經濟部中央標準局貝工消费合作社印製 404958 A7 __B7______ 五、發明説明（) 【發明有關之領域】 本發明係有關於一種直接酯化法聚對苯二甲酸丁二酯 (PBT)及製程用觸媒組成物，尤指將對苯二甲酸及丁二 醇（BDO)酯化，接著用聚縮合反應，以有機鈦化合物爲 主觸媒，硼酸類鹼金屬鹽爲副觸媒來製出PBT。 .[先前技術之敘述] 合成聚對苯二甲酸丁二酯（PBT)有關的文獻與專利 可說不勝枚舉。雖然大部份爲對苯二甲酸二甲酯（DMT) 的酯交換法製程，但是採用對苯二甲酸（TPA)直接酯化 法製程，已於1949年（US 3936421 )就出現。美國 Celanese公司等，於1970年底陸續以DMT法打入市場，但 是隨著PET製程逐漸由DMT法轉變爲TPA法之趨勢，因爲TPA 法比DMT法成本上佔優勢。70年代有較多TPA法製造PBT之 專利文獻報導，且大部份偏重於觸媒的選擇，組成、進料 比、反應機構與動力學方面的探討。 TPA法合成PBT在技術上最難突破的地方在於BD0在酸 催化下會環化生成TW，如果對每莫耳TPA之BDO損失大於 0.2莫耳、也就是說當BDO/TPA莫耳比爲1.7時，BDO之損失 若爲11 %以上，則TPA法就不比DMT法具經濟性，因此專利 上無不費盡心思設法降低THF之生成。 BDO環化生成THF，主要是受到酸的催化，即使BD0對 TPA之溶解度低’因TPA的酸性強，仍有足夠的酸來催化 BDO進行脫水，兩機構路徑如圖一所示。當酸根(r)存在 時，則會與氧原子多餘電子對形成（Carb〇nium_i〇n (請先閲讀背面之注$項再填寫本頁)Printed by 404958 A7, __B7______, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention () [Fields related to the invention] The present invention relates to a direct esterification method of polybutylene terephthalate (PBT) and its production process. Catalyst composition, especially esterification of terephthalic acid and butanediol (BDO), followed by polycondensation reaction, using organic titanium compounds as the main catalyst and boric acid alkali metal salt as the secondary catalyst to produce PBT . [Description of the prior art] The literature and patents related to the synthesis of polybutylene terephthalate (PBT) are endless. Although most of them are dimethyl terephthalate (DMT) transesterification process, the direct esterification process using terephthalic acid (TPA) has appeared in 1949 (US 3936421). Celanese and other companies in the United States successively entered the market with the DMT method at the end of 1970, but with the trend of the PET process gradually changing from the DMT method to the TPA method, because the TPA method has a cost advantage over the DMT method. In the 1970s, there were more patent literature reports on the manufacture of PBT by the TPA method, and most of them focused on the choice of catalyst, composition, feed ratio, reaction mechanism and kinetics. The most difficult technical breakthrough in the synthesis of PBT by TPA is that BD0 will cyclize to TW under acid catalysis. If the BDO loss per mole of TPA is greater than 0.2 mole, that is, when the BDO / TPA mole ratio is 1.7 At this time, if the loss of BDO is more than 11%, the TPA method is not more economical than the DMT method. Therefore, every effort is made in the patent to reduce the generation of THF. The cyclization of BDO to generate THF is mainly catalyzed by acids. Even if BD0 has a low solubility in TPA, because of the strong acidity of TPA, there is still enough acid to catalyze the dehydration of BDO. The two mechanisms are shown in Figure 1. When the acid radical (r) is present, it will form an extra electron pair with the oxygen atom (Carb〇nium_i〇n (Please read the note on the back before filling this page)
•1T 經濟部中央標準局貝工消费合作社印装 404958 五、發明説明（）• 1T Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 404958 V. Description of Invention ()
Intermediate)，再經由路徑1或路徑2开多成THF。 路徑1爲SNi型式之反應機構，先脫水再環化成爲一個 環狀的過渡態化合物，最後脫去氫離子而生成THF，其速 率決定於Primary Carbonium-ion中G與C4環化之鍵結快 慢，爲1階反應。路徑2爲SN2型式之反應機構，其中G位置 之 0H2 爲 Leaving Group，而 〇4 位置之 0H 爲 Entering Group，反應速率決定於Oft基離去與Η進入成環之快慢，爲 2階反應。 圖二爲ΡΒΤ聚合反應的路圖，其中用阿拉伯數字標示的 是各反應的活化能，由義大利人Pilati等人（polymer 17，799與22，1566)利用模型分子對ΡΒΤ直接酯化法的硏究 中發現：：600生成11正活化能爲30.9仟卡/莫耳，雖然比步 驟一活化能22.9爲高，但比步驟三（33.7)、步驟五 (33.7)爲低，因此高溫反應對提高酯化率有利，同時也 會增加BD0的環化；低溫反應雖有利於減少BD0的環化，但 酯化率卻無法提高。 有關直接酯化法合成ΡΒΤ的專利如下： US 3936421·.使用有機鈦與錫化合物爲觸媒，可減少丁二 醇的損失，本專利也提到反應物添加2-8%的水可增加對 苯二甲酸和丁二醇之混合與分散，提高初期酯化速率》 US 4014858:也是鈦與錫類觸媒的配合，以求最短的酯化 時間，使得THF生成量較少 US 4329444:使用鈦系觸媒先將丁二醇預熱至反應溫度， 再將對苯二甲酸慢慢加入以減少THF的生成。 4 1'--I--L---ΙΛ--------訂 I-----乘 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 404958 at __B7_ 五、發明説明（） ' US 5015759:也是使用鈦系觸媒，BDO:TPA莫耳比5]， 225〇C迅速完成酯化，減少THF之生成。 ·，在 US 4346213與US 4439597:達到澄淸前或是對苯二甲酸尙 有20-30%未轉化完畢時’就開始抽真空進入聚縮合^ 應。BDO/TPA進量莫耳比低，則酯化速率慢；反之則丁二 醇損失大，而最佳莫耳比爲1.5-1.8之間。酯化溫度在208 °(：至212乞之間。 邶4565241:反應初期61)0/1?八莫耳比爲〇.6-1.0，後期再 慢慢加入BD0 ° 【發明之一般說明】 本發明乃以鈦系主觸媒，配合適當副觸媒，以直接酯 化法製造聚對苯二甲酸丁二酯，期能減少副產物THF之生 成，而且能提昇其酯化率，以展現直接酯化法的經濟優 勢0 經濟部中央標準局員工消費合作社印裝 m-1^1 «ϋ» n i HJ tn I \為广 ^^^1 ^^^1 ^^^1 ^^^1 Kn {請先閲讀背面之注意事項再填寫本頁) 本發明乃是改良的直接酯化法製造聚對苯二甲酸丁二 酯的方法，其特徵在於使用對苯二甲酸與丁二醇反應時， 使用一特定的觸媒組成物，此觸媒組成物包含：（1) 一種 有機鈦系金屬化合物主觸媒，其用量爲對苯二甲酸的 0.01 -1.0重量％與(2)鹼金屬的硼酸、焦硼酸或偏硼酸鹽 爲副觸媒，其用量爲對苯二甲酸的0.001-1.0重量百分 比。有機鈦系金屬主觸媒有tetrabutyl titanate，tetra (isopropyl)titanate,tetrapropyl titanate,tetra-phenyl titanate等等，而以tetrabutyl titanate與 tetra(isopropyl)titanate爲宜:硼酸、焦硼酸或偏硼酸 5 本紙伕尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） 一 經濟部中央揉準局貝工消费合作社印製 404958 A7 B7 五、發明説明（） 之鹼金屬鹽副觸媒有鋰、鈉、鉀等金屬鹽等等，如sodium tetraborate(通常稱爲borax,硼砂），sodium pyroborate 與 sodium metaborate等，而以 sodium tetraborate與 sodium metaborate 爲宜。 使用此改良觸媒組成物時，主觸媒與副觸媒可同時加 入反應混合物中，而此反應混合物通常含有過剩的丁二醇 對應著對苯二甲酸，而以BD0/TPA莫耳比1.5-2.0爲宜；或 是有機鈦系主觸媒與對苯二甲酸混合而硼酸鹽與丁二醇混 合，混合物再混合成反應混合物。 誠如上面所述，反應機構包含兩階段，酯化階段與聚 縮合階段，而聚縮合階段的溫度通常比酯化階段的溫度爲 高而且也在較高真空下進行。通常酯化反應是在210-230 °C、大氣壓下進行，反應途中將生成的水與TEF靠氮氣帶 出；聚縮合反應則通常在260-280°C，0.1-3mmHg壓力下， 將過剩的丁二醇蒸出。 本發明所使用的鈦系化合物主觸媒和硼酸鹽類副觸媒 組成物，不只可減少副產物THF之生成量30%以上，而且 可提昇酯化反應速率20%以上。 爲了使貴審查委員能更進一步了解本發明之特點及技 術內容，請參閱以下有關本發明之附圖及詳細說明，然而 所附圖式僅提供參考與說明用，並非用來對本發明加以限 制者。 【圖示說明】 表一係爲轉化率與時間表 6 ϋί - , I — — — 訂 (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度逍用中國國家標準（CNS ) Α4规格（210X297公釐） 404958 at __ B7 五、發明説明（） 表二係爲生成量與時間表 圖一係爲BDO生成THF反應機構圖 圖二係爲PBT聚合反應路徑圖。 [實施例] 實施例一： 經濟部中央標準局貝工消费合作社印製 (請先W讀背面之注意事項再填寫本頁) 取TPA 0.5莫耳，BD0 0.85莫耳（BDO/TPA=1.7)，主 觸媒Ti(0Bii)4 0.068g (TPA的0.04重量百分比）與副觸媒 Na4B4〇7 0.017g (TPA的0.01重量百分比），置入附有蒸餾 管（通120°C的油，可使反應生成的水份與THF不被冷凝而 迴流到反應器），攪拌棒，氮氣通入口，溫度控制裝置之 反應器。加熱至215°C左右，並隨著反應時間的增加逐漸 升溫到225°C，並維持在228°C直到反應物變澄淸，且不再 有水和THF蒸出爲止，即爲完成第一階段的酯化反應。反 應溫度到達215°C起，每隔20分取樣分析TPA之轉化率以及 收集的蒸餾液中THF的含量，結果列於表1與表2。將第一 階段酯化完成的反應混合物升溫至260°C，將氮氣關掉， 並開始慢慢的抽真空，最後維持壓力在l.OmmHg左右，聚 縮合反應時間爲90分，所得的產品的極限粘（IV)値也表 示於表1。 實施例二： 實施例一中之副觸媒改爲NaB〇2其用量亦爲TPA之〇. 04 重量百分比。其餘反應條件均與實施一相同。結果也列於 表一與表二。 比較例一： Ί 本紙張尺度適用中國B家揉準（CNS >A4規格（210X297公釐） 404958 B7 五、發明説明（） 不加副觸媒外，其餘反應條件均與實施例一相同，分 析結果列於表一與表二 由表一與表二的結果可明顯看出，使用Na4B4〇7與NaB〇2 等副觸媒配合著主觸媒Ti((®u)4，不只可減少副產物THF生 成量40%以上，而且可提昇反應速率20%以上。 上述之具體實施例是用來詳細說明本發明之目的、特 徵及功效，對於熟悉此類技藝之人仕而言，根據上述說 明，可能對該具體實施例作部份變更及修改，而並不脫離 出本發明之精神範疇。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印裝 8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 404958Intermediate), and then multiply into THF via Path 1 or Path 2. Path 1 is a SNi type reaction mechanism. It is dehydrated and then cyclized to form a cyclic transition compound. Finally, the hydrogen ion is removed to form THF. The rate is determined by the speed of G and C4 cyclization in the Primary Carbonium-ion. , Is a first order reaction. Path 2 is a SN2 type reaction mechanism, where 0H2 at the G position is the Leaving Group and 0H at the 〇4 position is the Entering Group. The reaction rate is determined by the speed of the departure of the Oft base and the entry of plutonium into a ring, which is a second-order reaction. Figure 2 is a road map of PBT polymerization. The Arabic numerals indicate the activation energy of each reaction. The Italian molecule Pilati et al. (Polymers 17,799 and 22,1566) used model molecules to directly esterify PBT. It was found in the research that the positive activation energy of 600 generation 11 is 30.9 kcal / mole. Although it is higher than the activation energy of step 1 22.9, it is lower than that of step three (33.7) and step five (33.7). Increasing the esterification rate is beneficial, and it will also increase the cyclization of BD0. Although the low temperature reaction is beneficial to reduce the cyclization of BD0, the esterification rate cannot be improved. The patent related to the direct esterification of PBT is as follows: US 3936421 ·. The use of organic titanium and tin compounds as catalysts can reduce the loss of butanediol. This patent also mentions that the addition of 2-8% water to the reactants can increase the Mixing and dispersing of phthalic acid and butanediol to increase the initial esterification rate "US 4014858: It is also the combination of titanium and tin catalysts in order to achieve the shortest esterification time and make the amount of THF less. US 4329444: Use of titanium The catalyst is preheated to the reaction temperature first, and then terephthalic acid is slowly added to reduce the formation of THF. 4 1 '-I--L --- ΙΛ -------- Order I ----- Multiply (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards ( CNS) A4 specification (210 × 297 mm) 404958 at __B7_ V. Description of the invention () '' US 5015759: Also uses titanium catalyst, BDO: TPA Molar ratio 5], 225 ° C quickly completes the esterification and reduces the formation of THF . · Before US 4346213 and US 4439597: before reaching 淸 or when 20-30% of 尙 terephthalate has not been converted ’, start to evacuate into the polycondensation. The lower the molar ratio of BDO / TPA, the slower the esterification rate; otherwise, the loss of succinyl alcohol is large, and the optimal molar ratio is between 1.5 and 1.8. The esterification temperature is between 208 ° (: to 212 ° C. 邶 4565521: early reaction 61) 0/1? The mol ratio is 0.6-1.0, and then BD0 is added slowly in the later period. [General description of the invention] This The invention is based on titanium main catalyst, with appropriate auxiliary catalyst, to produce polybutylene terephthalate by direct esterification, which can reduce the generation of by-product THF, and can increase its esterification rate to show direct Economic advantages of the esterification method 0 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs m-1 ^ 1 «ϋ» ni HJ tn I \ Weiguang ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 Kn { (Please read the notes on the back before filling this page) The present invention is an improved method for producing polybutylene terephthalate by direct esterification. It is characterized in that when terephthalic acid is reacted with butanediol, A specific catalyst composition, the catalyst composition includes: (1) an organic titanium-based metal compound main catalyst in an amount of 0.01 to 1.0% by weight of terephthalic acid and (2) an alkali metal boric acid, Pyroboric acid or metaborate is a secondary catalyst, and its amount is 0.001-1.0 weight percent of terephthalic acid. Organo-titanium metal main catalysts include tetrabutyl titanate, tetra (isopropyl) titanate, tetrapropyl titanate, tetra-phenyl titanate, etc., and tetrabutyl titanate and tetra (isopropyl) titanate are suitable: boric acid, pyroboric acid or metaboric acid Standards are applicable to the Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Central Government Standards Bureau of the Ministry of Economic Affairs and printed by Shellfish Consumer Cooperatives. 404958 A7 B7 V. Description of the invention () Alkali metal salt secondary catalysts include lithium, sodium, Metal salts such as potassium and so on, such as sodium tetraborate (commonly called borax, borax), sodium pyroborate and sodium metaborate, etc., and sodium tetraborate and sodium metaborate are more suitable. When this modified catalyst composition is used, the main catalyst and the sub-catalyst can be added to the reaction mixture at the same time, and this reaction mixture usually contains excess butanediol corresponding to terephthalic acid, and the BD0 / TPA molar ratio is 1.5 -2.0 is suitable; or an organic titanium-based main catalyst is mixed with terephthalic acid and borate is mixed with butanediol, and the mixture is mixed into a reaction mixture. As described above, the reaction mechanism includes two stages, the esterification stage and the polycondensation stage, and the temperature of the polycondensation stage is usually higher than the temperature of the esterification stage and is also performed under a higher vacuum. Generally, the esterification reaction is carried out at 210-230 ° C under atmospheric pressure, and the generated water and TEF are taken out by nitrogen during the reaction. The polycondensation reaction is usually carried out at 260-280 ° C under the pressure of 0.1-3 mmHg. Butanediol was distilled off. The titanium catalyst main catalyst and the borate secondary catalyst composition used in the present invention can not only reduce the generation amount of the by-product THF by more than 30%, but also increase the esterification reaction rate by more than 20%. In order to allow your reviewers to further understand the features and technical contents of the present invention, please refer to the following drawings and detailed descriptions of the present invention. However, the drawings are for reference and explanation only, and are not intended to limit the present invention. . [Illustration] Table 1 is the conversion rate and timetable 6 ϋί-, I — — — Order (Please read the notes on the back before filling out this page) This paper standard is free to use Chinese National Standard (CNS) Α4 specifications (210X297 mm) 404958 at __ B7 V. Description of the invention () Table 2 shows the amount of production and timetable. Figure 1 shows the THF reaction mechanism for BDO. Figure 2 shows the PBT polymerization reaction path. [Example] Example 1: Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Take TPA 0.5 Mor, BD0 0.85 Mor (BDO / TPA = 1.7) , The main catalyst Ti (0Bii) 4 0.068g (0.04 weight percent of TPA) and the sub-catalyst Na4B4〇7 0.017g (0.01 weight percent of TPA), put in a distillation tube attached (pass 120 ° C oil, can The water and THF generated by the reaction are not condensed and refluxed to the reactor), a stirring rod, nitrogen is passed through the inlet, and the reactor of the temperature control device. Heating to about 215 ° C, and gradually increasing the temperature to 225 ° C as the reaction time increases, and maintaining at 228 ° C until the reaction becomes clear, and no more water and THF are distilled off, that is to complete the first Stages of esterification. After the reaction temperature reached 215 ° C, samples were taken every 20 minutes to analyze the conversion of TPA and the THF content in the collected distillate. The results are shown in Tables 1 and 2. The reaction mixture completed in the first stage of esterification was heated to 260 ° C, the nitrogen was turned off, and a vacuum was slowly evacuated. Finally, the pressure was maintained at about 1.0 mmHg, and the polycondensation reaction time was 90 minutes. The ultimate viscosity (IV) 値 is also shown in Table 1. Example 2: The secondary catalyst in Example 1 was changed to NaB〇2, and the amount was also 0.04 weight percent of TPA. The remaining reaction conditions were the same as those in the first implementation. The results are also shown in Tables 1 and 2. Comparative Example 1: Ί This paper size is applicable to Chinese B-households (CNS > A4 specification (210X297 mm) 404958 B7. V. Description of the invention () Except no auxiliary catalyst, the other reaction conditions are the same as in Example 1. The analysis results are listed in Tables 1 and 2. From the results of Tables 1 and 2, it can be clearly seen that the use of secondary catalysts such as Na4B407 and NaB〇2 in combination with the main catalyst Ti ((®u) 4 can not only reduce The amount of THF produced as a by-product is more than 40%, and the reaction rate can be increased by more than 20%. The specific examples described above are used to explain the purpose, characteristics and effects of the present invention in detail. Note that some changes and modifications to this specific embodiment may be made without departing from the spirit of the present invention. (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 8 This paper size applies to China National Standard (CNS) A4 (210X297 mm) 404958
S A7 B7 ΊΛ 補充 五、發明説明（） 表1轉化率與時間 酯化反應時間 :分润 f，ΤΡΑ之轉化率 聚縮合反應 副觸媒/時間 20分 40分 60分 80分 90分 100分 130分 時間(分） IV Na4B<07 22 43 70 90 clear 90 0.77 NaBO, 20 35 60 80 90 clear 90 0.75 Μ 16 30 58 70 76 82 clear 90 0.72 clear point(澄淸點)乃工業上用以判斷酯化反應完畢的指標·酯化反應物由混濁變 成澄淸表示TPA已反應完畢·可進入聚縮合反應· (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X：297公釐） 404958 A7 B7 蘇 ft7. 捕充 年月曰 五、發明説明（ 煩- ^是否變更^實：： 經濟部中央標隼局員工消費合作社印製 表2THF生成量 累集的THF生成量 rmol %) 副觸媒/時間 20分 40分 60分 8〇分 90分 100分 130分 Na4B407 〇_3g Ug 1.5g l-8g 2.〇g(3.3) (0.49) (1.8) (2.5) (2.9) (完成酯化） NaBO, 〇_5g l-3g 2.0g 2.5g 2-7g 3.0g(4.9) (0.82) (2.1) (3.3) (4.1) (4.4) (完成酯化） 赃 /«»» l.4g 2-5g 3-6g 4-2g 4.4g 4.7g 5.0g (8.2) P.3) (4.1) (5.9) (6.9) (7.2) (7.7) (完成酯化） (請先閱讀背面之注意事項再填寫本頁S A7 B7 ΊΛ Supplement V. Description of the invention (Table 1) Conversion rate and time Esterification reaction time: Fen Run f, TPA conversion rate Polycondensation reaction Paracatalyst / time 20 minutes 40 minutes 60 minutes 80 minutes 90 minutes 100 minutes 130 minutes (minutes) IV Na4B < 07 22 43 70 90 clear 90 0.77 NaBO, 20 35 60 80 90 clear 90 0.75 Μ 16 30 58 70 76 82 clear 90 0.72 clear point is used for industrial judgment Indicators of completion of the esterification reaction • The esterification reaction product changed from turbid to clear, indicating that the TPA has completed the reaction. The polycondensation reaction can be entered. (Please read the precautions on the back before filling out this page.) The paper size of the paper is in accordance with the Chinese National Standard (CNS) Λ4 specification (210X: 297 mm) 404958 A7 B7 Su ft7. The date of catching and charging 5. Description of the invention (Annoying-^ Whether to change ^ Real: Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives. 2 THF production volume accumulated mol rmol%) Paracatalyst / time 20 minutes 40 minutes 60 minutes 80 minutes 90 minutes 100 minutes 130 minutes Na4B407 0_3g Ug 1.5g 1-8g 2 .〇g (3.3) (0.49) (1.8) (2.5) (2 .9) (Complete esterification) NaBO, 〇_5g l-3g 2.0g 2.5g 2-7g 3.0g (4.9) (0.82) (2.1) (3.3) (4.1) (4.4) (Complete esterification) «» »L.4g 2-5g 3-6g 4-2g 4.4g 4.7g 5.0g (8.2) P.3) (4.1) (5.9) (6.9) (7.2) (7.7) (Complete esterification) (Please Read the notes on the back before filling out this page
,1T, 1T
-HI 本紙張尺度適用中國國家梯準（CNS ) A4規格（210X297公釐）-HI This paper size is applicable to China National Standard (CNS) A4 (210X297mm)