TW201116550A - Titanium oxide composition and the application thereof on poly-esterification - Google Patents

Abstract

This application discloses a Titanium oxide composition and the application thereof. The mentioned Titanium oxide composition comprises Titanium co-precipitate(s), organic acid, diol, and water. According to this application, a catalyzed poly-esterification with said Titanium oxide composition is also disclosed. The mentioned polyesterification comprises a step of adding said Titanium oxide composition into at least on process selected from Slurry stage, esterification stage, and polycondensation stage.

Description

201116550 六、發明說明： 【發明所屬之技術領域】 本發明揭露一種含鈦組合物’特別是關於一種具有含欽 共沈;殿物之含鈦組合物及其在聚醋反應中的應用。 【先前技術】 聚酯類的化合物在工業方面具有相當廣泛的應用。以pET (聚對苯二F酸乙二酯）為例，由於其機械強度、耐熱性、透 明性及阻氣性等均具有優異的表現，不僅適合用作果汁、清涼 飲料、碳酸飲料等飲料填充容器之材料，還適合用於薄膜、薄 板、.纖維等之製作材料。這類聚酯樹酯通常是以諸如對苯二甲 酸等的二元舰，和乙二醇之類的脂肪族二元醇為原料，通過 酯化反應來形成低縮聚物。接著在縮聚催化劑的存在下，使該 低縮聚物發生聚合反應（液相縮聚)並進行高分子化來製= 取得。目前31業生產細和研究财的催化触妓％、Ge、 Ti等三個系列的化合物喝（Ge)類催化劑可以製得較白亮的 聚酉旨，但是錯類催化劑之價格較為昂貴。銻⑽類催化劑在 反應中會還原成錄，使聚自旨呈灰霧色，且銻具有毒性，在生產 過財造j污染，導致後處理費用增加，使得ρΕτ生產成本 升高。目前被認為較好的觸媒是鈦⑼。使用鈦觸媒可以解決 重金屬汙染問題。但多數鈦類催化劑存在著溶解度不佳的問 題。當鈦_化敝項分鱗’物能形賴浮液，容 201116550 易造成反應不均勻’導致產品之品質不穩定。 為了改善前述鈦類催化劑反應不均勻的問題，許多研發 單位紛紛提出了不_解決方案 。例如，Lurgi Zimmer公司開 發出負載型的鈦類催化劑，以防止催化劑的團聚；專利 CN1403193採用有機改性方法來防止催化劑團聚；專利 CN1644601採用由乙醇、異丙醇、曱苯、混二曱苯的一種或數 種〉谷劑所組成的溶液，來製備出液態鈦類催化劑；日本特開平 • 7-207010利用驗金屬化合物來幫助鈦類催化劑的溶解；專利 CN1962723利用2-羥基羧酸化合物先肖鈦 化合物，再與磷化合物反應以得到具良好光穩定性的鈦系催化 劑’專利CN1809605利用脂肪族二元醇和三元以上多元醇及 水或和鹼性化合物得到含鈦溶液;CN163〇674將鈦化合物與鹼 金屬化合物及丙三醇或三抑基秘等增溶酸混合以提高鈦 化合物之溶解度;CN1328072使用納米級乙二醇鈦與有機酸及 # 配合使用1〜4價金屬離子的化合物來得到鈦系催化劑； CN1402653貝彳疋將鈦酸g旨加人絡合劑⑽基舰，鏈燒醇胺，氨 基舰或其混合物）、水或_溶敍次顧崎到液態催化 劑；CN1583823則是利用鹼金屬氫氧化物與乙二醇混合物來溶 解二氧化鈦及二氧倾的混合物進而制祕_催化劑。 前述的各種解決方案雖然可在—定程度上改善反應不均 的問題，但在催化_使用過財，前述的各轉決方案不可 避免地也㈣人許多不必要的雜f至反應體钟，導致產品的 r s 201116550 品質因雜質增多而下降。另外，鈦娜化綱第二個問題點在 於’鈦的催化活性高但熱穩定性差，容易引起聚醋裂解，使得 縮t程序和融炫成形加1程序巾產生大量不必要㈣產物，並 使聚酿色相變差。但是，若透過填系列熱穩定劑來減少副產物 產生’卻又會抑制習知技術中的鈦觸媒活性，使得反應性降低。 因此，如何提升鈦類催化劑之分散性使聚酯反應均勻進 行’同時又知以維持鈦催化劑之反應性，並可生產出對品質無 虞的聚@旨，已經成為聚_產品在生產工藝改革上亟待解決的 關鍵技術問題。 【發明内容】 馨於上述之背景中，為了符合產業上的需求，本發明提 t、種含鈦組合物及其在聚酯化反應之應用。 本發明之一目的在於提供一種含鈦組合物，藉由有機酸 之使用’轉到含餘合物巾之含縣沈麟可被㈣分散於 >谷液中的效果。 本發明之另一目的在於提供一種以含鈦組合物催化聚酯 反應之方法，藉由使用—根據本說明書之含鈦組合物，以達到 提高聚酯產品之品質的效果。 本發明揭露一種含鈦組合物，上述含鈇組合物包含一具 有由3 -氧化鈦(Ti〇2)/二氧化娃(Si〇2)和/或二氧化銥(Ti〇2)/二 氧化锆(Zr〇2)所組成之共沈澱物、有機酸、二元醇、以及水。 201116550 本發明亦揭露一種以含鈦組合物催化聚酯反應之方法。上述以 含鈦組合物催化聚酯反應之方法包含將含鈦組合物添加至原 料漿液調製工序、醋化工序、液相縮聚工序中之至少一工序中 的步驟。 【實施方式】 本發明在此所探討的方向為一種含鈦之酯化催化劑及其 應用。為了能徹底地瞭解本發明，將在下列的描述中提出詳盡 的步驟及其組成。顯然地，本發明的施行並未限定於該領域之 技藝者所熟習的特殊細節。另—方面，眾所周知敝成或步驟 並未描述於細節中，以避免造成本發明不必要之限制。本發明 的較佳實酬會詳細描述如下，然嫌了這些詳細描述之外， 本發明還可以獻地施行在其他的實施财，且本發明的範圍 不受限定’其以之後的專利範圍為準。 根據本說明書之一較佳實施例，係揭示一種含鈦組合 物。上述含鈦組合物包含：含鈦共沈澱物、有舰、二元醇 (diol)、以及水。其+’姆於含餘合物之總量，上述含欽 共沈澱物的重量百分比約為0.G1〜2G重量％，上述之有機酸的 重$百分比約為2〜8G% ’二元醇的重量百分比約為q〜％重 量％ ’水的重量百分比約為0.1〜99重量％。 根據本實施例，上述含鈦共沈_係含有二氧化欽⑽以 -氧化娃(SiQ2)的共沉丨殿物和/或二氧化鈦(叫)/二氧化錄 201116550 (Zr〇2)共沉殿物的鈦化合物。其中，上述二氧化欽匕氧化石圭的 細殿物中，Ti〇2 : Si〇2 = 9〇 : 1〇至2〇 · 8〇福編，上述二 氧化鈦/二氣化錯的共沉澱物中，Ti02 : Zr〇2 = 95 : 5至70 : 30 mol/mol ° 上述的有機酸可以是選自下列群組中之一者：甲酸，乙 酸，草酸，丙二酸，琥_，戊二酸，己二酸，庚二酸，酒石 酸，水楊酸，檸檬酸，乳酸，顏果酸，桂皮酸，咖啡酸。 上述的二元醇可以是選自下列群組中之一者：乙二醇， 丙一醇，丁二醇，戊二醇。 在根據本實施例之一較佳範例中，上述的含鈦組合物之 調製方法如下。將含鈦賊澱物、錢酸、乙二醇、及水混合 後，在常溫下擾拌’以得到一均勾透明溶液。在根據本實施例 之另一較佳範例中，上述的含鈦組合物之調製方法為，將含鈦 之共沉澱物、有機酸、乙二醇、及水混合後，進行加熱操作， 乂知到均勻透明》谷液。上述含鈦組合物之均勻透明溶液的濁 度可使用 HunterLab COLORQUEST XE 依照 ASTM D 1003 方 法進行測定。 範例1 :配製溶液blank 取99.5g的50〇/〇乙二醇水溶液，加入二氧化鈦/二氧化硅 的共沉澱物和/或組成為二氧化鈦/二氧化锆共沉澱物的鈦化合 物 C-94 (購自 Sachtleben Chemie GmbH) 0.5g，在室溫下攪拌 i 201116550 天，以得到一混合溶液。使用HunterLab COLORQUEST XE 機台依照ASTM D 1003方法測定上述溶液之霧度，測得上述 溶液之濁度為95%。 範例2 :配製溶液1-1201116550 VI. Description of the Invention: [Technical Field of the Invention] The present invention discloses a titanium-containing composition', particularly relates to a titanium-containing composition having a compound and a composition thereof, and its use in a polyester reaction. [Prior Art] Polyester-based compounds have a wide range of industrial applications. Taking pET (polyethylene terephthalate) as an example, it has excellent performance in terms of mechanical strength, heat resistance, transparency, and gas barrier properties, and is not only suitable for use as a juice, a refreshing beverage, or a carbonated beverage. The material for filling the container is also suitable for use in the production of films, sheets, fibers, and the like. Such polyester resins are usually formed by a glycolization reaction using a binary ship such as terephthalic acid or an aliphatic diol such as ethylene glycol to form a low polycondensate. Next, in the presence of a polycondensation catalyst, the low polycondensate is polymerized (liquid phase polycondensation) and polymerized to obtain a solution. At present, the 31 series of catalysts for the production of fine and research resources, such as %, Ge, Ti, etc., can produce a brighter white pigment, but the price of the wrong catalyst is more expensive. The ruthenium (10) type catalyst will be reduced to a record in the reaction, so that the color is fog-colored, and the ruthenium is toxic. In the production, the pollution is increased, resulting in an increase in the post-treatment cost, which increases the production cost of ρΕτ. The catalyst currently considered to be better is titanium (9). The use of titanium catalysts can solve the problem of heavy metal pollution. However, most titanium catalysts have problems with poor solubility. When the titanium _ 敝 敝 分 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 In order to improve the problem of uneven reaction of the aforementioned titanium catalysts, many R&D units have proposed no solution. For example, Lurgi Zimmer developed a supported titanium catalyst to prevent agglomeration of the catalyst; patent CN1403193 uses an organic modification method to prevent catalyst agglomeration; patent CN1644601 uses ethanol, isopropanol, anthracene, and diphenylene. a solution of one or several kinds of granules to prepare a liquid titanium catalyst; Japanese Patent Laid-Open No. 7-207010 uses a metal compound to assist in the dissolution of a titanium catalyst; Patent CN1962723 utilizes a 2-hydroxycarboxylic acid compound Titanium compound, which is then reacted with a phosphorus compound to obtain a titanium catalyst having good photostability. Patent CN1809605 utilizes an aliphatic diol and a ternary polyol and water or a basic compound to obtain a titanium-containing solution; CN163〇674 will be titanium. The compound is mixed with an alkali metal compound and a solubilizing acid such as glycerol or tris-primary to increase the solubility of the titanium compound; CN1328072 uses a compound of a nano-sized ethylene glycol titanium and an organic acid and #1 to a tetravalent metal ion. Obtaining a titanium-based catalyst; CN1402653Beiqi will add a human complexing agent (10) base ship, a chain alkalamine, a amino ship or The mixture), water or _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Although the foregoing various solutions can improve the problem of uneven reaction to a certain extent, in the catalysis _ use of the money, the above-mentioned various conversion schemes inevitably also (four) many unnecessary impurities f to the reaction body clock, The quality of the rs 201116550 that caused the product decreased due to increased impurities. In addition, the second problem of Titanium is that 'the catalytic activity of titanium is high but the thermal stability is poor, which is easy to cause the cracking of the polyester, so that the shrinking process and the melt forming and adding a program towel produce a large number of unnecessary (four) products, and The color of the brewed wine is poor. However, if the by-product generation is reduced by filling a series of heat stabilizers, the activity of the titanium catalyst in the prior art is suppressed, and the reactivity is lowered. Therefore, how to improve the dispersibility of the titanium-based catalyst to make the polyester reaction uniform; at the same time, it is known to maintain the reactivity of the titanium catalyst, and it can produce a quality-free poly@, which has become a poly-product in the production process reform. The key technical issues to be resolved. SUMMARY OF THE INVENTION In the above background, in order to meet the industrial requirements, the present invention provides a titanium-containing composition and its use in a polyesterification reaction. SUMMARY OF THE INVENTION One object of the present invention is to provide a titanium-containing composition which is transferred to a < valley liquid by the use of an organic acid. Another object of the present invention is to provide a method for catalyzing a polyester reaction by using a titanium-containing composition by using a titanium-containing composition according to the present specification to achieve an effect of improving the quality of the polyester product. The invention discloses a titanium-containing composition, the above cerium-containing composition comprising one having 3 - titanium oxide (Ti〇2) / silicon dioxide (Si 〇 2) and / or cerium oxide (Ti 〇 2) / dioxide A coprecipitate composed of zirconium (Zr〇2), an organic acid, a glycol, and water. 201116550 The present invention also discloses a method of catalyzing a polyester reaction with a titanium-containing composition. The above method for catalyzing a polyester reaction with a titanium-containing composition comprises the step of adding a titanium-containing composition to at least one of a raw material slurry preparation step, a acetification step, and a liquid phase polycondensation step. [Embodiment] The invention is directed to a titanium-containing esterification catalyst and its use. In order to fully understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. In other instances, it is to be understood that the details are not described in detail in order to avoid unnecessary limitation of the invention. The preferred embodiment of the present invention will be described in detail below, and the present invention may be embodied in other implementations without departing from the scope of the invention, and the scope of the invention is not limited. quasi. According to a preferred embodiment of the present specification, a titanium-containing composition is disclosed. The above titanium-containing composition comprises: a titanium-containing coprecipitate, a ship, a diol, and water. The weight percentage of the above-mentioned containing co-precipitate is about 0.G1~2G% by weight, and the weight of the above organic acid is about 2~8G% 'diol The weight percentage is about q~% by weight. The weight percentage of water is about 0.1 to 99% by weight. According to this embodiment, the titanium-containing co-precipitation system comprises a co-depositing chamber of the oxidized silicon (10)-oxide (SiQ2) and/or a titanium dioxide (called)/dioxide recording 201116550 (Zr〇2) Titanium compound. Among them, in the above-mentioned dioxide oxidized stone oxidized stone, Ti〇2: Si〇2 = 9〇: 1〇 to 2〇·8〇福编, in the above-mentioned titanium dioxide/digasification co-precipitate , Ti02 : Zr〇2 = 95 : 5 to 70 : 30 mol/mol ° The above organic acid may be one selected from the group consisting of formic acid, acetic acid, oxalic acid, malonic acid, a-succinic acid, glutaric acid , adipic acid, pimelic acid, tartaric acid, salicylic acid, citric acid, lactic acid, anaphoric acid, cinnamic acid, caffeic acid. The above diol may be one selected from the group consisting of ethylene glycol, propanol, butylene glycol, and pentanediol. In a preferred embodiment according to this embodiment, the above-described titanium-containing composition is prepared as follows. After mixing the titanium-containing thief, the acid, the ethylene glycol, and the water, the mixture is stirred at room temperature to obtain a uniform transparent solution. In another preferred embodiment of the present embodiment, the titanium-containing composition is prepared by mixing a titanium-containing coprecipitate, an organic acid, ethylene glycol, and water, and then performing a heating operation. To evenly transparent" valley liquid. The turbidity of the homogeneous clear solution of the above titanium-containing composition can be determined using a HunterLab COLORQUEST XE according to the ASTM D 1003 method. Example 1: Preparation of solution blank Take 99.5g of 50〇/〇 ethylene glycol aqueous solution, add titanium dioxide/silica coprecipitate and/or titanium compound C-94 composed of titanium dioxide/zirconia coprecipitate (purchased 0.5 g from Sachtleben Chemie GmbH), i 201116550 days at room temperature to obtain a mixed solution. The haze of the above solution was measured in accordance with ASTM D 1003 using a HunterLab COLORQUEST XE machine, and the turbidity of the above solution was found to be 95%. Example 2: Preparing Solution 1-1

取59.7g的50%乙二醇水溶液，加入39.8g酒石酸，攪拌 溶解後，加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧 化鈦/二氧化锆共沉澱物的鈦化合物c_94(購自Sachtleben Chemie GmbH)0.5g，在室溫下攪拌}天，得到澄清透明均勻 溶液。使用 HunterLab COLORQUEST XE 機台依^ASTM D 1003方法來測定上述溶液之霧度，測得該溶液之霧度為1 7%。 範例3 :配製溶液丨_2 取79.6g的50%乙二醇水溶液加入19.9g酒石酸，搜拌溶 解後加氧化欽/ 一氧化娃的共沉殿物和或組成為二氧化鈦/ 二氧化錯共沉殿物的鈦化合物c_94(購自SachtlebenTaking 59.7 g of a 50% aqueous solution of ethylene glycol, adding 39.8 g of tartaric acid, stirring and dissolving, adding a coprecipitate of titanium dioxide/silica and or a titanium compound c_94 composed of a titania/zirconia coprecipitate (purchased from Sachtleben) Chemie GmbH) 0.5 g, stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine according to the method of ASTM D 1003, and the haze of the solution was measured to be 1 7%. Example 3: Preparation of solution 丨_2 Take 79.6 g of 50% aqueous solution of ethylene glycol and add 19.9 g of tartaric acid, mix and dissolve, add oxidized chin / oxidized silicon, and or consist of titanium dioxide / oxidized Titanium compound c_94 (purchased from Sachtleben

GmbH)0.5g，在室溫下攪拌丨天，得到澄清透明均句溶液。使 用 HunterLab COLORQUEST XE 機台依照 ASTM D 1〇〇3 方法 來測定上述溶液之霧度，測得該溶液之霧度為u%。 範例4 :配製溶液j_3 取94.5g的50%乙二醇水溶液加入5g酒石酸，攪拌溶解 後，加入二氧化鈦/二氧化娃的共沉澱物和或組成為二氧化獻/ 二氧化錯共沉澱物的鈦化合物C-94(購自Sachtleben chemieGmbH) 0.5g, stirred at room temperature for a few days to obtain a clear transparent homogenous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with ASTM D 1〇〇3 method, and the haze of the solution was measured to be u%. Example 4: Preparation solution j_3 94.5 g of a 50% aqueous solution of ethylene glycol was added to 5 g of tartaric acid, and after stirring and dissolved, a coprecipitate of titanium dioxide/disiloxane was added and titanium which was composed of dioxide/dioxide coprecipitate was added. Compound C-94 (purchased from Sachtleben chemie

GmbH)0.5g ’在室溫下獅！天，得到澄清透明均句溶液。使 201116550 用 HunterLab COLORQUEST XE 機台，依照 ASTM D 1003 方 法來測定上述溶液之霧度，測得該溶液之霧度為l.8〇/〇。 範例5:配製溶液2-1 取59.7g的50%乙二醇水溶液加入39.8g水揚酸，擾拌溶 解後加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧化鈦/ 二氧化錯共沉澱物的鈦化合物C-94 (購自Sachtleben Chemie GmbH) 0.5g’在室溫下攪拌1天，得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台，依照 ASTM D 1003 方 法來測定上述溶液之霧度，測得該溶液之霧度為1.5%。 範例6:配製溶液2-2 取79.6g的50%乙二醇水溶液加入I9.9g水楊酸，擾拌溶 解後加入一氣化欽/—氧化娃的共沉殿物和或組成為二氧化欽/ 二氧化錯共沉澱物的鈦化合物C-94(購自Sachtleben Chemie GmbH)0.5g，在室溫下攪拌1天，得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台，依照 ASTM D 1003 方 法來測定上述溶液之霧度’測得該溶液之霧度1.5%。 範例7 :配製溶液2-3 取94.5g的50%乙二醇水溶液加入5g水楊酸，擾拌溶解 後加入一氧化鈦/二氧化娃的共沉殿物和或組成為二氧化鈦/二 氧化錯共沉澱物的鈦化合物C-94(購自Sachtleben Chemie GmbH)0.5g ’在室溫下攪拌1天’得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台，依照 ASTM D 1〇〇3 方 201116550 法來測定上述溶液之霧度，測得該溶液之霧度丨.6%。 範例8 :配製溶液3-1 取59.7g的50%乙二醇水溶液，加入39.8g琥拍酸，攪拌 溶解後加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧化 鈦/二氧化锆共沉澱物的鈦化合物C-94(購自Sachtleben Chemie GmbH)0.5g ’在室溫下攪拌1天，得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台依照 ASTM D 1003 方法 來測定上述溶液之霧度，測得該溶液之霧度U%。 範例9 :配製溶液3-2 取79.6g的50%乙二醇水溶液，加入19.9g琥珀酸，擾拌 溶解後加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧化 鈦/二氧化锆共沉澱物的鈦化合物C-94(購自SachtlebenChemie GmbH)〇.5g，在室溫下攪拌1天，得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台依照 ASTM D 1003 方法 來測定上述溶液之霧度，測得該溶液之霧度1.3%。 範例10:配製溶液3-3 取94.5g的50%乙二醇水溶液’加入5g琥珀酸，攪拌溶 解後加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧化鈦/ 一氧化錯：共沉殿物的欽化合物C-94(靖自Sachtleben Chemie GmbH)0.5g，在室溫下攪拌1天，得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台依照 ASTM D 1003 方法 來測定上述溶液之霧度，測得該溶液之霧度1.4%。 201116550 範例11 :配製溶液4-1 取59.7g的50%乙二醇水溶液，加入39 8g草酸，攪拌溶 解後，加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧化 鈦/二氧化锆共沉澱物的鈦化合物c_94(購自SachtlebenGmbH) 0.5g ‘Lion at room temperature! Days, get a clear transparent uniform solution. The haze of the above solution was measured by the HunterLab COLORQUEST XE machine using the HunterLab COLORQUEST XE machine according to the ASTM D 1003 method, and the haze of the solution was measured to be 1.8 〇/〇. Example 5: Preparation of Solution 2-1 59.7 g of a 50% aqueous solution of ethylene glycol was added to 39.8 g of salicylic acid, and the coprecipitate of titanium dioxide/silica was added after dissolution and the composition was titania/dioxide co-precipitation. Titanium compound C-94 (available from Sachtleben Chemie GmbH) 0.5 g' was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine according to the ASTM D 1003 method, and the haze of the solution was measured to be 1.5%. Example 6: Preparation of solution 2-2 79.6 g of 50% aqueous solution of ethylene glycol was added to I9.9 g of salicylic acid, and the mixture was dissolved and dissolved, and then a gasification of the chlorinated / oxidized baby was added and or 0.5 g of titanium compound C-94 (purchased from Sachtleben Chemie GmbH) of the dioxo-co-precipitate was stirred at room temperature for 1 day to obtain a clear transparent homogeneous solution. Using a HunterLab COLORQUEST XE machine, the haze of the solution was determined according to the ASTM D 1003 method, and the haze of the solution was measured to be 1.5%. Example 7: Prepare Solution 2-3 Take 94.5g of 50% aqueous solution of ethylene glycol and add 5g of salicylic acid. After dissolving and dissolving, add titanium oxide/dioxide to the co-precipitate and or make up titanium dioxide/dioxide. The coprecipitate titanium compound C-94 (available from Sachtleben Chemie GmbH) 0.5 g 'stirred at room temperature for 1 day' gave a clear transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine according to ASTM D 1〇〇3, 201116550 method, and the haze of the solution was measured to be 6%. Example 8: Prepare Solution 3-1 Take 59.7 g of 50% aqueous solution of ethylene glycol, add 39.8 g of succinic acid, stir to dissolve, add co-precipitate of titanium dioxide/silica and or coprecipitate with titanium dioxide/zirconia. Titanium compound C-94 (available from Sachtleben Chemie GmbH) 0.5 g ' stirred at room temperature for 1 day to give a clear transparent homogeneous solution. The haze of the solution was measured using a HunterLab COLORQUEST XE machine in accordance with ASTM D 1003 method, and the haze U% of the solution was measured. Example 9: Preparation of Solution 3-2 79.6 g of a 50% aqueous solution of ethylene glycol was added, 19.9 g of succinic acid was added, and the coprecipitate of titanium dioxide/silica was added after dissolution and the composition was coprecipitated with titanium dioxide/zirconia. Titanium compound C-94 (available from Sachtleben Chemie GmbH), 5 g, was stirred at room temperature for 1 day to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with ASTM D 1003 method, and the haze of the solution was measured to be 1.3%. Example 10: Preparation of Solution 3-3 Take 94.5 g of 50% aqueous solution of ethylene glycol' Add 5 g of succinic acid, stir to dissolve, add the coprecipitate of titanium dioxide/silica and or the composition of titanium dioxide / oxidization: common hall 0.5 g of the compound C-94 (Jingzi Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to obtain a clear transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine in accordance with ASTM D 1003 method, and the haze of the solution was measured to be 1.4%. 201116550 Example 11: Preparation of Solution 4-1 Take 59.7g of 50% aqueous solution of ethylene glycol, add 39 8g of oxalic acid, stir and dissolve, add co-precipitate of titanium dioxide/silica and or coprecipitate with titanium dioxide/zirconia. Titanium compound c_94 (purchased from Sachtleben

GmbH)0.5g，在室溫下攪拌丨天，得到澄清透明均勾溶液。使 用 HmtoLab COLORQUESTXE 機台依照 ASTMD 1〇〇3 方法 來測定上述溶液之霧度’測得該溶液之霧度1〇%。 範例12:配製溶液4-2 取79.6g的50%乙二醇水溶液，加入19 9g草酸，攪拌溶 解後加入二氧化鈦/二氧化硅的共沉澱物和或組成為二氧化欽/ 二氧化錯共沉殿物的鈦化合物C_94(購自Sachtleben chemieGmbH) 0.5g, stirred at room temperature for a few days to obtain a clear and transparent solution. The haze of the above solution was measured using a HmtoLab COLORQUESTXE machine in accordance with the ASTM D 1〇〇3 method, and the haze of the solution was measured by 1%. Example 12: Preparation of Solution 4-2 79.6 g of a 50% aqueous solution of ethylene glycol was added, and 19 9 g of oxalic acid was added, and after stirring, a coprecipitate of titanium dioxide/silica was added and or the composition was dioxin/dioxagen Titanium compound C_94 (purchased from Sachtleben chemie

GmbH)0.5g ’在室溫下攪拌1天’得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台依照 ASTM D 1〇〇3 方法 來測定上述溶液之霧度，測得該溶液之霧度1.1〇/〇。 範例13:配製溶液4-3 取94.5g的50%乙一醇水溶液’加入5g草酸，攪拌溶解 後加入二氧化鈇/二氧化硅的共沉澱物和或組成為二氧化鈦/二 氧化锆共沉澱物的鈦化合物C-94(購自Sachtleben Chemie GmbH)0.5g，在室溫下攪拌1天，得到澄清透明均勻溶液。使 用 HunterLab COLORQUEST XE 機台，依照 ASTM D 1003 方 法來測定上述溶液之霧度’測得該溶液之霧度1.0〇/〇。 前述範例1〜範例13之結果整理如下表1所示。GmbH) 0.5 g 'stirred at room temperature for 1 day' to give a clear, transparent homogeneous solution. The haze of the above solution was measured using a HunterLab COLORQUEST XE machine according to the ASTM D 1〇〇3 method, and the haze of the solution was measured to be 1.1 〇/〇. Example 13: Preparation of Solution 4-3 Take 94.5 g of 50% aqueous solution of ethyl alcohol. Add 5 g of oxalic acid, stir to dissolve, add co-precipitate of ceria/silica and or consist of titanium dioxide/zirconia coprecipitate. 0.5 g of titanium compound C-94 (available from Sachtleben Chemie GmbH) was stirred at room temperature for 1 day to obtain a clear transparent homogeneous solution. Using a HunterLab COLORQUEST XE machine, the haze of the solution was measured according to ASTM D 1003 method. The haze of the solution was measured to be 1.0 〇/〇. The results of the foregoing Examples 1 to 13 are organized as shown in Table 1 below.

Γ SI 11 201116550 表1 溶液 C-94 重量％ 有機酸 50%乙二醇水溶液 /有機酸（重量比） &gt;谷液外觀 霧度 Blank 0.50% — 100/0 卜 —--- 沉殿/白濁 95% 1-1 0.50% 酒石酸 60/40 ---〜 透明岣勻液 1.7% 1-2 0.50% 酒石酸 80/20 透明均勻液 1.8% 1-3 0.50% 酒石酸 95/5 透明均勻液 --—---- 透明均勻液 1.8% 2-1 0.50% 水楊酸 60/40 ------- 1.5% 2-2 0.50% 水楊酸 80/20 ----^ 透明均勻液 1.5% 2-3 0.50% 水楊酸 95/5 — 透明均勻液 1.6% 3-1 0.50% 琥珀酸 60/40 透明均勻液 1.3% 3-2 0.50% 琥珀酸 80/20 透明均勻液 1.3% 3-3 0.50% 琥珀酸 95/5 透明均勻液 1.4% 4-1 0.50% 草酸 60/40 透明均勻液 1.0% 4-2 0.50% 草酸 80/20 透明均勻液 1.1% 4-3 0.50% 草酸 95/5 透明均勻液 1.0% 一—----- 根據本說明書之另一實施例係揭露一種以含鈦組合物催 化聚酯化反應的方法。上述的聚酯化反應包含共聚酯化反應。 上述以含鈦組合物催化聚酯化反應的方法包含添加一含鈦組 合物至二羧酸酯之酯交換反應，或二羧酸與過量二元醇之縮聚 12 201116550 反應。其中，上述之含欽組合物包含含鈦共沈澱物'有機酸、 二元醇（did)、以及水。其中，相對於含鈦組合物之總量，上 述含鈦之共沈殿物的重量百分比約為〇.〇1〜2〇重量％，上述之 有機酸的重量百分比約為2〜80%，二元醇的重量百分比約為 0.1〜95重量％，水的重量百分比約為〇.1〜99重量〇/0。 根據本實施例’上述含鈦共沈殿物係含有二氧化鈦(乃〇2)/ 一氧化硅(Si〇2)的共沉澱物和/或二氧化鈦(Ti〇2)/二氧化锆 (Zr〇2)共沉澱物的鈦化合物。其中，上述二氧化鈦/二氧化娃的 共沉澱物中，Ti〇2 : Si〇2 = 90 : 1〇 至 20 : 80 mol/md，上述二 氧化鈦/二氡化锆的共沉澱物中，刃〇2 :办〇2 = % : $至π % mol/moi 〇 上述的有機酸可以是選自下列群組中之一者：甲酸，乙 酉义’草酸’丙二酸，.琥j峨，戊二酸，己二酸’庚二酸，酒石 酸，水揚酸’檸檬酸，概，蘋果酸，桂皮酸，咖哪酸。 上述的二元醇可以是選自下列群組中之一者：乙二醇， 丙一醇’ 丁二醇，戊二醇。 …在根據本實施例之一較佳範例中，上述的含鈦組合物之 调製方法如下。將含鈦之共沉殿物、有機酸、二元醇、及水混 合後’在常溫下授拌，以得到一均勾透明溶液。在根據本實施 例之另較佳範例中’上述的含鈦組合物之調製方法為，將含 鈦之共沉澱物、有機酸、乙二醇、及水混合後，進行加熱操作， 以得到一均勻透明溶液。 201116550 習知該項技藝者均知，不同的鈦類催化劑，通常需要透 過不同的雜方式以翻最佳的分散妓。娜本實施例，主 要係藉由有機_錢來完全分餘解於二元醇中的催化 劑’以徹底解決催化劑分散不均的問題，進而提高聚醋產品的 品質降低聚酯切片的Lb值。 在根據本實施例之-較佳範例中，上述以含鈦組合物催 化聚醋化反應的方法可更包含添加—磷化物至上述之二紐 酉曰之酉曰交換反應或二細镇過量二元醇之縮聚反應巾。上述之 破化物在上述之聚酿化反應中可以發揮熱安定劑之效果。上述 之磷化物可以是選自磷酸、亞磷酸、磷酸三甲酯TMp、磷酸 二乙酯TEP、磷酸三丙酯、磷酸三苯酯τρρ、磷酸三異丙酯、 磷酸二丁酯ΤΒΡ、苯基亞磷酸、苯基磷酸烷基酯、磷酸芳香酯、 亞磷酸一曱酯、亞鱗酸二乙酯、亞磷酸二丙酯、亞碌酸二異丙 酯、亞磷酸二丁酯、亞磷酸二苯酯等碟化合物或前述各礙化物 之鹽類。其中優選為磷酸、磷酸三乙酯、磷酸三曱酯等。上述 磷化合物的使用量，通常是相對於得到的聚酯樹酯，以磷原子 計約為1〜30 ppm。根據本範例，磷化合物可以單獨使用或組 合兩種以上使用。 在根據本實施例之另一較佳範例中，上述以含鈦組合物 催化聚酯化反應的方法可更包含添加一共觸媒至上述之二羧 酸酯之酯交換反應或二羧酸與過量二元醇之縮聚反應中。上述 之共觸媒係用以提升含鈦組合物之活性。上述之共觸媒可以是 201116550 選自锰、鋅、銘、鎂、銘、辑、錯、鐵、錄、銅、錄、錫、等 金屬的醋酸鹽、碳酸鹽、氣化物、硫酸鹽、雜鹽、或金屬氧 化物等金屬化合物。根據本制，在上述时鈦組合物催化聚 醋化反應的方法中，所有金屬原子的合計量，優選為小於5〇 ppm ’更優選為30 ppm以下。 在根據本實施例之另一較佳範例中，上述以含鈦組合物 催化聚反應的方法伽以製備—熱錄聚合物。上述之熱 塑性1合物係由-衍生自一二酸組份的重複單元A，與至少一 何生自-二醇組份的重複單元B所組成之聚g|。上述之二酸 組份可以1選自C2〜C16之脂職二___&amp; diearb〇xylic acid) C8 C16 之方香族一竣酸(aromatic dicarboxylie acid)、或 其組合。選擇性地，上述C8〜C16之芳香族二叛酸係為對苯二 甲酸。更佳地，上述熱塑性聚合物是聚對苯二甲酸乙二醇酯， 或聚對苯二甲酸之絲g旨。且較佳地，_二敵份的總莫爾 數计，對笨二甲酸是佔該二酸組份的至少6〇m〇i%，而以該二 酉予組份的總莫爾數計，乙二醇是佔該二醇組份的至少 mol% 〇 根據本範例，選擇性地，上述之二酸組份包含二匚^〜匸^ 之芳香族二叛酸，在本範例之一具體例中，上述二之 芳香族二羧酸分別為對苯二P酸以及間苯二甲酸。更佳地，上 述二酸組份包含96〜99mol%的對苯二甲酸及4〜I%m0l之間苯 二甲酸。 15 201116550 根據本範例，選擇性地，上述二醇組份包含至少一 C2〜C10之二醇。更佳地’該二醇組份包含至少一 之二 醇，且在聚合過程中，部分乙二醇會脫水形成二乙二醇 (diethyleneglycol，簡稱DEG) ’因此聚合產物之共聚醋中會存 在街生自二乙二醇的重複單元3。較佳地，在該聚醋中，以重 複單元B的總莫爾數計，衍生自乙二醇的重複單元b是佔 95〜99mol%，且衍生自二乙二醇的重複單元B是佔⑽抓。 • 町將以芳香族二缓酸或其相對應的酿（corresponding 和跡族二元醇或其相對應的g旨進行騎以製備聚醋 樹醋之過程作為本實施例之一示範性說明範例。然:而，本說明 書不應以此範例所述内容為限’應以其之後的申請專利範圍為 準。 〈聚酯樹酯的製造方法&gt; 〈醋化工序&gt; _ 首先，當製造聚酯樹酯時，使芳香族二羧酸或其相對應 酯和脂肪族二元醇或其相對應的酯調製成漿液後，連續供應到 酯化反應工序。通過酯化工序，得到作為芳香族二羧酸和脂肪 族二元醇的酯化反應的低縮聚物，其數均分子量約為 500〜5000左右。接著該低縮聚物被提供給液相縮聚工序。 〈液態聚合工序〉 在液態聚合工序中，於減壓條件下且通過加熱到聚酯樹 酯的熔點以上的溫度（通常為25〇〜28〇 口），使酯化工序中傳到 201116550 的低縮聚物進行縮聚。在縮聚反應中，期望使未反應的脂肪族 二兀醇去除’以進行上述之縮聚反應。經過液態聚合工序得到 固有黏度IV為0.4〜0.8 dl/g的液相縮聚樹酯後，進行切粒成為 液態聚合酯粒。 根據本實施例，含鈦之組合物以及其他依實際需要而添 加的的添加劑，例如含有金屬化合物的丼觸媒、以及含有磷化 合物之熱安定劑等，只要在縮聚反應時存在即可。因此，前述 含鈦之組合物與添加劑的添加時點，可以是在原料漿液調製工 序、S曰化工序、液相縮聚工序等之任一工序中加入。再者，根 據本實施例，前述含鈦之組合物與添加劑在使用時，可以一次 將用量添加完畢’也可以分數次添加至一道工序或數道不同工 序中。 &lt;固態聚合工序&gt; 供固相聚合工序中態聚合樹醋需先加熱到比進行固 相聚口時的溫度低的溫度崎行縣晶歧之後，再供應到固 態縮聚工。序。上·態聚合卫序可以是在氮氣氛圍下，於 90 24G C進行聚合。經過g]態聚合工序後可制固有黏度工乂 為0.4〜1.5 dl/g的固態聚合聚酯。 根據本實施例，採行上述之醋化工序和縮聚工序的聚醋 樹酉旨的製造功可以是採闕歇式、半連續式、連續式的任一 方式進行。經由本實施例所揭露的方法所得到_旨樹醋可用 作各種成形體的材料’例如，_成形並使瓶等中空成形 17 201116550 體、膠片、纖維等。 範例14 :比較例1鈦粉 將38.1 KG的對苯二曱酸(TPA)，及0.81 KG之間笨二甲 酸(IPA) ’以及18.16 KG的乙二醇（EG)加入攪拌槽中攪拌成 糊狀物。繼而將該糊狀物倒入酯化槽中，並升溫至255 t：以進 行酯化反應’反應時間約為6.5小時。當酯化率大於95%時， 可得一酯化物。將酯化物移行至聚合槽，添加範例丨的配方 blank所調製的鈦觸媒溶液3〇ppm (鈇原子相對於PET)，熱安 疋劑填酸35ppm ’以及調色劑醋酸姑35ppm。接著以約280 °C ’ 1 Torr的條件下進行縮聚反應。使其聚合至固有黏度約 〇.6dL/g左右°之後進行切粒以得到pet的液態聚合酯粒。接 著，將液態聚合酯粒倒入固聚反應器中，以15〇 t對所得到的 液態聚合酯粒進行2小時之預結晶。在235 °C，2 Torr的條件 下加熱4小時以得到固相縮聚物聚對苯二甲酸乙二醇酯之酯 粒。前述酯粒所測得之各項物性如表2所示。 範例15:酒石酸 將38.1KG的對苯二甲酸(TPA)，及〇 81KG之間苯二甲 酸(IPA)，以及18.16 KG的乙二醇（EG)加入攪拌槽中攪拌成 糊狀物。繼而將§亥糊狀物倒入醋化槽中，並升溫至Ms以進 行酉a化反應，反應時間約為6.5小時。當酿化率大於95%時， 可得一酯化物。將酯化物移行至聚合槽，添加範例4的配方 201116550 1-3所調製的鈦觸媒溶液30ppm (鈦原子相對於pET)，熱安定 劑磷酸35ppm，以及調色劑醋酸鈷35ppm。接著以約28〇乞， 1 Torr的條件下進行、縮$反應。使其聚合至固有黏度約〇 6岭 左右。之後進行切粒以得到PET的液態聚合酯粒。接著，將 液態聚合醋粒倒入固聚反應器中，α 15〇。〇對所得到的液態聚 合醋粒進行2小時之預結晶。在235，2 T〇rr的條件下加熱 4小時以得到_縮聚物聚對苯二甲酸乙二醇自旨之酉旨粒。前述 ® 酯粒所測得之各項物性如表2所示。 範例16:琥珀酸 將38.1 KG的對苯二甲酸(TPA),及〇.81 KG之間苯二甲 酸(IPA)，以及18.16 KG的乙二醇（EG)加入攪拌槽中攪拌成 糊狀物 '繼而將該糊狀物倒入酯化槽中，並升溫至.以進 行自曰化反應，反應時間約為6.5小時。當醋化率大於％%時， 可得一酯化物。將酯化物移行至聚合槽，添加範例7的配方 2-3所調製的鈦觸媒溶液3〇ppm (鈦原子相對於ρΕτ)，熱安定 35ppm，以及調色劑醋酸錄35ppm。接著以約280。〇， 1 Torr的條件下進行縮聚反應。使其聚合至固有黏度約ο/出 左右。之後進行切粒以得到PET的液態聚合酯粒。接著，將 液態聚合酯粒倒入固聚反應器中，以15〇。〇對所得到的液態聚 &amp; ®曰粒進行2小時之預結晶。在235 °C，2 Torr的條件下加熱 4小時以得到固相縮聚物聚對苯二曱酸乙二醇酯之酯粒。前述 酉旨粒所測得之各項物性如表2所示。 19 201116550 範例17 :水揚酸 將38.1KG的對苯二曱酸(TPA)，&amp; 〇 81KG之間苯二曱 酸(IPA)，以及18.16KG的乙二醇（EG)加入擾拌槽中攪拌成 糊狀物。繼而將該糊狀物倒入酯化槽中，並升溫至255以進 行酯化反應，反應時間約為6.5小時。當酯化率大於95%時， 可得一酯化物。將酯化物移行至聚合槽，添加範例1〇的配方 3- 3所調製的鈦觸媒溶液3〇ppm (鈦原子相對於pET)，熱安定 • 劑磷酸35PPm ’以及調色劑醋酸钻35ppm。接著以約28〇 〇c， 1 Torr的條件下進行縮聚反應。使其聚合至固有黏度約〇 6 dL/g 左右。之後進行切粒以得到PET的液態聚合酯粒。接著，將 液態聚合酯粒倒入固聚反應器中，以150它對所得到的液態聚 合酯粒進行2小時之預結晶。在235 〇C，2 T〇rr的條件下加熱 4小時，以得到固相縮聚物聚對苯二甲酸乙二醇酯之醋粒。前 述酯粒所測得之各項物性如表2所示。 • 範例18:草酸 將38.1KG的對苯二甲酸(TPA)，及0.81KG之間苯二甲 酸(IPA)，以及18.16 KG的乙二醇（EG)加入攪拌槽中撥拌成 糊狀物。繼而將該糊狀物倒入酯化槽中，並升溫至255 °c以進 行酯化反應，反應時間約為6.5小時。當酯化率大於97%時， 可得一酯化物。將酯化物移行至聚合槽，添加範例13的配方 4- 3所調製的鈇觸媒溶液30ppm (鈦原子相對於!&gt;£了），熱安定 劑峨酸35ppm，以及調色劑醋酸録35ppm。接著以約280 °C，Γ SI 11 201116550 Table 1 Solution C-94 wt% Organic acid 50% ethylene glycol aqueous solution / organic acid (weight ratio) &gt; Valley liquid appearance haze Blank 0.50% — 100/0 Bu —--- Shen Dian / white turbid 95% 1-1 0.50% tartaric acid 60/40 ---~ transparent 岣 1.7 1.7% 1-2 0.50% tartaric acid 80/20 transparent uniform liquid 1.8% 1-3 0.50% tartaric acid 95/5 transparent uniform liquid --- ---- Transparent uniform liquid 1.8% 2-1 0.50% Salicylic acid 60/40 ------- 1.5% 2-2 0.50% Salicylic acid 80/20 ----^ Transparent uniform liquid 1.5% 2-3 0.50% salicylic acid 95/5 — transparent homogeneous liquid 1.6% 3-1 0.50% succinic acid 60/40 transparent homogeneous liquid 1.3% 3-2 0.50% succinic acid 80/20 transparent uniform liquid 1.3% 3-3 0.50% succinic acid 95/5 transparent homogeneous liquid 1.4% 4-1 0.50% oxalic acid 60/40 transparent homogeneous liquid 1.0% 4-2 0.50% oxalic acid 80/20 transparent homogeneous liquid 1.1% 4-3 0.50% oxalic acid 95/5 transparent Homogeneous Liquid 1.0% One----- According to another embodiment of the present specification, a method of catalyzing a polyesterification reaction with a titanium-containing composition is disclosed. The above polyesterification reaction comprises a copolyesterification reaction. The above method for catalyzing a polyesterification reaction with a titanium-containing composition comprises a transesterification reaction of adding a titanium-containing composition to a dicarboxylic acid ester, or a polycondensation of a dicarboxylic acid with an excess of diol 12 201116550. Wherein, the above-mentioned composition contains a titanium-containing coprecipitate 'organic acid, a did, and water. Wherein, the weight percentage of the titanium-containing composite is about 〜1~2〇% by weight relative to the total amount of the titanium-containing composition, and the weight percentage of the above organic acid is about 2 to 80%, binary The weight percentage of the alcohol is about 0.1 to 95% by weight, and the weight percentage of water is about 0.1 to 99% by weight/0. According to the present embodiment, the above titanium-containing composite system contains a coprecipitate of titanium dioxide (Northene 2) / silicon monoxide (Si〇2) and/or titanium dioxide (Ti〇2) / zirconium dioxide (Zr〇2). A titanium compound that coprecipitates. Wherein, in the coprecipitate of the titanium dioxide/disiloxane, Ti〇2 : Si〇2 = 90 : 1 〇 to 20 : 80 mol/md, in the coprecipitate of the above titanium dioxide / zirconium dichloride, the blade 2 : 〇 2 = % : $ to π % mol / moi 〇 The above organic acid may be selected from one of the following groups: formic acid, acetaminophen 'oxalic acid' malonic acid, sucrose, glutaric acid , adipic acid 'pimelic acid, tartaric acid, salicylic acid' citric acid, general, malic acid, cinnamic acid, catechin acid. The above diol may be one selected from the group consisting of ethylene glycol, propanol&apos; butanediol, and pentanediol. In a preferred embodiment according to this embodiment, the above-described method for preparing a titanium-containing composition is as follows. After the titanium-containing common sediment, organic acid, glycol, and water are mixed, the mixture is stirred at room temperature to obtain a uniform transparent solution. In another preferred embodiment of the present embodiment, the method for preparing the titanium-containing composition described above is to mix a titanium-containing coprecipitate, an organic acid, ethylene glycol, and water, and then perform a heating operation to obtain a Uniform transparent solution. 201116550 It is well known to those skilled in the art that different titanium catalysts usually require different ways of mixing to achieve optimum dispersion. In the present embodiment, the main problem is to completely solve the problem of uneven dispersion of the catalyst by organically solving the catalyst ‘in the diol, thereby improving the quality of the vinegar product and lowering the Lb value of the polyester chip. In a preferred embodiment according to this embodiment, the above method for catalyzing a polyacetalization reaction with a titanium-containing composition may further comprise adding a phosphide to the above-mentioned bismuth oxime exchange reaction or a second fine excess Polycondensation reaction towel. The above-mentioned broken compound can exert the effect of a thermal stabilizer in the above-mentioned polymerization reaction. The above phosphide may be selected from the group consisting of phosphoric acid, phosphorous acid, trimethyl phosphate TMp, diethyl phosphate TEP, tripropyl phosphate, triphenyl phosphate τρρ, triisopropyl phosphate, dibutyl phosphate, phenyl. Phosphorous acid, alkyl phenyl phosphate, aromatic acid phosphate, monodecyl phosphite, diethyl sulphate, dipropyl phosphite, diisopropyl sulfite, dibutyl phosphite, phosphorous acid a dish compound such as phenyl ester or a salt of each of the foregoing barrier compounds. Among them, phosphoric acid, triethyl phosphate, tridecyl phosphate, and the like are preferable. The amount of the above phosphorus compound to be used is usually about 1 to 30 ppm based on the phosphorus atom relative to the obtained polyester resin. According to the present example, the phosphorus compounds may be used singly or in combination of two or more. In another preferred embodiment according to this embodiment, the above method for catalyzing the polyesterification reaction with the titanium-containing composition may further comprise adding a co-catalyst to the transesterification reaction of the above dicarboxylic acid ester or dicarboxylic acid and excess In the polycondensation reaction of glycols. The above common catalyst is used to enhance the activity of the titanium-containing composition. The above-mentioned common catalyst may be 201116550 selected from the group consisting of manganese, zinc, Ming, magnesium, Ming, series, wrong, iron, recorded, copper, recorded, tin, and other metals of acetate, carbonate, vapor, sulfate, miscellaneous a metal compound such as a salt or a metal oxide. According to the present invention, in the above method of catalyzing the polyacetalization reaction of the titanium composition, the total amount of all metal atoms is preferably less than 5 〇 ppm ', more preferably 30 ppm or less. In another preferred embodiment according to this embodiment, the above-described method of catalyzing the polymerization of a titanium-containing composition is used to prepare a thermosensitive polymer. The above thermoplastic 1 is derived from a repeating unit A derived from a diacid component and a polyg| consisting of at least one repeating unit B of the self-diol component. The above diacid component may be one selected from the group consisting of C2 to C16, a diterb〇xylic acid C8 C16 aromatic dicarboxylie acid, or a combination thereof. Alternatively, the above aromatic hydrocarbons of C8 to C16 are terephthalic acid. More preferably, the above thermoplastic polymer is polyethylene terephthalate or polyethylene terephthalate. And preferably, the total number of moles of the second enemy component is at least 6 〇m〇i% of the diacid component for the stearic acid, and the total number of moles of the component of the bismuth component. The ethylene glycol is at least mol% of the diol component. According to the present example, optionally, the above diacid component comprises an aromatic ditoponic acid of bismuth~~匸^, in one of the examples In the example, the above two aromatic dicarboxylic acids are p-benzene dicarboxylic acid and isophthalic acid, respectively. More preferably, the diacid component comprises 96 to 99 mol% of terephthalic acid and 4 to 1% by mole of benzenedicarboxylic acid. 15 201116550 According to this example, optionally, the above diol component comprises at least one C2 to C10 diol. More preferably, the diol component contains at least one diol, and during the polymerization, part of the ethylene glycol is dehydrated to form diethyleneglycol (DEG), so that the copolymerized vinegar of the polymerization product will exist in the street. Repetitive unit 3 derived from diethylene glycol. Preferably, in the polyacetate, the repeating unit b derived from ethylene glycol is 95 to 99 mol%, based on the total number of moles of the repeating unit B, and the repeating unit B derived from diethylene glycol is (10) Grab. • The town will use the aromatic sulphuric acid or its corresponding brewing (corresponding and trace diol or its corresponding g to ride to prepare the vinegar vinegar as an exemplary example of this embodiment) However, the description should not be limited to the content described in this example. It should be based on the scope of the patent application. <Production method of polyester resin> <Vination process> _ First, when manufacturing In the case of a polyester resin, an aromatic dicarboxylic acid or a corresponding ester thereof and an aliphatic diol or a corresponding ester thereof are prepared into a slurry, and then continuously supplied to an esterification reaction step. A low polycondensate of an esterification reaction of a dicarboxylic acid and an aliphatic diol having a number average molecular weight of about 500 to 5000. The low polycondensate is then supplied to a liquid phase polycondensation step. <Liquid polymerization step> In a liquid state In the polymerization step, the low polycondensate which is passed to 201116550 in the esterification step is subjected to polycondensation under reduced pressure and at a temperature higher than the melting point of the polyester resin (usually 25 〇 to 28 〇). In the reaction, it is desirable to make The reaction of the aliphatic diterpene alcohol is removed to carry out the above polycondensation reaction. After the liquid phase polycondensation resin having an intrinsic viscosity IV of 0.4 to 0.8 dl/g is obtained by a liquid polymerization step, the pellet is converted into a liquid polymerized ester pellet. In the examples, the titanium-containing composition and other additives added as needed, for example, a ruthenium catalyst containing a metal compound, and a heat stabilizer containing a phosphorus compound, may be present at the time of the polycondensation reaction. The addition of the titanium-containing composition and the additive may be carried out in any of the steps of the raw material slurry preparation step, the S gasification step, and the liquid phase polycondensation step. Further, according to the present embodiment, the titanium-containing composition may be added. When the additive is used, the dosage can be added at one time. It can also be added to one step or several different steps in fractions. &lt;Solid polymerization step&gt; The medium polymerization vinegar needs to be heated to the ratio before the solid phase polymerization step. When the temperature of the solid phase is low, the temperature is low, and then the crystal is dissipated to the solid state polycondensation. The upper state polymerization sequence can be The polymerization is carried out at 90 24 G C in a gas atmosphere. After the g] polymerization process, a solid polymerized polyester having an intrinsic viscosity of 0.4 to 1.5 dl/g can be produced. According to the present embodiment, the above-mentioned acetification process is carried out. The manufacturing work of the polyphenolic tree in the polycondensation step can be carried out in any one of a pick-up type, a semi-continuous type, and a continuous type. The obtained vinegar can be used as various shaped bodies by the method disclosed in the present embodiment. The material 'for example, _ shaped and hollowed out the bottle, etc. 17 201116550 body, film, fiber, etc. Example 14: Comparative Example 1 titanium powder will be 38.1 KG of terephthalic acid (TPA), and between 0.81 KG Formic acid (IPA)' and 18.16 KG of ethylene glycol (EG) were added to a stirred tank and stirred to form a paste. The paste was then poured into an esterification tank and heated to 255 t: to carry out the esterification reaction. The reaction time was about 6.5 hours. When the esterification rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and the formula of the ruthenium was added. The titanium catalyst solution prepared by blank was 3 〇 ppm (鈇 atom relative to PET), the heat ampoules were filled with acid 35 ppm ', and the toner acetic acid was 35 ppm. The polycondensation reaction was then carried out at about 280 ° C ' 1 Torr. It was polymerized to have an intrinsic viscosity of about 66 dL/g, and then granulated to obtain liquid polymerized ester granules of pet. Next, the liquid polymerized ester particles were poured into a solid polymerization reactor, and the obtained liquid polymerized ester particles were precrystallized at 15 Torr for 2 hours. The mixture was heated at 235 ° C, 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above ester granules are shown in Table 2. Example 15: Tartaric acid 38.1 KG of terephthalic acid (TPA), and 〇81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were placed in a stirred tank and stirred to form a paste. Then, the paste was poured into an acetalization tank, and the temperature was raised to Ms to carry out the oximation reaction, and the reaction time was about 6.5 hours. When the brewing rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and the formulation of Example 4 was added. The titanium catalyst solution prepared by the method of 201116550 1-3 was 30 ppm (titanium atom relative to pET), the heat stabilizer phosphoric acid was 35 ppm, and the toner cobalt acetate was 35 ppm. Then, the reaction was carried out under the conditions of about 28 Torr and 1 Torr. It is polymerized to an intrinsic viscosity of about 岭6 岭. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerization vinegar pellets were poured into a solid polymerization reactor, α 15 Torr. The obtained liquid polymer vinegar pellets were precrystallized for 2 hours. The mixture was heated under the conditions of 235, 2 T rr for 4 hours to obtain a condensed polymer of polyethylene terephthalate. The physical properties measured by the above ® ester granules are shown in Table 2. Example 16: Succinic acid 38.1 KG of terephthalic acid (TPA), and 81.81 KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) were added to a stirred tank to form a paste. Then the paste was poured into an esterification tank and heated to a temperature to carry out a self-deuteration reaction for about 6.5 hours. When the acetification rate is more than %%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and the titanium catalyst solution prepared in Formulation 2-3 of Example 7 was added at 3 〇 ppm (titanium atom relative to ρ Ετ), heat stabilized at 35 ppm, and toner acetic acid recorded at 35 ppm. Then take about 280. The polycondensation reaction was carried out under conditions of 1 Torr. It is polymerized to an inherent viscosity of about ο/out. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymeric ester granules were poured into a solid polymerization reactor at 15 Torr. The obtained liquid poly &amp; ® granules were precrystallized for 2 hours. The mixture was heated at 235 ° C, 2 Torr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester granule. The physical properties measured by the above-mentioned sputum particles are shown in Table 2. 19 201116550 Example 17: Salicylic acid Add 38.1KG of terephthalic acid (TPA), &amp; K81KG between benzoic acid (IPA), and 18.16KG of ethylene glycol (EG) to the scaffold Stir into a paste. The paste was then poured into an esterification tank and heated to 255 to carry out an esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 95%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and the titanium catalyst solution prepared by the formula 1 - 3 was added to a catalyst solution of 3 〇 ppm (titanium atom relative to pET), thermal stabilizer 35 ppm of phosphoric acid, and 35 ppm of toner acetic acid. The polycondensation reaction was carried out under conditions of about 28 〇 〇 c, 1 Torr. It is polymerized to an intrinsic viscosity of about d 6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymerized ester granules were poured into a solid polymerization reactor, and the obtained liquid polymer granules were precrystallized for 2 hours at 150 Å. The mixture was heated under conditions of 235 〇C, 2 T rr for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate vinegar. The physical properties measured by the above ester granules are shown in Table 2. • Example 18: Oxalic acid Add 38.1KG of terephthalic acid (TPA), and 0.81KG of phthalic acid (IPA), and 18.16 KG of ethylene glycol (EG) to a stirred tank and mix to form a paste. The paste was then poured into an esterification tank and heated to 255 ° C for esterification reaction for a reaction time of about 6.5 hours. When the esterification rate is more than 97%, an esterified product can be obtained. The esterified product was transferred to a polymerization tank, and 30 ppm of a ruthenium catalyst solution prepared by the formulation of Example 13 of Example 13 (titanium atom relative to !&gt;), a heat stabilizer citrate 35 ppm, and a toner acetic acid recorded 35 ppm were added. . Then at about 280 °C,

ί SI 20 201116550 1 T〇rr的條件下進行縮聚反應。使其聚合至固有黏度約0.6 dL/g 左右。之後進行切粒以得到PET的液態聚合酯粒。接著，將 液態聚合酯粒倒入固聚反應器中，以150。(：對所得到的液態聚 合醋粒進行2小時之預結晶。在235 〇C，2 Ton1的條件下加熱 4小時以得到固相縮聚物聚對苯二曱酸乙二醇酯之酯粒。前述 醋粒所測得之各項物性如表2所示。 表2 IV-MSP IV-SSP L La Lb 範例14 0.589 0.721 85.7 -1.5 6.5 範例15 0.592 0.738 85.7 -1.4 3.8 範例16 0.597 0.739 86.3 -1.2 4.3 範例17 0.601 0.743 85.3 -1.5 4.2 範例18 0.591 0.740 86.2 -1.3 4.7 21 1 IV-MSP :液態聚合醋粒之黏度 φ 1 IV-SSP :固聚後酯粒之黏度 *黏度數值是使用烏式(Ubbelohde)黏度進行測試，測試方法符合 ASTM D 4603。 木L、Lb、La之數值是使用日本電工（Nipp〇n Densh〇ku)ZE2000 色差計進行測試，測試方法符合ASTMD 1925。其中L數值越 大表示亮度越高；a&gt;0代表顏色偏紅，a&lt;〇代表顏色偏綠，b&gt; 〇代表顏色偏黃，b&lt;0代表顏色偏藍。ί SI 20 201116550 1 The polycondensation reaction is carried out under the conditions of T〇rr. It is polymerized to an intrinsic viscosity of about 0.6 dL/g. It is then diced to obtain liquid polymerized ester granules of PET. Next, the liquid polymeric ester granules were poured into a solid polymerization reactor at 150. (: The obtained liquid polymerized vinegar pellet was precrystallized for 2 hours. It was heated under conditions of 235 ° C, 2 Ton1 for 4 hours to obtain a solid phase polycondensate polyethylene terephthalate ester pellet. The physical properties measured by the above vinegar granules are shown in Table 2. Table 2 IV-MSP IV-SSP L La Lb Example 14 0.589 0.721 85.7 -1.5 6.5 Example 15 0.592 0.738 85.7 -1.4 3.8 Example 16 0.597 0.739 86.3 -1.2 4.3 Example 17 0.601 0.743 85.3 -1.5 4.2 Example 18 0.591 0.740 86.2 -1.3 4.7 21 1 IV-MSP: Viscosity of liquid polymerized vinegar φ 1 IV-SSP: viscosity of ester particles after solidification * Viscosity value is Uighur ( Ubbelohde) The viscosity is tested in accordance with ASTM D 4603. The values of wood L, Lb, and La are tested using a Japanese electrician (Nipp〇n Densh〇ku) ZE2000 colorimeter according to ASTM D 1925. The larger the L value Indicates that the brightness is higher; a&gt;0 represents a reddish color, a&lt;〇 represents a color greenish, b&gt; represents a yellowish color, and b&lt;0 represents a blueish color.

* 霧度··使用 HunterLab 的 COLORQUEST XE ’ 以符合 ASTM D 201116550 1003的規範進行檢測。 综合上述，本說明書揭露了一種含鈦組合物及其在聚酯/ 共聚酯製程方面之應用。上述之含鈦組合物包含一含鈦共沈澱 物、有機酸、二元醇、以及水。其中，上述之含鈦共沈殿物係 含有二氧化鈦(Ti〇2)/二氧化硅(Si〇2)的共沉澱物和/或二氧化 鈦(Τι〇2)/二氧化錯(Zr〇2)共沉澱物的鈦化合物。當上述含鈦組 合物應親/共親製辦的催化_，可藉由有機酸的 使用達到將含鈦催化劑完全分散溶解於二元醇之中的效果，進 而提高聚魅品之品質。上述含敝合物可賜加於原料裝液 調製工序、醋化工序、液相縮聚工序等任一工序中。再者，上 述含鈦組♦物可以―姐加，或乡麵加的方絲添加於上述 工序之一者，或多者。* Haze · Use HunterLab's COLORQUEST XE ' to test in accordance with ASTM D 201116550 1003. In summary, the present specification discloses a titanium-containing composition and its use in a polyester/copolyester process. The titanium-containing composition described above comprises a titanium-containing coprecipitate, an organic acid, a glycol, and water. Wherein, the above-mentioned titanium-containing composite system contains a coprecipitate of titanium dioxide (Ti〇2)/silica (Si〇2) and/or a coprecipitate of titanium dioxide (Τι〇2)/dioxin (Zr〇2) Titanium compound. When the above titanium-containing composition is to be catalyzed by the parent/co-manufacturing system, the effect of completely dispersing and dissolving the titanium-containing catalyst in the diol can be achieved by the use of the organic acid, thereby improving the quality of the enchanting product. The above-mentioned ruthenium-containing compound can be added to any of the steps of a raw material liquid preparation step, a acetification step, and a liquid phase polycondensation step. Further, the above-mentioned titanium-containing group ♦ may be added to one of the above processes, or a plurality of square wires added in the same manner.

顯然地，依照上面實施财_述，本發明可能有許多 的修正與差異。因此需要在編爾利要求項之範圍内加以 ，解’除了上述詳細的描述外，本發明還可以廣泛地在其他的 實知例中細·。上賴為本伽之健實施例而已，並非用以 限定本發明之Μ翻侧；凡其它未麟本發贿揭示之精 神下所完成的等效改變或修飾，均應包含在下述申請專利範圍 内0Obviously, the present invention may have many modifications and differences in light of the above implementation. Therefore, it is necessary to carry out the invention within the scope of the claims. In addition to the above detailed description, the present invention can be broadly described in other practical examples. The above is not intended to limit the squatting of the present invention; any equivalent changes or modifications made under the spirit of the disclosure of other uncovered licenses shall be included in the scope of the following patent application. Inside 0

22twenty two

Claims (1)

201116550 七、申請專利範圍： 1. 一種含鈦組合物，其包含： 含鈦共沈澱物，上述含鈦共沈澱物之重量百分比為〇 〇1〜2〇wt%， 其中上;述含鈦之共沈澱物包含二氧化鈦/二氧化硅的共沈澱物 和/或二氧化鈦/二氧化錯共沈澱物； 有機巧，上述有機酸之重量百分比為2〜8〇wt%; 一兀醇，二冗醇之重量百分比為0.1〜95wt% ;以及 水’水之重量百分比為〇丨〜奶加％。 2 專她邮1項之含鈦組合物，其中上述之含鈦共沈201116550 VII. Patent application scope: 1. A titanium-containing composition comprising: a titanium-containing coprecipitate, the weight percentage of the titanium-containing coprecipitate being 〇〇1~2〇wt%, wherein The coprecipitate comprises a coprecipitate of titanium dioxide/silica and/or a titania/diode co-precipitate; organically, the weight percentage of the above organic acid is 2 to 8 wt%; monodecyl alcohol, dilute alcohol The weight percentage is 0.1 to 95% by weight; and the weight percentage of water 'water is 〇丨~milk plus%. 2 She specializes in the titanium-containing composition of one item, in which the above-mentioned titanium contains a total of 、’（1 _2)/一氧化鍅(Zr〇2)共沉澱物的鈇化合物，其中，上述二 氧，鈦/二氧化麵共沉澱物中，TiQ2 : _ = 9。：丨。至2〇 : 8〇 =1/^)1 ’上述4條/二氧化 95:5至 70:30!11〇1/111〇卜 .以' 雙Γ專利圍第1項之含鈇組合物，其中上述之有機酸可 珀ί，、了2群組T之一者：甲酸’乙酸，草酸，丙二酸，琥 $丨=，t ，己二酸，庚二酸，酒石酸，水揚酸，檸檬酸， 礼酸，翱果酸，桂皮酸，咖啡酸。 4· 利範圍第1項之含鈦組合物，其中上述之二元醇可 ^選自下列群組中之—者：乙二醇，丙二醇，丁二醇，戊二 &gt;•:種以含敝合㈣崎g旨化反應 二親與二场之-聽I，上述之 :=£其=二二重含量二 -It--:- 23 201116550 6.根气申^專利範圍帛5項之以含鈦組合物催化聚醋化反應的方 ff ”述之,、幾酸係選自C2〜C16之脂肪族二驗(aliphatic d:carb〇xy lc acid) C8〜C16 之芳香族二幾酸 d賺bc^㈣ld)、或其組合，上述之二元醇包含至少一 c2〜ci〇 之二70醇。 7 f5 —周製二ΐΐ 3 ί組合物係添加於聚醋化反應中的原料毁液 樣工序、自旨化工序、液相縮紅序中之至少—工序中。 24An antimony compound of '(1 _2)/niobium oxide (Zr〇2) coprecipitate, wherein TiQ2: _ = 9 in the above-mentioned dioxane, titanium/oxide surface coprecipitate. : Hey. To 2〇: 8〇=1/^)1 'The above 4/dioxide 95:5 to 70:30!11〇1/111〇卜. The composition of the bismuth containing the first item of the double Γ patent, Wherein the above organic acid can be used as one of the two groups T: formic acid 'acetic acid, oxalic acid, malonic acid, succinic acid, t, adipic acid, pimelic acid, tartaric acid, salicylic acid, Citric acid, citric acid, citric acid, cinnamic acid, caffeic acid. 4. The titanium-containing composition of item 1, wherein the diol described above is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentane &gt;敝合(四)崎克的反应反应二亲与二场之- listening I, the above: =£其=二二重含量二-It--:- 23 201116550 6. The root gas application ^ patent scope 帛 5 items The aromatic acid is selected from the group consisting of a titanium-containing composition catalyzed by a polycondensation reaction, and the acid is selected from the group consisting of C2 to C16 aliphatic di(carboph xy lc acid) C8 to C16 aromatic diacid d earn bc ^ (four) ld), or a combination thereof, the above diol comprises at least one c2~ci〇 diol 70. 7 f5 - weekly bismuth 3 ί composition is added to the raw material in the polyacetalization reaction At least in the process of the liquid sample process, the self-directing process, and the liquid phase red-shrinking process.