reactor is equipped with a condenser, water rate switching device, oil water Separator; the oil is separated into the upper layer and refluxed into the reactor to continue the reaction, and the lower stream of the distillate, the ethyl alcohol solution and the secret water separator are collected and collected in the storage tank, and then the divergence should be linear or J, n-octanol, isooctanol, decyl alcohol, isodecyl alcohol, 癸J,
等燒醇可單獨使用-種，亦可組合兩種 ，。、巧U 使用C7.C1Q之鋪，更好為C8_CiG麟。用該鱗較好The co-alcohol can be used alone or in combination. Qiao U uses the C7.C1Q shop, better for C8_CiG Lin. Use this scale better
為促使酉旨交換反應順利進行，該脂肪鮮元醇相對於PET 200938570 成之反應混合物必須為過量 2置6 3tf i吉構單元計算)之比例為2·2领1莫耳比，更 式，可-段添加、分段添加，較合中不拘任何形 能必秋轉反應段使肖敎綱，此觸媒之效 St? 交換反應段乃至製程最後;且能夠得到-ί 化合物率ϋ特徵。此觸媒成份為草酸鹽 士放Βηί酸鎮¥酸錫、卓酸辞、草酸録、草酸經等。 仙鮭月中所用之觸媒成分’除了草酸鹽以外，尚可含有装 Ο itS二ϊ醋酸辞、醋酸錫、醋酸鎂、醋酸鈣、醋酸錳： 醋，綈等醋酸鹽；二乙酸二丁基錫、月桂酸 氧化單丁基錫等錫化合物；四異丙基鈦^、四丁 ^ 酸=:ϊ酸==月=之觸媒，可單獨使用ί 3ΐ^=ΐϊ：ΐ—種或數種輔觸媒。本發明中，較佳之組 為相對於t重量與之m用組^物°其各別添加量 〇.〇5-〇.3重量％量 重篁％，更適合之添加量為 更好，轉絲錄2GG_25crc^條件下， 好在23()_2贼之溫度下断。若醇解 若薛紘限之2GG°C之溫度，騎解速率過慢且不完全； 反應產生、=其上限250°c之溫度，則單元醇易劣解導致副 醇解反應段至少在釜壓大於2 .0k8/cm2錶壓下進 力形綱可以氮氣 : 00分鐘，較好為12_分鐘。若反應時間少 則可ί Σ能導致ΡΕΤ醇解程度不足；若多於雙分鐘， 2發明醇解後產生之乙二醇發生逆反應再生ΡΕΤ寡聚物。 的另一顯著特徵為在上述草酸鹽觸媒存在下，可促 200938570 進醋交換反應加速進行而且將乙二醇自PET絲體中醋交換 出來二酯交換反應可以在上述醇解反應爸中進行，也可以在另 換反f爸中進行’而不會產生不良影響。為徹底分離反 應體j之乙二醇以提高對苯二甲酸二醋純度，於醋交換反應蒼 上設有二油水分離n，贿得持_出之乙二醇水溶液經由油 水分離器底部排出收集於儲槽，單元醇則由油水分離器上層液 回流入反應蚤繼續參與反應。酯交換反應階段必須以相溶劑持 續自反應系以及單元醇相争溶出乙二醇，較合適之相溶劑為 水。相溶劑水加入系統之型態不拘，可以是液相、蒸汽與固態， • 較合適為液相的水與蒸汽，更好為過熱蒸汽。水或水基汽導〇入 〇 酉旨交換反應爸之量為： '' Χ^40*1/Υ (其中X為所加入之水或蒸氣莫耳數；γ為單元醇βΕΤ莫 耳比）。 、 相溶劑水或水蒸汽持續不斷加入酯交換反應蚤之時間從 2-10小時，較好為3-8小時，更好為4-7小時；低於此時間範 圍可能會令酯交換反應不完全，導致所製備之對苯二甲酸二酯 增塑劑純度偏低；高於此時間範圍則效率偏低浪費能源。酯交 換反應溫度通常控制在170-240°C，但在200-220°C條件下， Ο 酯交換反應效率較佳故而較好。酯交換反應壓力可在760至 200mmHg之壓力中進行，較佳之方式為減壓反應。真空度從 200-700毫米汞柱，較好在真空度為4〇〇_66〇毫米采柱範圍進 行。真空度<200毫米汞柱可能發生逆反應而使製品純度偏 低，真空度>700毫米汞柱則酯交換反應效率偏低，反應時間 過長。為了判斷酯交換反應終點，被相溶劑溶出之乙二醇溶液 必須是可被快速監測的，本發明中快速監測酯交換反應終點之 方法為利用折射計；當乙二醇溶液經折射計測得折射率小於 1.3334/25°C，更好小於1.3330/25。(：時，則視為已達反應終點 折射率在上述範圍内的乙二酵水溶液之乙二醇含量小於〇1重 11 200938570 量％。 本發明另一特徵為於上述酯交換反應之粗酯製品，經由純 化製程知到一純度尚、色相佳、酸價低之製品。此純化製程可 ，上述酯父換反應釜中或另接一蒸顧塔、或於薄膜蒸發器中進 行^發純化。純化製程在真空度<2毫米汞柱以及溫度< 240。。中持，進行；若真空度>2絲汞柱，咖收速度慢； 溫度>240°C，則對苯二甲酸二酯因高溫劣解導致製品 差、酸價升高，加工性能不佳。 ' 本發明的特徵是使用PET廢料與單元醇，在一特定觸媒 f在下，經由醇解反應、醋交換反應、純化程序，可以得到」 〇 咼純度、低色相、低酸價之對苯二甲酸二酯增塑劑製品。再者， 本方法因經純化製程，所以使用之PET廢料不限定為洗淨之 保特瓶碎片、包裝薄膜、保護膜、或纖維工業之紡紗，大為降 低洗滌廢水產生。其結果，使得PET廢料可再生回收，達成 省資源化、綠色產品化以及降低環境污染之衝擊。 本發明將以下列實施例詳細加以說明，惟該等實施例僅為 說明目的，而非用以限制本發明之範圍。 實施例1 在一個裝有攪拌器、溫度計、壓力計、油水分離器、流量 Q 控制器及冷凝器的高壓反應爸中，將未經洗淨之PET保護膜 (*獲自奇美電子股份有限公司)碎片3〇〇克、2-乙基己醇712克、 草f鋅0.6克、四丁基敍;酸酯〇·6克投入反應釜中。反應爸在 氮氣下充分攪拌並加壓至錶壓為2 〇kg/cm2，反應溫和昇溫 至230°C，最後錶壓穩定在4.5kg/cm2，經反應2 5小時後徐徐 ，，、冷卻至200。(：。其次施以真空，將壓力由常壓降至66〇毫 米采柱，將純水250克經由流量控制器定速導入反應釜底部， 於反應溫度介於180-200t：條件下持續餾出於油水分離器中， 下層^二醇水溶液自分離器底部脫出；2-乙基己醇上層液則經 回流管返回反應釜繼續參與反應，以折射計監測乙二醇水溶液 12 200938570 其折射率為1.3333/25°C，酯交換反應終了，脫出乙二醇水溶 液計345克，歷程5.5小時。其次，將壓力由660毫米汞柱逐 漸降低至2毫米汞柱以下，回收過量之2-乙基己醇，粗醋製品 598克(產率=98.0%)。粗酯製品經由凝膠滲透層析儀分析得 DOTP(對苯二甲酸二異辛酯)/PET寡聚體=98.2/1.8(面積比)，因 此純度為98.2%。粗酯製品經真空度<2毫米汞柱與蒸餾溫度 為235°C條件下蒸出，所得之D0TP為一色相(翻_録)8、酸^ 0.08mgKOH/g之無臭味製品。 • 實施例2 ，.除觸媒四丁基欽酸醋以醋酸辞取代外，其他反應設備、製 ❾ 程、配方如同實施例卜粗酯製品595克(產率=97.5%);粗醋 製品經由凝膠滲透層析儀分析得DOTP(對苯二甲酸二異^ 醋)/PET寡聚體=98.1/1.9(面積比），因此純度為98.1%。粗酯製 品經真空度<2毫米汞柱與蒸餾溫度為235°C條件下蒸出，所 得之DOTP為一色相(鉑-鈷)15、酸價0.18 mgKOH/g之無臭味 製品。 … 實施例3 同實施例1之反應設備’將未經洗淨之同實施例丨2PET 保護膜碎片300克、2-乙基己醇569克、草酸鋅〇·3克、四丁 Ο 基鉢酸酯0.6克投入反應釜中。反應爸在氮氣流下充分攪拌並 ^壓至錶壓為2.0kg/cm2，反應溫和昇溫至23(rc，最後錶壓穩 定在3.8 kg/cm2，經2.5小時後徐徐洩壓、冷卻至2〇〇c>(^其次 施以真空，將壓力由常壓降至660毫米汞柱，純水4〇〇克經 由、/’11_量控制器定速導入反應爸底部，反應溫度介於2〇〇_21〇。〇 巧件下持績餾出收集於油水分離器，下層乙二醇水溶液由分離 器底部脫出，2·乙基己醇上層液則經回流管返回反應釜繼續參 與反應。以折射計監測乙二醇水溶液其折射率為; 酉旨交換反應終了，脫出乙二醇水溶液計485克，歷程6.3小時。 其次，將真空度由660毫米汞柱逐漸降低至2毫米汞柱以 13 200938570 下，回收過量之2-乙基己醇，粗酯製品6〇2克(產率=98 6%)。 粗酯製品經由凝膠滲透層析儀分析得D〇Tp(對苯二甲酸二異 辛酯)/PET寡聚體=98.8/1.2(面積比）’因此純度為98.8。/。。粗酯 製品經一薄膜蒸發器連續真空度<2毫米汞柱與蒸餾溫 235°C條件下蒸出，所得之DOTP為一色相(鉑-鈷)20'、酸價〇 ^ mgKOH/g之無臭味之製品。 · 實施例4 同實施例1之反應設備，將未經洗淨之同實施例1之ΡΕτ 保護膜碎片300克、異壬醇675克、草酸錫0.3克、四丁基鈦 酸酯0.6克投入反應釜中。反應爸在氮氣流下充分攪拌並加壓 〇 至錶壓為，反應溫和昇溫至23(TC，最後錶壓穩定在 3.8 kg/cm2，經2.5小時後徐徐洩壓、冷卻至2〇〇t：。其施以 真空’將壓力由常壓降至660毫米汞柱，以5kg/cm2高壓蒸氣 經由流量控制閥定速導入反應釜底部，反應溫度介於 190-211°C條件下持續餾出收集於油水分離器中，下層乙二醇 水溶液則經由分離器底部脫出，異壬醇上層液則經回流管返回 反應釜繼續參與反應。以折射計監測乙二醇水溶液其折射率為 1.3331/25°C，醋交換反應終了，脫出乙二醇水溶液計克， 歷程6.3小時。其次’將真空度由66〇毫米汞柱逐漸降低至2毫 ❹ 米汞柱以下，回收過量之異壬醇，粗酯製品620克(產率 =95.0%)。製品經由凝膠滲透層析儀分析得DINTp(對苯二甲酸 二異壬酯)/PET寡聚體=98.4/1.6(面積比），因此純度為 98.4%。。粗酯製品經真空度丨毫米汞柱與蒸餾溫度為24〇。〇 條件下蒸出，所得之DINTP為一色相(銘-鈷)5〇、酸價〇 3〇 KOH/g之無臭味之製品。 實施例5 同實施例1之反應設備，將未經洗淨之pET保護膜碎片 300克、2_匕基己醇528克、草酸錫〇.6克、四丁基欽酸醋μ 克投入反應釜中。反應蚤在氮氣流下充分攪拌並加壓至錶壓為 200938570 .g/fm」反應溫和昇溫至23〇。〇，最後錶壓穩定在w ^/cm ’經2.5小時後徐徐賴、冷卻至2〇〇〇c。其次施 二力由常壓降至_毫米汞柱，以他加2高壓蒸氣 ^^量蝴峡料人反絲底部，反應溫度條187-21〇 下持_出㈣於油水分離器巾，下層乙二醇水溶液由 二，底稍^，2_乙基己醇上層液則經回流管返回反應爸繼 續乂 /、反應。以折射計持續監測排出乙二醇水溶液其 1.3329/坑，醋交換反應終了，脫出乙二醇水溶液計 為In order to facilitate the smooth exchange reaction, the ratio of the fat fresh alcohol to the PET 200938570 reaction mixture must be an excess of 2 3 tf i ji units. The ratio is 2·2 collar 1 molar ratio, more It can be added in sections and added in stages. It is better to combine the reaction and the reaction section to make Xiao Xiaogang, the effect of this catalyst, St? exchange reaction section and even the end of the process; and can obtain the characteristics of -ί compound rate. The catalyst component is oxalate, Β ί 酸 acid town ¥ acid tin, Zhuo acid, oxalic acid, oxalic acid and so on. In addition to oxalate, the catalyst component used in the immortal month can contain S S itS ϊ acetic acid, tin acetate, magnesium acetate, calcium acetate, manganese acetate: vinegar, hydrazine and other acetate; dibutyltin diacetate , lauric acid oxidation of monobutyltin and other tin compounds; tetraisopropyl titanium ^, tetrabutyl acid =: tannic acid == month = the catalyst, can be used alone ί 3 ΐ ^ = ΐϊ: ΐ - species or several kinds of auxiliary Media. In the present invention, the preferred group is the amount of 添加.〇5-〇.3 wt% and the amount of 添加.〇5-〇.3 wt% relative to the weight of t and m, which is more suitable for the addition. Under the condition of 2GB_25crc^, it is good to break at the temperature of 23()_2 thief. If the alcoholysis is limited to 2GG °C, the riding rate is too slow and incomplete; the reaction produces, = the upper limit of 250 ° C, the unit alcohol is easy to inferior to cause the secondary alcoholysis reaction stage at least in the kettle The pressure is greater than 2.0 k8 / cm2 under the gauge pressure can be nitrogen: 00 minutes, preferably 12_ minutes. If the reaction time is small, the degree of sterolation may be insufficient; if more than two minutes, the ethylene glycol produced by the alcoholysis of the invention undergoes a reverse reaction to regenerate the oxime oligomer. Another significant feature is that in the presence of the above oxalate catalyst, the 200938570 vinegar exchange reaction can be accelerated and the glycol exchange from the PET filaments in the diester exchange reaction can be carried out in the above alcoholysis reaction dad. It can also be carried out in another exchange of anti-f dad' without adverse effects. In order to completely separate the ethylene glycol of the reactant j to increase the purity of the terephthalic acid diacetate, a second oil-water separation is provided on the vinegar exchange reaction, and the aqueous glycol solution obtained by the bribe is discharged through the bottom of the oil-water separator. In the storage tank, the unit alcohol is returned to the reaction by the upper layer of the oil-water separator and continues to participate in the reaction. In the transesterification reaction stage, the phase solvent must be continuously evolved from the reaction system and the unit alcohol phase to dissolve ethylene glycol. The suitable phase solvent is water. The phase of the solvent water added to the system is not limited, it can be liquid phase, steam and solid state, • water and steam which are more suitable for the liquid phase, and more preferably superheated steam. The amount of water or water-based vapor intrusion into the exchange reaction is: '' Χ^40*1/Υ (where X is the number of water or vapor moles added; γ is the unit alcohol βΕΤ molar ratio) . The solvent or water vapor is continuously added to the transesterification reaction for a period of from 2 to 10 hours, preferably from 3 to 8 hours, more preferably from 4 to 7 hours; below this time range, the transesterification reaction may not be caused. Completely, the purity of the prepared terephthalic acid diester plasticizer is low; above this time range, the efficiency is low and waste energy. The ester exchange reaction temperature is usually controlled at 170-240 ° C, but at 200-220 ° C, the oxime transesterification reaction is better and better. The transesterification reaction pressure can be carried out at a pressure of from 760 to 200 mmHg, preferably by a reduced pressure reaction. The degree of vacuum is from 200 to 700 mm Hg, preferably in the range of 4 〇〇 66 〇 mm. The degree of vacuum < 200 mm Hg may cause a reverse reaction and the purity of the product is low. The degree of vacuum > 700 mm Hg is low in transesterification reaction and the reaction time is too long. In order to judge the end point of the transesterification reaction, the ethylene glycol solution eluted by the phase solvent must be rapidly monitored. The method for rapidly monitoring the end point of the transesterification reaction in the present invention is to use a refractometer; when the ethylene glycol solution is refracted by a refractometer The rate is less than 1.3334/25 ° C, more preferably less than 1.3330 / 25. (At the time of the present invention, the ethylene glycol content of the aqueous solution of the aqueous solution of Ethylene glycol having a refractive index within the above range is less than 〇1 weight 11 200938570%. Another characteristic of the present invention is the crude ester of the above transesterification reaction. The product is obtained through a purification process, and a product with good purity, good color and low acid value is obtained. The purification process may be carried out in the above-mentioned ester replacement reactor or by another steaming tower or in a thin film evaporator. The purification process is carried out at a vacuum degree < 2 mm Hg and a temperature < 240 。; if the vacuum degree > 2 silk mercury column, the coffee collection speed is slow; temperature > 240 ° C, the benzoic acid Due to the high temperature inferior solution, the formic acid diester leads to poor product, high acid value and poor processing property. ' The invention is characterized in that PET waste and unit alcohol are used, under a specific catalyst f, via alcoholysis reaction and vinegar exchange reaction. , Purification procedure, can obtain "purine purity, low hue, low acid value of terephthalic acid diester plasticizer products. Furthermore, this method is not limited to cleaning due to the purification process. Pinter bottle fragments, packaging film, protection The spinning of the film or fiber industry greatly reduces the generation of washing wastewater. As a result, the PET waste can be recycled and recycled, achieving resource saving, green productization and reducing the impact of environmental pollution. The present invention will be described in detail in the following examples. It is to be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the invention. Embodiment 1 In a high pressure equipped with a stirrer, thermometer, pressure gauge, water separator, flow Q controller and condenser In the reaction dad, the unprotected PET protective film (* obtained from Chi Mei Electronics Co., Ltd.) 3 pieces of gram, 2-ethylhexanol 712 grams, grass f zinc 0.6 grams, tetrabutyl sulphate; Ester 〇·6g was put into the reaction kettle. The reaction dad was fully stirred under nitrogen and pressurized to a gauge pressure of 2 〇kg/cm2, the reaction was gently warmed to 230 °C, and the final gauge pressure was stabilized at 4.5 kg/cm2. 2 After 5 hours, slowly,,, and cooled to 200. (:. Secondly, vacuum is applied, the pressure is reduced from normal pressure to 66 mm, and 250 g of pure water is introduced into the bottom of the reactor via a flow controller at a constant rate. The reaction temperature is between 180-200t: under the condition Distilled in the oil-water separator, the lower aqueous solution of diol is taken out from the bottom of the separator; the upper layer of 2-ethylhexanol is returned to the reaction vessel through the reflux pipe to continue to participate in the reaction, and the aqueous solution of ethylene glycol is monitored by a refractometer 12 200938570 The refractive index is 1.3333/25 ° C, the end of the transesterification reaction, 345 g of ethylene glycol aqueous solution is removed, and the process is 5.5 hours. Secondly, the pressure is gradually reduced from 660 mmHg to below 2 mm Hg, and the excess is recovered. -ethylhexanol, 598 g of crude vinegar product (yield = 98.0%). The crude ester product was analyzed by gel permeation chromatography to obtain DOTP (diisooctyl terephthalate) / PET oligomer = 98.2 / 1.8 (area ratio), so the purity is 98.2%. The crude ester product was distilled off under a vacuum of < 2 mm Hg and a distillation temperature of 235 ° C, and the obtained D0TP was an odorless product of one hue (reversed), and acid (0.08 mg KOH/g). • Example 2, except that the catalyst tetrabutyl vinegar was replaced with acetic acid, the other reaction equipment, process, and formulation were as in the example 595 g of crude ester product (yield = 97.5%); crude vinegar products DOTP (diisophthalic acid terephthalate) / PET oligomer = 98.1/1.9 (area ratio) was analyzed by gel permeation chromatography, and thus the purity was 98.1%. The crude ester product was distilled off under a vacuum of < 2 mm Hg and a distillation temperature of 235 ° C to obtain a odor-free product having a monochromic phase (platinum-cobalt) 15 and an acid value of 0.18 mg KOH/g. Example 3 The reaction apparatus of the same example as in Example 1 was treated with the same Example 丨 2 PET protective film pieces 300 g, 2-ethylhexanol 569 g, zinc oxalate 〇 3 g, tetrabutyl fluorenyl hydrazine 0.6 g of the acid ester was charged into the reaction vessel. The reaction dad was fully stirred under nitrogen flow and pressed to a gauge pressure of 2.0 kg/cm2, and the reaction was gently warmed to 23 (rc, and the final gauge pressure was stabilized at 3.8 kg/cm2. After 2.5 hours, the pressure was gradually relieved and cooled to 2 Torr. c> (^ secondly apply a vacuum, the pressure is reduced from normal pressure to 660 mm Hg, pure water 4 g, via the /'11_ quantity controller, the speed is introduced into the bottom of the reaction dad, the reaction temperature is between 2〇〇 _21〇. The distillate is collected and collected in the oil-water separator. The lower aqueous solution of ethylene glycol is taken off from the bottom of the separator. The upper layer of ethyl 2-hexanol is returned to the reactor through the return pipe to continue to participate in the reaction. The refractometer monitors the refractive index of the aqueous solution of ethylene glycol; the end of the exchange reaction, the extraction of 485 grams of aqueous glycol solution, 6.3 hours. Secondly, the vacuum is gradually reduced from 660 mm Hg to 2 mm Hg. 13 200938570, the excess of 2-ethylhexanol was recovered, and the crude ester product was 6〇2g (yield=98 6%). The crude ester product was analyzed by gel permeation chromatography to obtain D〇Tp (terephthalic acid). Diisooctyl ester) / PET oligomer = 98.8 / 1.2 (area ratio) 'The purity is therefore 98.8%. A thin film evaporator is continuously distilled under the condition of 2 mm Hg and a distillation temperature of 235 ° C, and the obtained DOTP is a hue (platinum-cobalt) 20', and the acid value is mg^ mgKOH/g. [Example 4] The reaction apparatus of the same example as in Example 1, 300 g of the τ protective film fragments of the same example as in Example 1, 675 g of isodecyl alcohol, 0.3 g of tin oxalate, and tetrabutyl titanate 0.6. The gram was put into the reaction kettle. The reaction dad was fully stirred under nitrogen flow and pressurized to the gauge pressure. The reaction was gently warmed to 23 (TC, and the final gauge pressure was stabilized at 3.8 kg/cm2. After 2.5 hours, the pressure was gradually relieved and cooled. 2〇〇t: The vacuum is applied to reduce the pressure from normal pressure to 660 mmHg, and the high pressure vapor is introduced into the bottom of the reactor via a flow control valve at a constant rate of 5 kg/cm2. The reaction temperature is between 190 and 211 °C. The continuous distillate is collected in the oil-water separator, the lower aqueous solution of ethylene glycol is taken out through the bottom of the separator, and the upper layer of isodecyl alcohol is returned to the reaction vessel through the reflux pipe to continue to participate in the reaction. The refraction of the aqueous solution of ethylene glycol is monitored by a refractometer. The rate is 1.3331/25 ° C, the vinegar exchange reaction is finished, and the ethylene glycol is dissolved. The liquid count was 6.3 hours. Secondly, the vacuum was gradually reduced from 66 mmHg to below 2 mHm, and excess isodecyl alcohol was recovered. The crude ester product was 620 g (yield = 95.0%). The product was analyzed by gel permeation chromatography to obtain DINTp (diisononyl terephthalate) / PET oligomer = 98.4 / 1.6 (area ratio), so the purity was 98.4%. The crude ester product was vacuumed by 丨 mm. The mercury column was distilled at a temperature of 24 Torr and distilled under the conditions of hydrazine. The obtained DINTP was an odorless product having a color phase (M-cobalt) of 5 Å and an acid value of 〇3 KOH/g. Example 5 In the same manner as in the reaction apparatus of Example 1, 300 g of unwashed pET protective film chips, 528 g of 2-methylhexanol, 6 g of oxalic acid, and 4 g of tetrabutyl vinegar were put into reaction. In the kettle. The reaction enthalpy was thoroughly stirred under a nitrogen stream and pressurized to a gauge pressure of 200938570 g/fm. The reaction was gently warmed to 23 Torr. 〇, the final gauge pressure stabilized at w ^ / cm ' after 2.5 hours, slowly cooled to 2 〇〇〇 c. Secondly, the second force is reduced from normal pressure to _mmHg, and he adds 2 high-pressure steam ^^ quantity to the bottom of the butterfly material, and the reaction temperature is 187-21〇 under the _out (four) in the oil-water separator towel, the lower layer The aqueous solution of ethylene glycol is composed of two, the bottom is slightly, and the upper layer of 2-ethylhexanol is returned to the reaction via a reflux tube to continue the reaction. The 1.3329/ pit of the discharged ethylene glycol aqueous solution was continuously monitored by a refractometer, and the vinegar exchange reaction was terminated.
歷程I.6小時。其次，將真空度由660毫米汞柱逐漸降低至2 毫，汞柱以下，回收過量之2_乙基己醇，粗酯製品592克(產 率-97.0%)。此製品經由凝膠滲透層析儀分析得D〇Tp(對苯二 曱酸二異辛醋)/PET寡聚體=98〇/2〇(面積比），因此純度為 98.0%。粗酯製品經一薄膜蒸發器連續真空度<2毫米果柱與 蒸餾溫度為235。(：條件下蒸出，所得之D0TP為一色相(始_ 錄)8、酸價〇.〇8 mg KOH/g之無臭味製品。 實施例6 除觸媒四丁基鈦酸酯未添加外，其他反應設備、製程、配 方如同實施例1。粗酯製品591克(產率=96.9%);粗酯製品經 由凝膠滲透層析儀分析得D0TP(對苯二甲酸二異辛酯)/PET寡 聚體=95.0/5.0%(面積比），因此純度為95 〇%。粗酯製品經真 空度<2毫米汞柱與蒸餾溫度為235。〇237。(：條件下蒸出，所 得之D0TP為一色相(翻銘)12、酸價〇· 13 mg KOH/g，益臭味 製品。 …、 比較例1 同實施例1之反應設備’將未經洗淨之同實施例1之PET 保護膜碎片300克、2-乙基己醇650克、醋酸鋅0.3克、四丁 基鈦酸酯0.6克投入反應釜f。反應爸在氮氣流下充分攪拌並 加壓至錶壓為2.0kg/cm2 ’反應溫和昇溫至23(TC，最後錶壓穩 定在3.9kg/cm2，經2.5小時後徐徐洩壓、冷卻至2〇〇°C。其次 15 200938570History I.6 hours. Secondly, the vacuum was gradually reduced from 660 mmHg to 2 mM, below the mercury column, and an excess of 2-ethylhexanol was recovered, and the crude ester product was 592 g (yield - 97.0%). This product was analyzed by gel permeation chromatography to obtain D〇Tp (diisophthalic acid diisooctyl vinegar) / PET oligomer = 98 〇 / 2 〇 (area ratio), and thus the purity was 98.0%. The crude ester product was subjected to a continuous vacuum of a thin film evaporator < 2 mm fruit column with a distillation temperature of 235. (: Distilled under the conditions, the obtained D0TP is a one-color phase (starting record) 8, an acid value 〇. 〇 8 mg KOH / g of the odorless product. Example 6 except the catalyst tetrabutyl titanate was not added In addition, other reaction equipment, processes, and formulations were as in Example 1. Crude ester product 591 g (yield = 96.9%); crude ester product was analyzed by gel permeation chromatography to obtain D0TP (diisooctyl terephthalate). /PET oligomer = 95.0 / 5.0% (area ratio), so the purity is 95%. The crude ester product has a vacuum degree of < 2 mmHg and a distillation temperature of 235. 〇237. (: Distillation under conditions, The obtained D0TP is a hue (flip) 12, an acid value of mg 13 mg KOH / g, an odorous product. ..., Comparative Example 1 The reaction apparatus of the same as Example 1 will be unwashed as in Example 1 300 g of PET protective film fragments, 650 g of 2-ethylhexanol, 0.3 g of zinc acetate, and 0.6 g of tetrabutyl titanate were put into the reaction vessel f. The reaction dad was thoroughly stirred under nitrogen flow and pressurized to a gauge pressure of 2.0. Kg/cm2 'The reaction gently warmed to 23 (TC, the final gauge pressure was stabilized at 3.9 kg/cm2, after 2.5 hours, the pressure was gradually relieved and cooled to 2 ° C. Next 15 200938570
，力由㈣降至_絲采柱，純水_克經 二控制器定速導入反應爸底部，反應溫度介於191_2⑽。C ϊί:持續餾出收集於油水分離器，下層乙二醇水溶液由分離 二=脫出，2_乙基己醇上層液則細流管返回反應爸繼續參 、‘w。，脫出乙二醇水溶液計425克，歷程6.3小時。其次， 將真空度由660毫米采柱逐漸降低至2毫米汞柱以下，回收 過量之2-乙基己醇，粗酯製品575克(產率=94 3%)。過濾此粗 酯品得一酸價〇.10 mg K〇H/g ‘色相(鉑-鈷)300製品。此製品 經由凝膠滲透層析儀分析得D〇Tp(對笨二 • 絲體嘲.2/9.8(面積比），因此純度為9().2%。㈣Θ)/ΡΕΤ ^ 比較例2 同實施例1之反應設備，將未經洗淨之ΡΕΤ保護膜碎片 300克、2-乙基己醇650克、醋酸鎮〇.3克、四丁基欽酸酯〇 6 克投入反2應爸中。反應釜在氮氣流下充分攪拌並加壓至錶壓為 2.0kg/cm2，反應溫和昇溫至230。〇，最後錶壓穩定在 3.9kg/cm2，經2_5小時後徐徐洩壓、冷卻至2〇〇t。其；施以 ，空，將壓力由常壓降至660毫米汞柱，純水300克經由流 量控制器定速導入反應爸底部，反應溫度介於185_19〇c»c條件 下1續餾出收集於油水分離器，下層乙二醇水溶液由分離器底 Ο 部脫出，2-乙基己醇上層液則經回流管返回反應簽繼續參與反 應。，脫出乙二醇水溶液計379克，歷程5.3小時。其次，將 真空度由660毫米汞柱逐漸降低至2亳米汞柱以下，回收過 量之2-乙基己醇，粗酯製品570克(產率=93.4%)。遍濾此粗酯 品得一酸價0.10 mg KOH/g、色相(鉑-鈷)3〇〇製品。此製品經 由凝膠滲透層析儀分析得DOTP(對苯二曱酸二異辛_g旨)/pET寡 聚體=89.5/10.5(面積比），因此純度為89.5%。 比較例3 同實施例1之反應設備，經洗淨之保特甑碎片3〇〇克、2-乙基己醇813克、醋酸鋅〇.3克、四丁基鈦酸酯〇.1克投入反 16 200938570 應釜中。反應蚤在氮氣流下充分攪拌並溫和加溫至19〇<t， 間30分鐘，反應持續進行5.5小時。其二欠施以真空，將 由常壓降至610毫米汞柱，反應溫度維持在182<t，餾出之 2-乙基己醇經冷凝管回流返回反應釜繼續參與 小時反應終止。將真空度由610毫米果柱逐漸 汞柱以下，回收過量之2_乙基己醇，粗酯製品535克(產率 -87.7%)。過濾此粗酯品得一酸價〇 1〇 mg奶敗、色相(翻- 鈷)60製品。此製品經由凝膠渗透層析儀分析得DQTp(對苯二 曱酸一異辛酯)/PET寡聚體=76.9/23.1(面積比），因此純度為 < 76.9%。 〇 由上述之實施例與比較例，可了解依據本發明之方法，利 用草酸鹽作為醇解觸媒’可獲得純度高於94.0%，更好高於 98.0%、色相低於APHA 25且酸價小於〇.img KOH/g之對苯 二甲酸二酯’而比較例中未使用本發明之草酸鹽作為醇解觸 媒，所得之對苯二甲酸二酯之色相相當高，且純度相對較低。 【圖式簡單說明】 【主要元件符號說明】 〇 17, force from (four) down to the _ silk mining column, pure water _ gram by the two controller fixed speed into the reaction dad bottom, the reaction temperature is between 191_2 (10). C ϊί: Continuous distillation is collected in the oil-water separator, the lower aqueous solution of ethylene glycol is separated by two = out, and the upper layer of 2-ethylhexanol is returned to the reaction tube to continue the reaction, ‘w. , 425 grams of aqueous solution of ethylene glycol was removed, and the process was 6.3 hours. Secondly, the vacuum was gradually reduced from 660 mm to less than 2 mm Hg, and an excess of 2-ethylhexanol was recovered, and 575 g of crude ester product (yield = 94 3%). This crude ester was filtered to give an acid value of 10.10 mg K 〇H/g ‘hue (platinum-cobalt) 300 product. This product was analyzed by gel permeation chromatography to obtain D〇Tp (for idiots • silk body mock. 2/9.8 (area ratio), so the purity was 9 (). 2%. (4) Θ) / ΡΕΤ ^ Comparative Example 2 In the reaction apparatus of Example 1, 300 grams of unwashed protective film fragments, 650 grams of 2-ethylhexanol, 3 grams of acetic acid, 3 grams of tetrabutyl-decanoate, and 6 grams of anti-2 should be used. in. The reaction vessel was thoroughly stirred under a nitrogen stream and pressurized to a gauge pressure of 2.0 kg/cm2, and the reaction was gently heated to 230. 〇, the final gauge pressure is stable at 3.9kg/cm2, and after 2_5 hours, it is gradually relieved and cooled to 2〇〇t. It is applied, empty, and the pressure is reduced from normal pressure to 660 mmHg, and 300 g of pure water is introduced into the bottom of the reaction dad by a flow controller at a constant speed. The reaction temperature is between 185_19〇c»c and 1 continuous distillation is collected. In the oil-water separator, the lower aqueous solution of ethylene glycol is taken off from the bottom of the separator, and the upper layer of 2-ethylhexanol is returned to the reaction mark through the reflux pipe to continue to participate in the reaction. , 379 g of ethylene glycol aqueous solution was taken out, and the course was 5.3 hours. Next, the degree of vacuum was gradually reduced from 660 mmHg to below 2 MH, and excess 2-ethylhexanol was recovered, and 570 g of crude ester product (yield = 93.4%). The crude ester was filtered to give an acid product of 0.10 mg KOH/g and a color (platinum-cobalt) product. This product was analyzed by a gel permeation chromatography to obtain DOTP (diisoxin terephthalate _g)/pET oligomer = 89.5/10.5 (area ratio), and thus the purity was 89.5%. Comparative Example 3 The reaction apparatus of the same example as in Example 1, washed 保 甑 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Investing in the counter 16 200938570 should be in the kettle. The reaction enthalpy was thoroughly stirred under a nitrogen stream and gently warmed to 19 Torr <t for 30 minutes, and the reaction was continued for 5.5 hours. The vacuum is applied to 610 mmHg from normal pressure, and the reaction temperature is maintained at 182 lt. t. The distilled 2-ethylhexanol is returned to the reactor via a condenser to continue the reaction. The vacuum was gradually reduced from the 610 mm fruit column to the mercury column, and an excess of 2-ethylhexanol was recovered, and the crude ester product was 535 g (yield -87.7%). The crude ester product was filtered to obtain an acid value of 1 〇 mg of milk, hue (turn-cobalt) 60 product. This product was analyzed by gel permeation chromatography to obtain DQTp (isooctyl p-benzoate) / PET oligomer = 76.9/23.1 (area ratio), and thus the purity was < 76.9%. From the above examples and comparative examples, it can be understood that the method according to the present invention utilizes oxalate as the alcohol desorbing agent to obtain a purity higher than 94.0%, more preferably higher than 98.0%, and a hue lower than APHA 25 and acid. The price is less than 〇.img KOH/g of terephthalic acid diester', and in the comparative example, the oxalate of the invention is not used as the alcohol decomposing agent, and the obtained chromate diester has a relatively high hue and relatively pure purity. Lower. [Simple description of the diagram] [Explanation of main component symbols] 〇 17