經濟部中央梂準局貝工消费合作社印装 A7 B7____ 五、發明説明（） 1 發明領域 本發明有關用以製備聚苯二甲酸伸乙酯之方法，更特別Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs A7 B7____ V. Description of the Invention (1) Field of the Invention The present invention relates to a method for preparing poly (ethylene terephthalate), which is more special
I 的是用以製備其中可以有效地達成聚對苯二甲酸伸乙酯預 結晶作用之聚對苯二甲酸伸乙酯之方法。 發明背景 聚對苯二甲酸伸乙酯通常係經由酯化反應步驟、液相 聚縮反應步騍以及固相聚縮反應步驟製備。然而，在液相 聚縮反應步驟所製得之聚對苯二甲酸伸乙酯片係無定形， 因此假如其進行固相聚縮反應時，可能會產生結塊作用》 因此，在固相聚縮反應步騍之前，通常提出預結晶步驟， 其中將經由液相聚縮反應步驟所製得之聚對苯二甲酸伸乙 酯加熱至結晶，然後對該結晶聚對苯二甲酸伸乙酯進行固 相聚縮反應步驟。然而，假如該聚對苯二甲酸伸乙酯以驟 增溫度或以高溫加熱以便容易進行預結晶作用，該系統中 會發生該聚對苯二甲酸伸乙酯片結塊或熔融。因此，習用 相當溫和之加溫條件。 例如 Japanese Patent Laid-Open Publication No. 45229/1983揭示以1 5 0°C熱空氣處理該聚對苯二甲酸伸 乙酯1小時，然後以1 9 5 °C氮氣處理2 . 5小時以結晶 該聚對苯二甲酸伸乙酯。然而，此等條件並不恰當，因爲 用以結晶之所需時間長，造成製造成本增加。 此外，在某此包含少量共聚體之共聚聚對苯二甲酸伸 乙酯實例中，因爲該共聚物結晶度較低而且熔點較低之故 本紙張尺度適用中國國家梂準（CNS ) A4规格（210X297公釐） —^ϋ·' ϋ·— I ^^—^1 m l#m ^i_^i * - . (請先閲讀背面之注意事項再填寫本頁) 訂I is a method for preparing polyethylene terephthalate in which polyethylene terephthalate precrystallization can be effectively achieved. BACKGROUND OF THE INVENTION Polyethylene terephthalate is generally prepared via an esterification step, a liquid phase polycondensation step, and a solid phase polycondensation step. However, the polyethylene terephthalate sheet obtained in the liquid phase polycondensation step is amorphous, so if it undergoes a solid phase polycondensation reaction, agglomeration may occur. Therefore, in the solid phase polycondensation reaction, Before step 骒, a pre-crystallization step is usually proposed, in which the polyethylene terephthalate obtained through the liquid phase polycondensation reaction step is heated to crystallize, and then the crystallized polyethylene terephthalate is solid-phase polymerized. Shrinking reaction step. However, if the polyethylene terephthalate is heated at a sudden increase in temperature or at a high temperature to facilitate the pre-crystallization, agglomeration or melting of the polyethylene terephthalate sheet may occur in the system. Therefore, the use of fairly mild heating conditions is common. For example, Japanese Patent Laid-Open Publication No. 45229/1983 discloses that the polyethylene terephthalate is treated with hot air at 150 ° C for 1 hour, and then treated with nitrogen at 195 ° C for 2.5 hours to crystallize the Polyethylene terephthalate. However, these conditions are not appropriate because the time required for crystallization is long, resulting in increased manufacturing costs. In addition, in this example of copolymerized poly (ethylene terephthalate) containing a small amount of copolymers, because the copolymer has a low crystallinity and a low melting point, the paper size is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) — ^ ϋ · 'ϋ · — I ^^ — ^ 1 ml # m ^ i_ ^ i *-. (Please read the precautions on the back before filling this page) Order
I -4, ·. 經濟部中央揉準局員工消费合作社印装 A7 __ B7 五、發明説明（2 ) ’迄今尙未發現可以有效結晶該共聚物，但是不會致使結 塊或熔融之加熱條件。 發明目的 已在上述環境中進行本發明，本發明目的係提出一種 用以製備聚對苯二甲酸伸乙酯之方法，其包括預結晶步驟 ，其中聚對苯二甲酸伸乙酯以及經共聚之聚對苯二甲酸伸 乙酯可以有效地預結晶。 發明摘要 本發明提出一種製備聚對苯二甲酸伸乙酯之方法，其 包括加熱由酯化反應步驟與液相聚縮反應步驟製得之聚對 苯二甲酸伸乙酯片，使該聚對苯二甲酸伸乙酯結晶之預結 晶步驟，以及將該預結晶聚對苯二甲酸伸乙酯片加熱至高 於預結晶溫度之固相聚縮作用，其中該預結晶步驟包括： 其中該預結晶步驟包括（A)以不低於Tg且不高於 1 80 °C溫度（Ti)加熱PET片，並搅拌該PET片 ，使該PET結晶至結晶度至少3 0% ; (B)加熱該PET片，使其保持在自（Tbn - 4 0 °C)至高達Tbm -範圍內之溫度（T2)，使該聚對苯 二甲酸伸乙酯結晶至結晶度至少3 0%，其中Tbm定義 爲利用差別掃瞄量熱器（D S C )以1 〇 °c /分加熱率加 熱聚對苯二甲酸伸乙酯時，所觀察得吸熱尖峰中之次要尖I -4, ·. Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs A7 __ B7 V. Description of the Invention (2) 'So far no heating conditions have been found which can effectively crystallize the copolymer, but will not cause agglomeration or melting . Object of the invention The present invention has been carried out in the above-mentioned environment. The object of the present invention is to propose a method for preparing polyethylene terephthalate, which includes a precrystallization step, in which polyethylene terephthalate and copolymerized Polyethylene terephthalate can be effectively pre-crystallized. SUMMARY OF THE INVENTION The present invention provides a method for preparing polyethylene terephthalate, which comprises heating a polyethylene terephthalate tablet prepared by an esterification reaction step and a liquid-phase polycondensation reaction step to make the polyethylene terephthalate A pre-crystallization step of crystallization of ethylene terephthalate, and a solid-phase polycondensation of heating the pre-crystallized polyethylene terephthalate sheet above a pre-crystallization temperature, wherein the pre-crystallization step includes: wherein the pre-crystallization step Including (A) heating the PET sheet at a temperature not lower than Tg and not higher than 1 80 ° C (Ti), and stirring the PET sheet to crystallize the PET to a crystallinity of at least 30%; (B) heating the PET sheet To keep it at a temperature (T2) in the range from (Tbn-40 ° C) to as high as Tbm-to crystallize the polyethylene terephthalate to a crystallinity of at least 30%, where Tbm is defined as the utilization Differential scanning calorimeter (DSC) heating the polyethylene terephthalate at a heating rate of 10 ° C / min.
I 峰開始吸熱溫度；以及 本紙張尺度逍用中國困家標準（CNS ) A4规格（210X297公釐) (請先閲讀背面之注$項再填寫本頁) - f: -5 - 經濟部中央樣準局貝工消费合作社印製 A7 B7_ 五、發明説明（3 ) (c )加熱並攪拌該PET片，使PET片之溫度升 高到固相聚縮溫度。即使在共聚聚對苯二甲酸伸乙酯實例 中仍可以有效達成聚對苯二甲酸伸乙酯之預結晶作用。 本發明中，步驟（B)以在1 90±30t：範圍內之 最終樹脂溫度加熱1至3小時爲佳。 本發明中，固相聚縮作用係於2 0 0至2 3 or溫度 範圍內進行爲佳》 發明詳述 下文詳細敍述根搛本發明製備聚對苯二甲酸伸乙酯之 方法。 本發明製備聚對苯二甲酸伸乙酯之方法包括加熱聚對 苯二甲酸伸乙酯片（其經由酯化反應步驟及液相聚縮步驟 製得）以結晶該聚對苯二甲酸伸乙酯之預結晶步驟，以及 將該經預結晶聚對苯二甲酸伸乙酯片加熱至高於預結晶作 用溫度之固相聚縮反應步驟，其中骸預結晶步驟係於下述 特定條件下進行。 酯化反應步親 該酯化反應步驟通常使用含對苯二甲酸與乙二醇之 1 镀中進行。以1莫耳對苯二甲酸爲基準，該漿液含有之乙 二醇量通常爲1.02至2.0莫耳，以1.03至 1.5莫耳爲佳。該漿液連續至供應酯化反應步驟。 本發明中’使用對苯二甲酸與乙二醇作爲原材料製備 本紙張尺度適用中國國家揉準（CNS ) A4规格(210X297公漦) ----·--k---------訂------Ί (讀先閲讀背面之注意事項再填寫本頁) -6- 經濟部中央揉準局員工消費合作社印装 A7 B7 ____ 五、發明説明（，） 4 聚對苯二甲酸伸乙酯，但是可使用數量不多於2 0莫耳％ 之其它二羧酸及/或其它乙二酵類》 對苯二甲酸似外之其它二羧酸實例（可用於共聚縮作 用者）包括芳族二羧酸，諸如苯二甲酸（鄰苯二甲酸、異 苯二甲酸、萘二羧酸、二苯基二羧酸以及二苯氧基之烷二 羧酸；脂族二羧酸，諸如己二酸、癸二酸、壬二酸及癸烷 二羧酸；以及脂環二羧酸，諸如環己烷二羧酸。 乙二醇以外之其它乙二醇實例（可用於共聚聚作用者 )包括脂族乙二醇類，諸如三甲二酵、丙二酤、四甲二酵 、新戊二醇、六甲二醇以及十二甲二醇；脂環二酵類，諸 如環己烷二甲醇；以及芳族二羧基化合物，諸如雙酚類、 氫醌以及2，2—雙（4 一石一羥基乙氧基苯基）丙烷。 本發明中，除對苯二甲酸之外，使用異苯二甲酸作爲 二羧酸組份爲佳，以整體二羧酸組份爲基準，其用量爲1 至5莫耳％ » 該酯化反應係使用由至少二個酷化反應器彼此依序連 接所組成之裝置，在乙二醇回流下進行，該反應所形成的 水或醇係利用分皤柱排出該系統。 該酯化反應可在下列條件下進行：第一階段酯化反應 中溫度通常爲2 4 0至2 7 0 °C，以2 4 5至2 6 5 °C爲 佳，壓力通常爲0 . 2至3kg/cm2 — G，以0 . 5 至2 k g/cm2 — G爲佳；在最後階段酯化反應中，溫 度通常爲250至280 °C，以255至275 °C爲佳， 壓力通常爲0至1 . 5kg/cm2 — G，以0至1 . 3 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁) ' VI ϋ . 訂 A7 B7 五、發明説明（） 5 k g/cm2 — G 爲佳。 該酯化反應以二階段進行時，第一與第二酯化反應條 件分別在上述第一與最後步驟範圍內進行。當該酯化反應 以三個或以上階段進行時，第二至最後階段之酯化反應條 件中有一個係選自介於上述第一與最未階段之條件。 例如，以三階段進行酯化反應時，該第二階段酯化反 應一般係以245至275t溫度（以250至270t 爲佳 > ，一般爲0至2kg/cm2 — G壓力（以0.2 至1 . 5kg /cm2 — G爲佳）進行。 每一階段之酯化轉化率並無特殊限制，但是每一階段 之轉化率逐漸增加爲佳。最終階段之酯化轉化率不低於 90%，不低於93%爲佳。 經濟部中央揉準局貝工消费合作社印製 (讀先閱讀背面之注意事項再填寫本頁) 雖然該酯化反應可在不添加對苯二甲酸及乙二醇以外 之組份下進行，但是可以添加少量鹼性化合物，例如三胺 類，諸如三甲胺、三正丁胺及爷基二甲胺，四級銨化合物 ，諸如四甲銨化氫氧、四正丁銨化氫氧、以及三甲基苄銨 化氫氧，與另外之碳酸鉀、碳酸鈉、碳酸鉀與醋酸鈉。在 酯化反應中添加鹸性化合物爲佳，因爲其可使聚對苯二甲 酸伸乙酯主鏈中之對苯二甲酸二氧乙烯組份單位保持在相 當低水準。 經由上述酯化反應步驟製得之酯化產物（低縮合物） 通常具有5 0 0至5 0 0 0之數量平均分子量。然後將製 得之酯化產物供應至液相聚縮反應步驟》 本紙張尺度適用中國Η家揉準（CNS ) A4規格（210X297公釐) -8- 經濟部中央標準局貝工消費合作社印製 A7 B7___ 五、發明説明（） 6 液相聚縮反應步騣 液相聚縮反應步驟中，以不低於所形成之聚對苯二甲 酸伸乙酯熔點之溫度於減壓並存在聚縮觸媒下加熱該系統 進行聚縮作用，自該系統餾除反應所形成之乙二醇。 該液相縮合反應可以以單一或多重階段進行。當該液 相縮合反應以多重階段進行時，第一階段聚縮反應係以一 般爲250至290 °C溫度（以260至280 °C爲佳） ，500至20托耳（200至30托耳爲佳）之壓力下 進行，最末階段聚縮反應係以265至300 °C (以27 0至295 °C爲佳）溫度，10至0 . 1托耳（以5至 0 . 1托耳爲佳，特別是2至0 . 1托耳）之壓力下進行 〇 當該液相聚縮反應係以二階段進行時，第一與第二階 段之聚縮反應條件係分別在上述第一與最終階段範圍內。 當以三或以上階段進行聚縮反應時，第二至最終階段之一 的聚縮反應條件係選自介於上述第一與最終階段之條件。 例如，當以三階段進行液相聚縮作用時，該第二階段 聚縮反應係以一般2 60至2 9 5 °C (以2 7 0至2 8 5 °C爲佳）之溫度，一般50至20托耳（以40至5托耳 爲佳）之壓力下進行。 由液相聚縮反應製備之聚對苯二甲酸伸乙酯固有粘度 (I V)並無特殊限制，但是該固有粘度隨著每個階段逐 漸增加爲佳。最終階段聚縮反應所製得之聚苯二甲酸伸乙 酯之固有粘度（IV)通常爲0 · 35至0 .80d 1/ 本紙張尺度適用中國國家搮準（CNS ) A4規格（210X297公釐） I.----.------ΙΤΛ-------訂------ (請先閲讀背面之注意事項再填寫本頁) -9 - 經濟部中央揉準局貝工消費合作社印簟 A7 B7 五、發明説明（，） g，以0.45至0.75dl/g爲佳，自0.55至 0 . 7 5 d 1 / g 更佳。 該固有粘度（I V)可由溶液粘度計算，該溶液粘度 係在2 5 °C溶液中測得，該溶液係加熱將1 . 2 g聚對苯 二甲酸伸乙酯溶解於1 5 c c鄰氯酚中然後冷卻製得。 最終階段液相聚縮反應所製得之對苯二甲酸伸乙酯結 晶度通常小於2 % » 該液相聚縮反應必須於存在聚縮觸媒與安定劑下進行 。本文可使用之聚縮觸媒實例包括鍺化合物，諸如二氧化 鍺、四乙氧化鍺及四-正丁氧化鍺；銻化合物，諸如三氧 化鍺、醋酸銻、四乙氧化鍺以及四-正丁氧化鍺：以及鈦 化合物，諸如四丁氧化鈦及四丙氧化鈦。該聚縮觸媒中， 二氧化鍺爲佳，其係因爲所形成之聚對苯二甲酸伸乙酯具 有良好色調及透明性之故。三氧化鍺及醋酸銻亦爲較佳者 ，因爲所形成之聚苯二甲酸伸乙酯具有良好結晶率與色調 〇 安定劑實例係磷化合物，包括磷酸酯類，諸如磷酸三 甲酯、磷酸三乙酯、磷酸三正丁酯、磷酸三辛酯、磷酸三 苯酯以及磷酸三甲苯酯；亞磷酸酯類，諸如亞磷酸三苯酯 、亞磷酸三十二酯以及亞磷酸三壬基苯酯；酸磷酸酯類， 諸如磷酸甲酸酯、磷酸異丙酸酯、磷酸丁酸酯、磷酸二丁 酯、磷酸-丁酯以及磷酸二辛酯；磷酸；以及多磷酸。藉 由添加磷化合物至酯化容器中，可以改良所形成聚對苯二 甲酸伸乙酯之色調與熱安定性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 -10- ----^---*---^乂------tr------^ - · > . {請先閱讀背面之注意事項再填寫本頁) 經濟部中央棋準局貝工消費合作社印裝 A7 B7 __ 五、發明説明（8 ) 本發明中，除了聚縮觸媒之外，可添加鈷化合物，錳 化合物或鎂化合物。 該钴化合物之實例包括氯化鈷、硫酸鈷、氫氧化鈷、 硝酸鈷、草酸鈷、甲酸鈷、醋酸鈷、酼基α-羥基異丁酸 鈷以及苯酸鈷。藉由添加鈷化合物至酯化容器中，可以加 速該酯化反應》 錳化合物實例包括醋酸錳、醯基α —羥基異丁酸錳、 硫酸錳、碳酸錳以及硝酸錳。藉由添加錳化合物至酯化容 器可加速該酯化反應。 該鎂化合物實例包括硫酸鎂、硝酸鎂、醋酸鎂、氯化 鎂、碳酸鎂、檸檬酸鎂、乳酸鎂與草酸鎂。藉由添加鎂化 合物至酯化容器中可以加速該酯化反應。 上述化合物通常係以其水溶液形式添加，而且其中所 使用之水量愈少愈好》 以1莫耳對苯二甲酸爲基準，該磷化合物之用置以磷 原子表示通常爲5至200ppm，10至lOOppm 爲佳* 以1莫耳對苯二甲酸爲基準，該鈷化合物之用量以金 屬鈷形式表示，通常爲5至200ppm，以1 〇至60 P P m爲佳。 以1奠耳對苯二甲酸爲基準，該錳化合物之用量以金 屬Μ形式表示，通常爲1 〇至2〇〇ppm，以20至 1 〇 〇 P P m 爲佳。 以1莫耳對苯二甲酸爲基準，該鎂化合物之用置以金 本紙張尺度適用中鬮两家揉準（CNS ) A4规格（2丨0X297公釐） (請先閲讀背面之注意事項再填寫本頁)I peak starting endothermic temperature; and this paper size is in accordance with China Standard for Household Standards (CNS) A4 (210X297 mm) (Please read the note on the back before filling this page)-f: -5-Central Ministry of Economy Printed by the Zhuhai Bureau Shellfish Consumer Cooperative A7 B7_ 5. Description of the invention (3) (c) The PET sheet is heated and stirred to raise the temperature of the PET sheet to the solid phase condensation temperature. Even in the case of copolymerized polyethylene terephthalate, the precrystallization effect of polyethylene terephthalate can be effectively achieved. In the present invention, it is preferable that the step (B) is performed by heating the final resin temperature in the range of 1 90 ± 30 t: for 1 to 3 hours. In the present invention, the solid phase polycondensation is preferably performed in a temperature range of 200 to 23 or more. DETAILED DESCRIPTION OF THE INVENTION The method for preparing polyethylene terephthalate according to the present invention is described in detail below. The method for preparing polyethylene terephthalate according to the present invention comprises heating a polyethylene terephthalate tablet (made by an esterification reaction step and a liquid phase polycondensation step) to crystallize the polyethylene terephthalate. The ester pre-crystallization step and the solid-phase polycondensation reaction step of heating the pre-crystallized polyethylene terephthalate sheet to a temperature higher than the pre-crystallization temperature. The pre-crystallization step is performed under the following specific conditions. Esterification reaction step The esterification reaction step is usually performed using a plating method containing terephthalic acid and ethylene glycol. Based on 1 mole of terephthalic acid, the amount of ethylene glycol in the slurry is usually 1.02 to 2.0 moles, preferably 1.03 to 1.5 moles. This slurry is continued to the supply esterification reaction step. In the present invention, the paper is prepared by using terephthalic acid and ethylene glycol as the raw materials. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 cm) ---- · --k -------- -Order ------ Ί (Read the precautions on the back before filling in this page) -6- Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs A7 B7 ____ 5. Description of the invention (,) 4 Polyparaphenylene Ethyl dicarboxylate, but other dicarboxylic acids and / or other adipic acids not exceeding 20 mol% can be used. Examples of other dicarboxylic acids other than terephthalic acid (can be used for copolymerization) (Both) include aromatic dicarboxylic acids such as phthalic acid (phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenoxyalkanedicarboxylic acid; aliphatic dicarboxylic acid Acids such as adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples of ethylene glycol other than ethylene glycol (can be used for copolymerization (Polymers) include aliphatic glycols such as trimethione, malondiamine, tetramethyrate, neopentyl glycol, hexamethylene glycol, and dodecyl glycol; Alicyclic dienzymes such as cyclohexanedimethanol; and aromatic dicarboxy compounds such as bisphenols, hydroquinones, and 2,2-bis (4-monolithic-hydroxyethoxyphenyl) propane. In the present invention, In addition to terephthalic acid, it is better to use isophthalic acid as the dicarboxylic acid component. Based on the overall dicarboxylic acid component, the amount is 1 to 5 mol%. »The esterification reaction uses at least Two quenching reactors are sequentially connected to each other, and the device is carried out under reflux of ethylene glycol. The water or alcohol formed by the reaction is discharged from the system by using a column. The esterification reaction can be performed under the following conditions. : In the first-stage esterification reaction, the temperature is usually 2 40 to 27.0 ° C, preferably 2 4 5 to 2 6 5 ° C, and the pressure is usually 0.2 to 3 kg / cm2 — G, 0. 5 to 2 kg / cm2 — G is preferred; in the final esterification reaction, the temperature is usually 250 to 280 ° C, preferably 255 to 275 ° C, and the pressure is usually 0 to 1.5 kg / cm2 — G, From 0 to 1.3 This paper size applies to China National Standards (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling in this Page) 'VI ϋ. Order A7 B7 V. Description of the invention () 5 kg / cm2 — G is preferred. When the esterification reaction is carried out in two stages, the first and second esterification conditions are above the first and last respectively. It is carried out in the range of steps. When the esterification reaction is carried out in three or more stages, one of the conditions of the esterification reaction in the second to the last stage is selected from the conditions between the first and the last stages. For example, to When the esterification reaction is carried out in three stages, the second-stage esterification reaction is generally carried out at a temperature of 245 to 275 t (preferably 250 to 270 t >, generally 0 to 2 kg / cm 2 —G pressure (at 0.2 to 1.5 kg / cm2 — G is preferred). There is no particular limitation on the conversion of esterification at each stage, but it is better to increase the conversion at each stage gradually. The final esterification conversion rate is not less than 90%, and preferably not less than 93%. Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (read the precautions on the back, then fill out this page) Although the esterification reaction can be performed without adding components other than terephthalic acid and ethylene glycol, but Small amounts of basic compounds, such as triamines, such as trimethylamine, tri-n-butylamine, and dimethyl dimethylamine, and quaternary ammonium compounds, such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, and triamine can be added. Methyl benzyl ammonium hydroxide, with additional potassium carbonate, sodium carbonate, potassium carbonate and sodium acetate. It is preferable to add a tertiary compound to the esterification reaction because it can keep the diethylene terephthalate component unit in the main chain of polyethylene terephthalate at a relatively low level. The esterified product (low condensate) obtained through the above-mentioned esterification reaction step usually has a number average molecular weight of 500 to 5000. The prepared esterified product is then supplied to the liquid-phase polycondensation reaction step. "This paper size is applicable to China's Standards (CNS) A4 (210X297 mm) -8- Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7___ V. Description of the invention (6) Liquid-phase polycondensation reaction step 騣 In the liquid-phase polycondensation reaction step, a pressure of not less than the melting point of the polyethylene terephthalate formed is decompressed and polycondensation exists The system is heated under a medium to perform polycondensation, and ethylene glycol formed by the reaction is distilled off from the system. This liquid phase condensation reaction can be carried out in a single or multiple stages. When the liquid-phase condensation reaction proceeds in multiple stages, the first-stage polycondensation reaction is generally at a temperature of 250 to 290 ° C (preferably 260 to 280 ° C), 500 to 20 Torr (200 to 30 Torr) It is preferably carried out under pressure. The final stage of the polycondensation reaction is at a temperature of 265 to 300 ° C (preferably 27 0 to 295 ° C), 10 to 0.1 Torr (5 to 0.1 Torr). Preferably, especially under pressure of 2 to 0.1 Torr). When the liquid-phase polycondensation reaction is carried out in two stages, the conditions of the polycondensation reaction in the first and second stages are respectively in the first and second stages described above. Within the final stage. When the polycondensation reaction is performed in three or more stages, the conditions of the polycondensation reaction in one of the second to final stages are selected from the conditions between the first and final stages described above. For example, when liquid phase polycondensation is performed in three stages, the second stage polycondensation reaction is generally at a temperature of 2 60 to 2 5 5 ° C (preferably 2 70 to 2 8 5 ° C), and generally 50 to 20 Torr (preferably 40 to 5 Torr). The inherent viscosity (IV) of polyethylene terephthalate prepared by the liquid phase polycondensation reaction is not particularly limited, but it is preferable that the inherent viscosity gradually increase with each stage. The intrinsic viscosity (IV) of poly (ethylene terephthalate) produced in the final polycondensation reaction is usually from 0.35 to 0.80d 1 / This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ) I .----.------ ΙΤΛ ------- Order ------ (Please read the notes on the back before filling out this page) -9-Central Ministry of Economic Affairs Inner shell A7 B7 of the local shellfish consumer cooperative V. Description of the invention (,) g, preferably from 0.45 to 0.75 dl / g, more preferably from 0.55 to 0.75 d 1 / g. The intrinsic viscosity (IV) can be calculated from the viscosity of the solution, which is measured in a 25 ° C solution. The solution is heated to dissolve 1.2 g of polyethylene terephthalate in 15 cc of o-chlorophenol. Medium and then made by cooling. The crystallinity of ethylene terephthalate produced in the final phase of the liquid phase polycondensation reaction is usually less than 2% »The liquid phase polycondensation reaction must be performed in the presence of a polycondensation catalyst and a stabilizer. Examples of polycondensation catalysts that can be used herein include germanium compounds, such as germanium dioxide, germanium tetraethoxylate, and tetra-n-butylgermanium oxide; antimony compounds, such as germanium trioxide, antimony acetate, germanium tetraethoxide, and tetra-n-butyl Germanium oxide: and titanium compounds, such as titanium tetrabutoxide and titanium tetrapropionate. Among the polycondensation catalysts, germanium dioxide is preferred because the formed polyethylene terephthalate has good color tone and transparency. Germanium trioxide and antimony acetate are also preferred because the formed poly (ethylene terephthalate) has good crystallinity and hue. Examples of stabilizers are phosphorus compounds, including phosphates, such as trimethyl phosphate, triphosphate Ethyl esters, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, and tricresyl phosphate; phosphites such as triphenyl phosphite, dodecyl phosphite, and trinonylphenyl phosphite ; Acid phosphates such as phosphate formate, isopropyl phosphate, butyrate phosphate, dibutyl phosphate, butyl phosphate, and dioctyl phosphate; phosphoric acid; and polyphosphoric acid. By adding a phosphorus compound to the esterification vessel, the hue and thermal stability of the polyethylene terephthalate formed can be improved. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -10- ---- ^ --- * --- ^ 乂 ------ tr ------ ^- · ≫. {Please read the notes on the back before filling in this page) Printed by the Central Bureau of Gossip Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative A7 B7 __ 5. Description of the invention (8) In the present invention, in addition to the polycondensation catalyst You can add cobalt compounds, manganese compounds or magnesium compounds. Examples of the cobalt compound include cobalt chloride, cobalt sulfate, cobalt hydroxide, cobalt nitrate, cobalt oxalate, cobalt formate, cobalt acetate, fluorenyl α-hydroxyisobutyrate, and cobalt benzoate. The esterification reaction can be accelerated by adding a cobalt compound to the esterification vessel. Examples of the manganese compounds include manganese acetate, fluorenyl α-hydroxyisobutyrate, manganese sulfate, manganese carbonate, and manganese nitrate. The esterification reaction can be accelerated by adding a manganese compound to the esterification vessel. Examples of the magnesium compound include magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium chloride, magnesium carbonate, magnesium citrate, magnesium lactate, and magnesium oxalate. The esterification reaction can be accelerated by adding a magnesium compound to the esterification vessel. The above compounds are usually added in the form of an aqueous solution, and the smaller the amount of water used, the better. Based on 1 mole of terephthalic acid, the use of the phosphorus compound is usually expressed in terms of phosphorus atoms, which is usually 5 to 200 ppm, and 10 to 100 ppm is better * Based on 1 mole of terephthalic acid, the amount of cobalt compound used is expressed in the form of metallic cobalt, usually 5 to 200 ppm, preferably 10 to 60 PP m. Based on 1 mol terephthalic acid, the amount of the manganese compound is expressed in the form of metal M, usually 10 to 200 ppm, and preferably 20 to 1,000 P P m. Based on 1 mol terephthalic acid, the magnesium compound is set on the gold paper scale. Applicable to the two standards (CNS) A4 (2 丨 0X297 mm) (Please read the precautions on the back first) (Fill in this page)
-11 - 經濟部中央標準局貝工消費合作社印製 " A7 B7 五、發明説明（。） 屬鎂表示，通常爲5至200PPm，以1 5至50 p p m爲佳。 以對苯二甲酸與乙二醇之混合物重量爲基礎，該聚縮 觸媒所需用量以聚縮觸媒中之金屬表示，爲0 . 000 5 至0 . 2重置％，以0 . 001至0 . 05重量％爲佳。 以該對苯二甲酸與乙二酵之混合物重量爲基礎，該安 定劑所需用量以安定劑中磷原子表示，爲0 . 0 〇 1至〇 .1重置％以0.002至0.2重量％爲佳。 該聚縮觸媒與安定劑可以進料到下述酯化反應步驟， 或者液相聚縮反應步驟之第一階段反應器中》 如上述，該經由液相聚縮反應步騍製得之聚對苯二甲 酸伸乙酯可能包含自對苯二甲酸以外之二羧酸衍生之組份 單位，以及自乙二醇以外之乙二醇衍生之組份單位，其數 量不多於2 0莫耳％。以全部二羧酸單位爲基礎，所包含 衍生自異苯二甲酸之組份單位數置爲1至5莫耳％特佳。 本發明中，由下列化學式（I )表示之對苯二甲酸伸 乙酯組份單位含量必須在9 5 . 0至9 9 · 0%範圍內， 而下列化學式（I I )表示之對苯二甲酸二氧乙烯組份單 位之含量在1.0至5.0%範圍內： —< ooc~(^)- COOCH2CH2^- …(I) —e〇OC-(^- COOCH2CH2OCH2CH2·)—…(Π) 該最終液相聚縮反應器所製得之聚對苯二甲酸伸乙酯 本紙張尺度適用中國國家揉準（CNS ) Α4规格（210X297公釐) ' " -12- (讀先W讀背面之注f項再填寫本頁) A. 訂· ."> 五、發明説明（ 10 A7 B7 趣濟部中央標準局負工消費合作社印裝 通常由熔融擠模製方法模製成粒狀（小片）。該聚對苯二 甲酸伸乙酯片之平均直徑通常爲2.0至5.0 mm，以2 . 2至4 · 0mm爲佳。然後將液相聚縮反應 步驟所製得無定形或結晶度低於3%之聚對苯二甲酸伸乙 酯片（下文稱爲"PET片〃）進行預結晶步驟》 預結晶步驟 在預結晶步驟中，將P E T片加熱至下文所述進行固 相聚縮反應溫度，或加熱至略低於固相聚縮溫度之溫度下 使該PET片結晶。更特別的是，步驟（A)係以（Ti )不低於Tg (玻璃化溫度）且不高於1 8 0°C之溫度（ T!)爲1 2 0至1 75°C爲佳）加熱該PET片以結 晶於聚對苯二甲酸伸乙酯，至到聚對苯二甲酸伸乙酯結晶 度變成3%或以上爲止》 使用具有攪拌刮刀之水平或垂直攪拌裝置進行步驟（ A)。該攪拌裝置係連續型爲佳，於一側進料PET片， 而自另一側送出該片。 例如，當上述攪拌裝置用於步驟（A)時，該PET 片進料至裝置一側，於其中以經加熱氣流加熱並攪拌之， 並自該裝置另一側送.出。 步驟（A )必須在惰性氣氛中進行。惰性氣體之實例 包括氮氣、氬氣及二氧化碳氣。 該PET片於步驟（A)中之逗留時間（加熱時間） 在1至20分鐘範圍內爲佳，3至10分鐘更佳。 諳 先 面 之 注 意. 事 項 .再-11-Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics " A7 B7 V. Description of the invention (.) It is magnesium, usually 5 to 200 PPm, preferably 15 to 50 p p m. Based on the weight of the mixture of terephthalic acid and ethylene glycol, the required amount of the polycondensation catalyst is expressed by the metal in the polycondensation catalyst, which is 0.005% to 0.2 reset%, and is 0.001 Preferably it is 0.05% by weight. Based on the weight of the mixture of terephthalic acid and glyoxal, the required amount of the stabilizer is represented by the phosphorus atom in the stabilizer, which is 0.0% to 0.1% reset% 0.002 to 0.2% by weight as good. The polycondensation catalyst and stabilizer can be fed to the following esterification reaction step, or the first-stage reactor of the liquid phase polycondensation reaction step. As described above, the polymer obtained through the liquid phase polycondensation reaction step Ethyl terephthalate may contain component units derived from dicarboxylic acids other than terephthalic acid, and component units derived from ethylene glycol other than ethylene glycol, in quantities not exceeding 20 moles %. On the basis of all dicarboxylic acid units, the number of component units derived from isophthalic acid is preferably 1 to 5 mol%. In the present invention, the unit content of the ethylene terephthalate component represented by the following chemical formula (I) must be in the range of 95.0 to 99.0%, and the terephthalic acid represented by the following chemical formula (II) The content of the dioxyethylene component unit is in the range of 1.0 to 5.0%: — < ooc ~ (^)-COOCH2CH2 ^-… (I) —e〇OC-(^-COOCH2CH2OCH2CH2 ·) —... (Π) The final Polyethylene terephthalate prepared by a liquid phase polycondensation reactor. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) '" -12- (Read the first note on the back f) Please fill in this page again. A. Order ·. " > V. Description of the invention (10 A7 B7) The work of the Central Standards Bureau of the Ministry of Interest of the Ministry of Work and Consumer Cooperatives is usually printed into pellets by melt extrusion molding (small pieces) ). The average diameter of the polyethylene terephthalate tablet is usually 2.0 to 5.0 mm, preferably 2.2 to 4.0 mm. Then the liquid phase polycondensation reaction step is used to obtain amorphous or low crystallinity. Pre-crystallization step is performed on a 3% polyethylene terephthalate tablet (hereinafter referred to as " PET sheet〃). Pre-crystallization step In the pre-crystallization step, PE is The T sheet is heated to a temperature for conducting solid phase polycondensation reaction as described below, or the PET sheet is crystallized at a temperature slightly lower than the solid phase polycondensation temperature. More specifically, step (A) is performed with (Ti) not lower than Tg (glass transition temperature) and a temperature not higher than 180 ° C (T!) Is preferably 120 to 75 ° C) The PET sheet is heated to crystallize in polyethylene terephthalate until Until the crystallinity of polyethylene terephthalate becomes 3% or more >> Step (A) is performed using a horizontal or vertical stirring device with a stirring blade. The stirring device is preferably a continuous type, and a PET sheet is fed on one side, and the sheet is fed from the other side. For example, when the above-mentioned stirring device is used in step (A), the PET sheet is fed to one side of the device, heated and stirred by a heated air current therein, and sent out from the other side of the device. Step (A) must be performed in an inert atmosphere. Examples of the inert gas include nitrogen, argon, and carbon dioxide. The stay time (heating time) of the PET sheet in step (A) is preferably in the range of 1 to 20 minutes, and more preferably 3 to 10 minutes.谙 Attention first. Things. Then
Jt 訂 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） • 13 - 五、發明説明（u ) 11 然後，進行步驟（B)，其中加熱該PET片，使其 保持在自（TbD1-40)(以（Tbm_30°C)爲佳， 以（Tbm-20°C)特佳）範圍內之溫度（T2)至高 Tbm，使聚對苯二甲酸伸乙酯結晶至結晶度至少3 0% ，其中Tbm定義爲利用差別掃瞄置熱器（D S C )以 1 0°C / cm加熱率加熱聚對苯二甲酸伸乙酯時，所觀察 之吸熱尖峰之次要尖峰開始吸熱溫度》 當該P E T片係使用D S C進行加熱分析時，在高溫 側觀察到具有大型尖峰區（主要尖峰）之吸熱尖峰，而在 較主要尖峰低溫一側觀察到具有小型尖峰區（次要尖峰之 吸熱尖峰。本發明中，步驟（B )之加熱溫度係由次要尖 峰測得之吸熱開始溫度（Tbm)。 該吸熱尖峰係使用D S C以下列方式測得》 經濟部中央揉準局貝工消费合作社印簟 (請先閲讀背面之注$項再填寫本頁) 將收集自以大約1 4 0°C大約5mmHg壓力乾燥大 約5小時之PET片中央部分大約1〇mg樣本（薄片） 置於氮氣氛中之液體用鋁盤中。封閉該鋁盤，並利用由 Perkin Elmer Co.所製之DSC-2型差別掃瞄量熱器在下列 測量條件下測量吸熱作用。以1 0 t/分加熱率自室溫加 熱該樣本至偵測吸熱尖峰，並發現該偵測吸熱尖峰之開始 吸熱溫度》圖1顯示以DSC測得聚對苯二甲酸伸乙酯之 DSC曲線實例之一。 與步驟（A)不同的是，步驟（B )中不進行攪拌作 用。因此，可使用例如具有接受進料、加熱以及排出 P E T片功能之分批型裝置，或者連續型裝置，其中可於 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） -14- 經濟部中央榣準局MC工消费合作社印装 A7 B7 _— 五、發明説明（^ ) 12 —側進料PET片，該PET片在加熱氣流中藉由重力移 動，並自該裝置另一側排出P ET片。 、加熱該P E T片並維持該情況〃一辭係指加熱期間 未確實攪拌P E T片，包括例如P E T片在加熱裝置中不 流動情況以及PET片在加熱裝置中藉由重力移動（流動 )情況。 當加熱溫度（T2)高於Tbm時，會發生p E T片 結塊或熔融作用。當加熱溫度低於（TbD> — 4 0°C)時 ，該聚對苯二甲酸伸乙酯結晶緩慢，因此預結晶作用所費 時間長。 該次要尖峰之開始吸熱溫度（Tbm)會隨著加熱時 間過去，換言之，隨著結晶作用而升到更高溫一側，因此 利用D S C加熱分析定時進行分析爲佳，並依分析結果爲 基礎改變加熱條件。步驟（B)之加熱條件設爲該PET 片之加熱溫度逐漸增加爲佳。 以分批方法進行之步驟（B )係於最初溫度大約 1 5 0°C而最終溫度大約1 9 0°C之加熱條件下進行爲佳 。以連續方法進行時，測量P E T片之移動率與加熱氣體 之進料率’該入口溫度大約1 5 〇1而出口溫度大約 1 9 0 °C爲佳。 步驟（B )係於步驟（A)所採用之相同情性氣氛下 進行爲佳。 步驟（B)中PET片之加熱時間（連績方法中之逗 留時間）在3 0分鐘至5小時範圃內，以1至3小時爲隹 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐) I----1------II (請先閲讀背面之注$項再填寫本頁) 訂 -15- 經濟部中央標準局貝工消费合作社印裝 A7 B7___ 五、發明説明（13 ) 0 然後，自前述溫度（T2)加熱該PET片至固相聚 縮溫度並攬拌之，進行步驟（C) 步驟（C )係於步驟（A)所使用之相同攪拌裝置中 進行。該攪拌裝置以連續型爲佳，於其一側進料P E T片 ，自另一側排出該片。 例如，步驟（C)使用上述攬拌裝置，由其一側進料 P E T片，邊it拌邊於加熱氣流中加熱，並自該裝置另一 側排出。 步驟（C )在上述相同惰性氣氛下進行爲佳。 步驟（C)中之PET片逗留時間（加熱時間）在1 至2 0分鐘範圍內，以3至1 0分鐘爲佳。 經由步驟（A)至（C)所組成之預結晶步驟，聚對 苯二甲酸伸乙酯結晶至至少3 0%結晶度，以4 5%爲佳 。然後將預結晶之P E T片進行固相聚縮反應步驟。 固相聚縮反應步驟 該固相聚縮反應步驟包括至少一個階段，而且在溫度 —般爲190至230 °C (以195至225 °C爲佳）與 一般爲1 k g/cm2 — G至1 〇托耳（以大氣壓力至 1 0 0托耳爲佳）之壓力條件下進行，聚合時間1至5 0 小時’以5至2 0小時爲佳。該固相聚縮反應係於情性氣 氛’諸如氮氣、氬氣或二氧化碳氣下進行爲佳》此等惰性 氣氛中，以氮氣爲佳。亦可於較高溫減壓下進行該固相聚 本紙張尺度適用中國國家揉準（CNS λΑ4规格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 -16- 經濟部中央樣隼局貝工消費合作社印製 A7 B7___ 五、發明説明（） 14 縮作用。 經由該固相聚縮反應製得之聚對苯二甲酸伸乙酯之固 有粘度通常不小於0 · 5d Ι/g，不小於〇 . 54 d 1/g爲佳，不小於0 . 70d 1/g更隹，不小於 0.72d1/g特佳，密度通常不小於1.37 g/cm3，不小於1 . 38g/cm3爲佳，不小於 1 . 39g/cm3更佳》 該聚對苯二甲酸伸乙酯包含之齊聚物（以上述化學式 (I )表示之苯二甲酸伸乙酯組份單位之環形三聚物）含 量不多於0 . 6重量％，不多於0 . 5重量％爲佳，不多 於0 . 4 5重量％更佳，不多於0 . 4重量％特佳》 本發明效應 根據本發明方法，可以有效地達成聚對苯二甲酸伸乙 酯之預結晶作用，而且不會產生P E T片結塊或熔融。另 外，即使是經共聚聚對苯二甲酸伸乙酯之預結晶條件亦可 輕易決定》 實施例 參照下列實施例另外說明本發明，但是必須解釋的是 本發明不受限於該實施例。 實施例1 在一個由第一至第四容器型反應器以及第五水平雙螺 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） (讀先W讀背面之注意事項再填寫本頁)Jt paper size is applicable to China National Standard (CNS) A4 (210X297 mm) • 13-V. Description of Invention (u) 11 Then, proceed to step (B), where the PET sheet is heated to keep it at (TbD1-40) (preferably (Tbm_30 ° C), especially (Tbm-20 ° C)) at a temperature (T2) to high Tbm, so that the polyethylene terephthalate crystallizes to at least crystallinity 30%, where Tbm is defined as the temperature at which the secondary peak of the observed endothermic peak of the endothermic peak starts when the polyethylene terephthalate is heated by a differential scanning heater (DSC) at a heating rate of 10 ° C / cm 》 When the PET sheet was subjected to heating analysis using DSC, endothermic spikes with large spikes (primary spikes) were observed on the high temperature side, and small spikes (heat absorption of minor spikes) were observed on the lower temperature side than the major spikes. Spike. In the present invention, the heating temperature in step (B) is the endothermic start temperature (Tbm) measured from the minor spike. The endothermic spike is measured using DSC in the following manner. Seal (please read the note $ on the back before (Fill in this page) Approximately 10 mg of the sample (flakes) collected from the central part of the PET sheet dried at a pressure of about 5 mmHg at about 140 ° C for about 5 hours is placed in an aluminum pan for liquid in a nitrogen atmosphere. The aluminum pan is closed The DSC-2 differential scanning calorimeter made by Perkin Elmer Co. was used to measure the endothermic effect under the following measurement conditions. The sample was heated from room temperature at a heating rate of 10 t / min to detect the endothermic spike, and Found that the endothermic peak of the detected endothermic peak "Figure 1 shows one of the DSC curve examples of polyethylene terephthalate measured by DSC. Unlike step (A), stirring is not performed in step (B) Therefore, for example, a batch type device or a continuous type device with functions of receiving feed, heating, and discharging PET flakes can be used, in which the Chinese National Standard (CNS) A4 specification (210X297 mm) can be applied to this paper size. -14- A7 B7 is printed by MC Industrial Consumer Cooperatives of Central Bureau of Standards, Ministry of Economic Affairs _— V. Description of the Invention (^) 12 — The side feeds the PET sheet, which is moved by gravity in a heated air stream, and from the device The other side discharges the P ET sheet. Heating the PET sheet and maintaining it is a term that refers to the fact that the PET sheet is not agitated during heating, including, for example, the case where the PET sheet does not flow in the heating device and the PET sheet moves (flows) by gravity in the heating device. When heating When the temperature (T2) is higher than Tbm, agglomeration or melting of the p ET sheet may occur. When the heating temperature is lower than (TbD >-40 ° C), the polyethylene terephthalate crystallizes slowly, so The crystallization takes a long time. The starting endothermic temperature (Tbm) of this minor spike will increase with the elapse of heating time, in other words, it will rise to a higher temperature side with crystallization, so it is better to use DSC heating analysis for regular analysis and change based on the analysis results. Heating conditions. It is preferable that the heating condition in step (B) is that the heating temperature of the PET sheet is gradually increased. The step (B) performed by a batch method is preferably performed under heating conditions of an initial temperature of about 150 ° C and a final temperature of about 190 ° C. In the continuous method, it is better to measure the moving rate of the PET sheet and the feed rate of the heated gas. The inlet temperature is about 15001 and the outlet temperature is about 190 ° C. Step (B) is preferably performed under the same sympathetic atmosphere used in step (A). In step (B), the heating time of the PET sheet (the dwell time in the continuous method) is within 30 minutes to 5 hours, with 1 to 3 hours as the standard. The paper size is applicable to the Chinese National Standard (CNS) A4. (210X297 mm) I ---- 1 ------ II (Please read the note on the back before filling in this page) Order-15- Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7___ Five Description of the invention (13) 0 Then, the PET sheet is heated from the aforementioned temperature (T2) to the solid-phase polycondensation temperature and stirred, and step (C) is performed. Step (C) is the same stirring device used in step (A). In progress. The stirring device is preferably a continuous type, and a P E T sheet is fed on one side, and the sheet is discharged from the other side. For example, in step (C), the above-mentioned mixing device is used, and the P E T sheet is fed from one side thereof, heated in a heating air stream while it is stirred, and discharged from the other side of the device. Step (C) is preferably performed under the same inert atmosphere as described above. The stay time (heating time) of the PET sheet in the step (C) is in the range of 1 to 20 minutes, and preferably 3 to 10 minutes. Through the pre-crystallization step consisting of steps (A) to (C), the polyethylene terephthalate crystallizes to at least 30% crystallinity, preferably 45%. The pre-crystallized P E T sheet is then subjected to a solid phase polycondensation reaction step. Solid-phase polycondensation reaction step This solid-phase polycondensation reaction step includes at least one stage, and the temperature is generally 190 to 230 ° C (preferably 195 to 225 ° C) and generally 1 kg / cm2-G to 100 Torr. It is carried out under the pressure condition of the ear (preferably atmospheric pressure to 100 Torr), and the polymerization time is from 1 to 50 hours', preferably from 5 to 20 hours. The solid-phase polycondensation reaction is preferably performed in an inert atmosphere such as nitrogen, argon, or carbon dioxide. In such an inert atmosphere, nitrogen is preferred. This solid-phase polymerization can also be performed at a higher temperature and reduced pressure. The paper size is applicable to Chinese national standards (CNS λΑ4 size (210X297 mm) (Please read the precautions on the back before filling out this page). A7 B7___ printed by the Bureau of Shellfish Consumer Cooperatives V. Explanation of the invention () 14 Shrinkage. The inherent viscosity of polyethylene terephthalate produced through the solid-phase polycondensation reaction is usually not less than 0 · 5d Ι / g, Not less than 0.54 d 1 / g, more preferably not less than 0.70d 1 / g, particularly not less than 0.72d1 / g, density is usually not less than 1.37 g / cm3, and preferably not less than 1.38g / cm3 , Not less than 1. 39g / cm3 is better》 Content of the oligomer (cyclic terpolymer of the ethylene terephthalate component unit represented by the above chemical formula (I)) contained in the polyethylene terephthalate Not more than 0.6% by weight, not more than 0.5% by weight, more preferably not more than 0.45% by weight, not more than 0.4% by weight are particularly preferred "Effect of the present invention According to the method of the present invention , Can effectively achieve the pre-crystallization of polyethylene terephthalate, and will not produce agglomeration or melting of PET sheet. In addition, even the pre-crystallization conditions of copolymerized poly (ethylene terephthalate) can be easily determined. EXAMPLES The present invention will be further explained with reference to the following examples, but it must be explained that the present invention is not limited to this example. Implementation Example 1 In the first to fourth container-type reactors and the fifth horizontal double-spiral paper, the Chinese national standard (CNS) A4 size (210X297 mm) is applied. (Read the precautions on the back before filling in this. page)
-17- 經濟部中央樣準局貝工消费合作社印製 A7 B7 五、發明説明（u) 15 旋旋轉型反應器所組成之連續聚縮反應裝置中，以下列方 式連續進行乙二醇與對苯二甲酸之聚縮作用，以製備聚對 苯二甲酸伸乙酯（PET) » 在第一反應器中事先置入3 7 5 0重量份數之反應溶 液，其邊攪拌於氮氣氛中保持2 5 5 °C與1 . 7 kg/cm2 — G。將藉由混合高純度對苯二甲酸、乙二 醇以及三氧化銻所製備之漿液連續進料至第一反應器，其 方式係該高純度對苯二甲酸以每小時1 4 3 7重量份數速 率進行，乙二酵以每小時6 4 5重量份數速率進料，而三 氧化銻係以每小時0.57重量份數速率進料，進行第一 階段酯化反應，期間每小時餾除2 0 3重量份數的水以及 3重置份數乙二醇。控制第一階段酯化反應使該漿液平均 逗留時間變成2 . 0小時。將第一反應器排出之漿液連續 導入保持260 °C及0 . 8kg/cm2 — G之第二容器 中並邊搅拌之。 將8 5%磷酸與乙二醇均勻溶液連續進料到第二反應 器，其方式係以每小時0 . 4 6重量份數速率進料該8 5 %磷酸，以每小時9重量份數速率進料該乙二醇，並且分 別以每小時8 4重量份數速率以及每小時7重量份數速率 連續餾除水及乙二醇，以進行第二階段酯化反應，並控制 使該漿液平均逗留時間變成2. 0小時》將第二反應器排 出之漿液連續送入保持在2 7 5及7 OmmHg之第三反 應器中並攪拌之。 第三反應器中，分別以每小時6 2重量份數速率及每 本紙張尺度適用中國國家揉丰（CNS ) A4规格（210X297公釐） (請先Μ讀背面之注意事項再填寫本頁) 訂 -18 - 經濟部中央標準局貝工消费合作社印氧 A7 B7_____ 五、發明説明（） 16 小時6重量份數速率連績饍除乙二酵與水，以進行第一階 段聚縮反庚，控制使其反應混合物之平均逗留時間變.爲1 • 0小時/將第三反應器所排出之聚縮反應產物連績送到 保持在2 8 0°C及5mmHg之第四反應器中，並攪拌之 〇 第四反應器中，分別以每小時2 6重童份數速率及每 小時3重量份數速率餾除乙二酵與水，控制使該反應混合 物平均逗留時間變成1.〇小時。將第四反應器排出之聚 縮反應產物連續導入保持在2 8 2至2 8 5 °C及1 .8至 2 . 5mmHg之第五反應器（水平雙螺旋旋轉型反應容 器）並攪拌之。 第五反應器中，分別以每小時1 2重量份數速率與每 小時，重量份數速率餾除乙二醇與水，進行第三階段聚縮 反應，控制使該聚縮反應產物之平均逗留時間變成2 . 5 小時。利用聚酯拉絲機將該聚縮反應產物以線形式自反應 器連續拉出。然後將該線浸在水中冷卻並以線裁切機裁切 ，製得片狀形式聚對苯二甲酸伸乙酯。 以上述液相聚縮作用製得之聚對苯二甲酸伸乙酯之固 有粘度（於25°C鄰氯酚中測量）爲0 . 58d Ι/g， 二乙二醇單位含置爲Ο . 9 5重量％，而以密度方法測量 之結晶度爲1 % 〇 然後，將上述製得之聚對苯二甲酸伸乙酯液相聚縮片 連續進料至如圖2所亦之反應裝置，其包括水平連續加熱 容器2、垂直連續加熱容器3、水平連續加熱容器4 ,以 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐) (讀先閲讀背面之注項再填寫本頁 λ. •19- 經濟部中央梯準局貝工消费合作社印製 A7 B7 五、發明説明（） 17 及液相聚縮反應容器7，以進行預結晶作用及固相聚縮反 應。參照圓2，數字1表示進料漏斗、數字5表示空氣， 淸潔器、數字6表示空氣加熱器、數字8表示冷卻器、數 字9表示氮淸潔器、數字10表示鼓風器而數字11表示 加熱器β 預結晶作用之一般程序： 在反應裝置之水平連續加熱容器2中進行步驟（A ) 。在容器2—側進料該聚對苯二甲酸伸乙酯液相聚縮片， 然後邊攪拌邊加熱，並由該容器另一側排出。在垂直連續 加熱容器3中進行步驟（B) »將通過步驟（A)之聚對 苯二甲酸伸乙酯片進料至容器3頂部，然後於氮氣流中加 熱並自容器底部排出。在此垂直連續加熱容器3中，以重 力移動該聚對苯二甲酸伸乙酯片。使用水平連續加熱容器 4進行步驟（C)。將通過步驟（B)之聚對苯二甲酸伸 乙酯片進料至容器4的一側，然後搅拌加熱之，並由容器 另一側排出。 將以上述方式製備之聚對苯二甲酸伸乙酯液相聚縮片 , ' (其結度度1 . 0%，溫度50°C)進料至步驟（A)所 用之水平連續加熱容器2 —側，並以1 7 0 °C氣氛溫度加 熱攪拌之，逗留時間3分鐘。以DSC測量之步驟（A) 製得之聚對苯二甲酸伸乙酯次要尖峰之開始吸熱溫度（ Tbm)爲1 7 5°C。以密度方法測量，此聚對苯二甲酸 伸乙酯之結晶度爲41%，步驟（A)片之出口溫度爲 本紙張尺度適用中國國家梂準（CNS ) A4规格（2丨0父297公兼1 —a·—-n_i M—9 aT— ^^^1 emmi ϋ -d (請先閲讀背面之注意事項再填寫本頁) 訂 ^ -20- 經濟部中央梂準局貝工消费合作社印裝 A7 B7 五、發明説明（) 18 1 7 0 t。 然後將步驟（A)之聚對苯二甲酸片進料至步驟（B )所用之水平活塞式流動連續加熱容器3，並以1 7 0°C 氣氛溫度加熱，逗留時間1 〇 8分》以密度方法測量，步 驟（B )所製得之聚對苯二甲酸伸乙酯結晶度爲4 8%， Tbn«爲183°C。步驟（B)片之出口溫度爲170°C。 然後將步驟（B )之聚對苯二甲酸伸乙酯片進料至步 驟（C )用之水平連續加熱容器4，以2 1 2 °C氣氛溫度 加熱並攪拌之，逗留時間1 2 5秒。以密度方法測量，步 驟（C )所製得之聚對苯二甲酸伸乙酯結晶度爲5 1 %。 然後在固相聚縮反應容器7中將上述預結晶步驟所製 得之聚對苯二甲酸伸乙酯片在2 1 0°C氮氣氛中加熱1 5 小時，進行固相聚縮作固。 上述每個步驟中可製備不會產生結塊或熔融之聚對苯 二甲酸伸乙酯片。 官施例2 以實施例1相同方式製備聚對苯二甲酸伸乙酯，但是 使用1 3 9 4重量份數高純度對苯二甲酸與4 3重量份數 異苯二甲酸代替1 4 3 7重量份數高純度對苯二甲酸，該 三氧化銻用量改成0 . 4 6重量份數，8 5%磷酸用量改 成0.20重量份數。 所形成之聚對苯二甲酸伸乙酯液相聚縮片之固有粘度 於25t鄰氣酚中測量，爲0 . 60d l/g，二甘酯單 本纸張尺度適用中國國家揉準（CNS > A4规格（210X297公釐） (請先閲讀背面之注項再填寫本頁) 訂 -21 - 經濟部中央標準局貝工消费合作社印装 A7 B7 五、發明説明（） 19 位含量爲0 · 9 8重量％，以密度方法測量之結晶度爲1 然後’使用圖2所示之反應裝置對上述製備之聚苯二 甲酸伸乙酯液相聚縮片進行預結晶作用與固相聚縮作用》 將結晶度爲0 . 9，溫度爲5 0 °C之聚對苯二甲酸液 相聚縮片先進料至步驟（A)所用之具備攪拌刮刀的水平 連續加熱容器2中’以17 0°C氣氛溫度加熱該片，逗留 時間2 . 5小時。以DSC測量步驟（A)所製得對苯二 甲酸伸乙酯次要尖峰之開始吸熱溫度（Tbm)爲1 7 4 °C。以密度方法測量，該聚對苯二甲酸伸乙酯之結晶度爲 3 9%。步驟（A)之片於出口溫度爲1 6 5eC。步驟（ A)中，不會產生該片結塊現象。 然後將聚對苯二甲酸伸乙酯片進料至步驟（B )所用 之垂直連續加熱容器3，其中以1 7 0°C氣氛溫度加熱該 片，該溫度低於1 7 4°C之開始吸熱溫度，逗留時間 1 1 8分鐘。以密度方法測量步驟（B)所製得之聚對苯 二甲酸伸乙酯結晶度爲4 5%，Tbm爲1 8 5°C，出口 溫度1 7 0 0 然後將步驟（B )之聚對苯二甲酸伸乙酯片進料至步 驟（C)所用之水平連續加熱容器4，其中以2 1 2°C氣 氛溫度加熱該片，逗留時間1 3 3秒，並撹拌之。以密度 方法測量，步驟（C )所製得之聚對苯二甲酸伸乙酯結晶 度爲48%，出口溫度爲209 °C。步驟（C)中，不會 產生該片結塊或熔融。然後將該聚對苯二甲酸伸乙酯進料 本纸張尺度適用ts國家揉準（CNS ) A4规格（210X297公m —ί 1—τ"ΐ (請先閱讀背面之注意Ϋ項再填寫本頁) •tr -22- 經濟部中央揉準局員工消费合作社印裝 A7 £7_ 五、發明説明（） 20 至固相聚縮反應容器7，以進行固相聚縮反應。此步驟中 ’不會發生該片之結塊或熔融。 實施例3 將實施例2步驟（A)中製得之聚對苯二甲酸伸乙酯 進料至步驟（B)所用之垂直流塞式流動連續加熱容器3 中，其中以1 7 0°C氣氛溫度加熱該片，該溫度低於聚對 苯二甲酸伸乙酯之開始吸熱溫度，逗留時間爲6 3分鐘》 以密度方法測得步驟（B)製得之聚對苯二甲酸伸乙酯結 晶度爲43%，Tbm爲1 79°C，出口溫度1 70°C » 然後將步驟（B)之聚對苯二甲酸伸乙酯片進料到步 驟（C )所用之水平連續加熱容器4，以2 1 2 °C氣氛溫 度加熱，逗留時間7 1秒，並攪拌之》以密度方法測量步 驟（C )製得之聚對苯二甲酸伸乙酯結晶度爲4 9%，出 口溫度爲2 0 2 °C。 然後，將上述預結晶步驟製得之聚對苯二甲酸伸乙酯 片在固相聚縮反應容器7中以2 1 0 °C氮氣氛下加熱1 5 小時，進行固相聚縮反應。 上述每個步驟中，可製備不產生結塊或熔融之聚對苯 二甲酸伸乙酯片。 對照實例1 使用圖2所示之反應裝置，預結晶以實施例2相同方 式製備之聚對苯二甲酸伸乙酯液相聚縮片。 本紙張尺度適用中國國家揲準（CNS ) A4规格（2丨0)<297公# ) ——•—ϋ1 - ^^1 n 卜 i ^^1 βι^Λιί· -- 1 (請先Η讀背面之注意事項再填寫本頁) 訂 -23 - 經濟部中央樣準局員工消费合作社印装 A7 _____B7___ 五、發明説明（） 21 將聚對苯二甲酸伸乙酯液相聚縮片進料至步驟（A) 所用具備攪拌刮刀之水平連續加熱容器2，其中以1 7 0 °C溫度加熱該片。逗留時間1分鐘後，以該片出口溫度 1 2 5 °C將該片排出容器2。以D S C測量步驟（A )所 製得聚對苯二甲酸伸乙酯之開始吸熱溫度（Tbm)，爲 1 6 Ot。以密度方法測量，該聚對苯二甲酸伸乙酯之結 晶度爲1 . 6 %。 然後將步驟（A)之聚對苯二甲酸伸乙酯片進料至步 驟（B )所用之垂直連續加熱容器3，並以1 6 5 °C加熱 。不過，發生片狀物結塊，因此無法在隨後步驟中加熱。 對照實例2 使用圖2所示之反應裝置預結晶實施例2相同方式所 製備之聚對苯二甲酸伸乙酯液相聚縮片。 將聚對苯二甲酸伸乙酯液相聚縮片進料至步驟（A) 所用之水平連續加熱容器2，並以1 7 0°C氣氛溫度加熱 。逗留時間1.5分鐘後，以片狀物出α溫度135t將 該片送出容器2。以DSC測量該步驟（A)製得之聚對 苯二甲酸伸乙酯開始吸熱溫度爲1 6 8°C。以密度方法測 量，該聚對苯二甲酸伸乙酯之結晶度爲3% » 然後將步驟（A)製備之聚對苯二甲酸伸乙酯片進料 至步驟（B)所用之垂直連續加熱容器3。步驟（B)中 加熱該片之溫度爲1 7 0°C，其高於1 6 8°C之開始吸熱 溫度（Tbm)，逗留時間4 0分鐘。以密度方法測置步 本紙張尺度適用中國國家標準（CNS ) Α4规格（210X297公釐） (請先閲讀背面之注項再填寫本頁)-17- Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (u) In a continuous polycondensation reaction device consisting of a rotary-rotation reactor, ethylene glycol and Polycondensation of phthalic acid to prepare polyethylene terephthalate (PET) »In the first reactor, 3750 parts by weight of the reaction solution is placed in advance, and it is kept in a nitrogen atmosphere while stirring 2 5 5 ° C and 1.7 kg / cm2 — G. The slurry prepared by mixing high-purity terephthalic acid, ethylene glycol, and antimony trioxide was continuously fed to the first reactor in a manner that the high-purity terephthalic acid was 1 4 3 7 parts by weight per hour The feed rate is 6 to 5 parts by weight per hour, while the antimony trioxide is fed at a rate of 0.57 parts by weight per hour. The first stage of the esterification reaction is carried out, during which 2 are distilled off per hour. 0 3 parts by weight of water and 3 reset parts of ethylene glycol. The first stage esterification reaction was controlled so that the average residence time of the slurry became 2.0 hours. The slurry discharged from the first reactor was continuously introduced into a second container maintained at 260 ° C and 0.8 kg / cm2-G and stirred. 85% phosphoric acid and a homogeneous solution of ethylene glycol were continuously fed to the second reactor by feeding the 85% phosphoric acid at a rate of 0.46 parts by weight per hour at a rate of 9 parts by weight per hour Feed the ethylene glycol, and continuously distill off water and ethylene glycol at a rate of 84 parts by weight per hour and a rate of 7 parts by weight per hour to perform the second-stage esterification reaction and control to average the slurry The residence time becomes 2.0 hours. "The slurry discharged from the second reactor is continuously fed into a third reactor maintained at 275 and 70 mmHg and stirred. In the third reactor, at the rate of 62 parts by weight per hour and the size of each paper, the Chinese national kneading (CNS) A4 specification (210X297 mm) is applicable (please read the precautions on the back before filling this page) ORDER-18-Printed oxygen A7 B7_____ of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () 16 hours 6 parts by weight rate continuous elimination of adipic acid and water for the first stage of polycondensation Control the average residence time of the reaction mixture to be changed to 1 • 0 hours / send the polycondensation reaction product discharged from the third reactor to the fourth reactor maintained at 28 ° C and 5 mmHg, and In the fourth reactor of agitation, the glyoxin and water were distilled off at a rate of 26 weight parts per hour and 3 weight parts per hour, respectively, so that the average residence time of the reaction mixture became 1.0 hour. The polycondensation reaction product discharged from the fourth reactor was continuously introduced into a fifth reactor (horizontal double-helix rotating type reaction container) maintained at 2 8 to 2 8 5 ° C and 1.8 to 2.5 mmHg and stirred. In the fifth reactor, ethylene glycol and water are distilled off at a rate of 12 parts by weight per hour and per hour at a rate of parts by weight, and a third stage polycondensation reaction is performed to control the average residence of the polycondensation reaction product. The time becomes 2.5 hours. The polycondensation reaction product was continuously pulled out of the reactor in a linear form using a polyester drawing machine. The thread was then immersed in water to cool and cut with a thread cutter to obtain a sheet of polyethylene terephthalate. The inherent viscosity of polyethylene terephthalate (measured at 25 ° C o-chlorophenol) prepared by the above-mentioned liquid phase polycondensation is 0.58d Ι / g, and the diethylene glycol unit content is 0. 95% by weight, and the degree of crystallinity measured by the density method is 1%. Then, the poly (ethylene terephthalate) liquid-phase polycondensation sheet prepared above was continuously fed to the reaction device shown in FIG. 2, It includes a horizontal continuous heating container 2, a vertical continuous heating container 3, and a horizontal continuous heating container 4. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (read the notes on the back before filling in this Page λ. • 19- Printed by A7 B7, Shellfish Consumer Cooperatives, Central Government Bureau of the Ministry of Economic Affairs 5. Description of the invention () 17 and liquid-phase polycondensation reaction container 7 for pre-crystallization and solid-phase polycondensation reactions. Refer to circle 2 The number 1 indicates the feed funnel, the number 5 indicates air, the cleaner, the number 6 indicates an air heater, the number 8 indicates a cooler, the number 9 indicates a nitrogen cleaner, the number 10 indicates an air blower, and the number 11 indicates a heater. General procedure of β pre-crystallization: Step (A) is performed in a flat continuous heating container 2. The polyethylene terephthalate liquid phase polycondensation sheet is fed on the side of the container 2 and then heated while stirring and discharged from the other side of the container. Step (B) is performed in the vertical continuous heating container 3 »The polyethylene terephthalate flakes passed through step (A) are fed to the top of the container 3, and then heated in a nitrogen stream and discharged from the bottom of the container. Here vertical In the continuous heating container 3, the polyethylene terephthalate sheet is moved by gravity. Step (C) is performed using a horizontal continuous heating container 4. The polyethylene terephthalate sheet passed through step (B) is fed. To one side of container 4, and then stirred and heated, and discharged from the other side of the container. Polyethylene terephthalate liquid-phase polycondensation sheet prepared in the above manner, '(its degree of knot 1.0% , Temperature 50 ° C) Feed to the horizontal continuous heating container 2 side used in step (A), and heat and stir it at 170 ° C atmosphere temperature, the residence time is 3 minutes. Measured by DSC in step (A). The starting endothermic temperature (Tbm) of the secondary spike of polyethylene terephthalate was 17 5 ° C. Measured by density method, the crystallinity of this poly (ethylene terephthalate) is 41%, and the exit temperature of step (A) is based on the paper standard. Applicable to China National Standard (CNS) A4 (2 297 public and 1 —a · —-n_i M—9 aT— ^^^ 1 emmi ϋ -d (Please read the notes on the back before filling out this page) Order ^ -20- Consumption by shellfish of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative printed A7 B7 V. Description of the invention () 18 1 7 0 t. Then the polyterephthalic acid sheet of step (A) is fed to the horizontal piston flow continuous heating container 3 used in step (B), and 1 70 ° C Heating at atmospheric temperature, residence time 108 minutes "Measured by density method, the crystallinity of polyethylene terephthalate obtained in step (B) is 48%, and Tbn« is 183 ° C . The outlet temperature of step (B) is 170 ° C. Then, the polyethylene terephthalate sheet in step (B) is fed to the horizontal continuous heating container 4 used in step (C), and it is heated and stirred at an atmospheric temperature of 2 12 ° C, and the residence time is 1 2 5 seconds. . As measured by density method, the crystallinity of the polyethylene terephthalate obtained in step (C) was 51%. Then, in the solid-phase polycondensation reaction container 7, the polyethylene terephthalate sheet obtained in the above-mentioned precrystallization step was heated in a nitrogen atmosphere at 210 ° C for 15 hours to perform solid-phase polycondensation. In each of the above steps, polyethylene terephthalate tablets can be prepared without agglomeration or melting. Guanshi Example 2 Polyethylene terephthalate was prepared in the same manner as in Example 1, except that 1 3 9 4 parts by weight of high-purity terephthalic acid and 4 3 parts by weight of isophthalic acid were used instead of 1 4 3 7 For high-purity terephthalic acid, the amount of antimony trioxide is changed to 0.46 parts by weight, and the amount of 8 5% phosphoric acid is changed to 0.20 parts by weight. The inherent viscosity of the formed poly (ethylene terephthalate) liquid-phase polycondensation tablets was measured in 25t o-phenol, and it was 0.60d l / g. > A4 size (210X297 mm) (Please read the note on the back before filling this page) Order-21-Printed by A7 B7, Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of invention () 19-bit content is 0 · 98% by weight, the degree of crystallinity measured by the density method is 1 and then using the reaction device shown in FIG. 2 to perform precrystallization and solid phase polycondensation on the poly (ethylene terephthalate) liquid-phase polycondensation tablet prepared above. 》 Polycrystalline poly (terephthalic acid) liquid polycondensation tablets with a crystallinity of 0.9 and a temperature of 50 ° C into the horizontal continuous heating container 2 with a stirring blade used in step (A) 'at 17 0 ° The sheet was heated at an atmospheric temperature of C, and the residence time was 2.5 hours. The starting endothermic temperature (Tbm) of the secondary peak of ethylene terephthalate prepared by DSC measurement step (A) was 17 4 ° C. With density According to the method, the crystallinity of the polyethylene terephthalate was 39%. The temperature is 1 6 5eC. In the step (A), the sheet does not agglomerate. Then the polyethylene terephthalate sheet is fed to the vertical continuous heating container 3 used in the step (B), where 1 is The sheet was heated at 70 ° C, the temperature was lower than the endothermic temperature of 174 ° C, and the residence time was 118 minutes. The polyethylene terephthalate obtained in step (B) was measured by density method. The crystallinity of the ester is 45%, the Tbm is 18.5 ° C, and the outlet temperature is 1700. Then the polyethylene terephthalate flakes in step (B) are fed to the level used in step (C) for continuous heating. Container 4, in which the sheet is heated at an atmospheric temperature of 2 1 2 ° C for a residence time of 13 seconds and mixed. The density of the polyethylene terephthalate obtained in step (C) is measured by the density method. It is 48% and the outlet temperature is 209 ° C. In step (C), the sheet does not agglomerate or melt. Then the polyethylene terephthalate is fed. CNS) A4 size (210X297mm — — 1—τ " ΐ (Please read the note on the back before filling out this page) • tr -22- Central Ministry of Economic Affairs A7 £ 7_ printed on the cooperative of the staff of the prospective bureau. 5. Description of the invention () 20 to the solid-phase polycondensation reaction container 7 to carry out the solid-phase polycondensation reaction. In this step, no agglomeration or melting of the tablet will occur. The polyethylene terephthalate obtained in the step (A) of Example 2 was fed into the vertical flow plug type continuous continuous heating vessel 3 used in the step (B), and heated at an atmospheric temperature of 170 ° C. The temperature of the sheet is lower than the endothermic temperature of polyethylene terephthalate and the residence time is 63 minutes. The crystallinity of the polyethylene terephthalate obtained in step (B) is measured by the density method. 43%, Tbm 1 79 ° C, outlet temperature 1 70 ° C »Then feed the polyethylene terephthalate flakes from step (B) to the level used in step (C) to continuously heat the container 4 to 2 Heating at an atmospheric temperature of 1 2 ° C, a residence time of 71 seconds, and stirring. The crystallinity of the polyethylene terephthalate obtained in step (C) measured by density method is 49%, and the outlet temperature is 2 0 2 ° C. Then, the polyethylene terephthalate sheet obtained in the above pre-crystallization step was heated in a solid-phase polycondensation reaction container 7 under a nitrogen atmosphere at 210 ° C for 15 hours to perform a solid-phase polycondensation reaction. In each of the above steps, poly (ethylene terephthalate) tablets can be prepared without agglomeration or melting. Comparative Example 1 Using a reaction apparatus shown in FIG. 2, a poly (ethylene terephthalate) liquid polycondensation tablet prepared in the same manner as in Example 2 was pre-crystallized. This paper size applies to China National Standards (CNS) A4 specifications (2 丨 0) < 297 公 #) —— • —ϋ1-^^ 1 n i ^^ 1 βι ^ Λιί ·-1 (Please first (Please read the notes on the back, and then fill out this page) Order-23-Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs A7 _____B7___ V. Description of the invention () 21 Feed Polyethylene Terephthalate Liquid Polycondensation Tablets Up to step (A), the horizontal continuous heating container 2 equipped with a stirring blade is used, and the sheet is heated at 170 ° C. After a residence time of 1 minute, the tablet was discharged from the container 2 at an outlet temperature of the tablet of 1 2 5 ° C. The DSC measurement of the starting endothermic temperature (Tbm) of the polyethylene terephthalate obtained in step (A) was 16 Ot. As measured by density method, the crystallinity of the polyethylene terephthalate was 1.6%. Then, the polyethylene terephthalate sheet of step (A) is fed to the vertical continuous heating container 3 used in step (B), and heated at 16 ° C. However, agglomeration of the flakes occurred and therefore could not be heated in subsequent steps. Comparative Example 2 A poly (ethylene terephthalate) liquid polycondensate prepared in the same manner as in Example 2 was pre-crystallized using a reaction apparatus shown in FIG. The polyethylene terephthalate liquid-phase polycondensation sheet was fed to the horizontal continuous heating container 2 used in step (A), and heated at an atmospheric temperature of 170 ° C. After a dwell time of 1.5 minutes, the sheet was sent out of the container 2 at a temperature of 135 t, which was the temperature at which the sheet came out. The starting endothermic temperature of the polyethylene terephthalate obtained in this step (A) was measured by DSC at 168 ° C. Measured by density method, the crystallinity of the polyethylene terephthalate is 3% »Then, the polyethylene terephthalate sheet prepared in step (A) is fed to the vertical continuous heating used in step (B) Container 3. The temperature of heating the sheet in step (B) is 170 ° C, which is higher than the endothermic temperature (Tbm) of 168 ° C, and the residence time is 40 minutes. Measured by density method This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the note on the back before filling this page)
-IWL -24 - 經濟部中央梯準局貝工消费合作社印装 A7 B7 _ 五、發明説明（） 22 驟（B )所製得聚對苯二甲酸伸乙酯結晶度爲4 0%。步 驟（B )中發生片狀物結塊，因此隨後步驟無法加熱。 附圖簡述 圖1顯示以D S C測得之聚對苯二甲酸伸乙酯之 D S C曲線實例之一。 圖2係實施例中加熱裝置之示意圖。 1 :進料漏斗 2 :水平連續加熱容器 3 :垂直連續加熱容器 4 :水平連續加熱容器 5 :空氣淸潔器 6 :空氣加熱器 7 :固相聚縮反應容器 8 :冷卻器 9 :氮氣淸潔器 1 0 :吹氣器 1 1 :加熱器 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） n·—' ^^^1 m· I— m —m n I - · / (請先閲讀背面之注意事項再填寫本頁) 訂 -25--IWL -24-Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives A7 B7 _ V. Description of Invention () 22 (B) The crystallinity of polyethylene terephthalate is 40%. Agglomeration of the flakes occurred in step (B), so subsequent steps could not be heated. Brief Description of the Drawings Fig. 1 shows one example of a D S C curve of polyethylene terephthalate measured by D S C. FIG. 2 is a schematic diagram of a heating device in the embodiment. 1: Feeding funnel 2: Horizontal continuous heating vessel 3: Vertical continuous heating vessel 4: Horizontal continuous heating vessel 5: Air purifier 6: Air heater 7: Solid-phase polycondensation reaction vessel 8: Cooler 9: Nitrogen purging 1 0: blower 1 1: heater The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) n · — '^^^ 1 m · I— m —mn I-· / (Please (Read the precautions on the back before filling out this page.)