經濟部中央標準局員工消費合作社印製 403765 A7 __, ___B7____五、發明説明（1 ) 本發明係指由對苯二甲酸與1，3丙二醇生產聚對苯二甲 酸丙二醇酯。 現在因爲可以低價大量取得1,3丙二醇，所以聚對苯二 甲酸丙二醇酯將是未來一種很有前途的塑料，它具有長鏈 分子結構，而且其大部份性能界於聚對苯二甲酸乙二醇酯 與聚對苯二甲酸丁二醇酯之間，可適用於整個纖維和鑄塑 領域。 專利文獻曾述及藉常用的催化劑之助，由對苯二甲酸 二甲酯生產聚對苯二甲酸丙二醇酯（美國專利：第2, 465, 319號，第4, 611，049號，第5, 340, 909號及德國專利：（OLS) 第1,954, 527號），而由對苯二甲酸合成聚對苯二甲酸丙二 I 醇酯的唯一先例，乃是美國專利第5, 340, 909號，此法係以 1，3 丙二醇與對苯二甲酸在沒有催化劑或在含鈦有機化合 物或含錫有機化合物的幫助下，進行酯化反應，最後再經 過錫催化劑之助，完成聚縮。 在合成聚對苯二甲酸丙二醇酯的過程中，由於熱分解 而得之附產品丙烯醛與烯丙醇，其中一部份隨聚縮蒸汽而 排出（美國專利第4, 611，049號，第5, 459,229號），而另一 部份則遺留在聚合物內，此兩者毒性極大，（丙烯醛工作 環境最大允許濃度爲0.1 ppm )並會剌激眼睛與內分泌膜。 所以，本發明旨在減少聚對苯二甲酸丙二醇酯內的丙 烯醛與烯丙醇的含量，並特別在提供一種方法，俾使目前 由對苯二甲酸合成的聚對苯二甲酸丙二醇酯，降低其丙烯 醛與烯丙醇的含量的希望，變爲可能。 本紙張尺度適用中國國家標準（CNS) A4規格（2丨0 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) 403765 A7 ,._/ _B7^_^_ 五、發明説明（2 ) 根據本發明所得的聚對苯二甲酸丙二醇酯，其丙烯醛 含量不會超過5 ppm，烯丙醇含量也不超過3 ppm，其方 法爲： · ' (a) 以含鈦量30至200 ppm爲無機酯化反應催化劑，進行直接 酯化反應，催化劑內含至少50摩爾％11〇2沈澱物。 (b) 酯化反應後，加入含磷量在10至lOOppm間的磷、氧化合 物，以封住酯化反應催化劑的活性。 (c) 藉常用的含銻聚縮反應催化劑之助，進行預聚縮與聚縮 反應，其冲銻用量爲100至300 ppm，同時也可依照需要 ，添加著色劑。 以上係本發明之簡介，但不得因此而視爲對本發明的限制 ，所有在本說明內引用的專利與出版物，與其原文內容並 無出入。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 本專利的原料是商業上常用於生產聚酯的對苯二甲酸 和1，3丙二醇，對苯二甲酸與1，3丙二醇也可部份以 其他二元羧酸或（與）其他二元醇替代，其含量可達15摩 爾％，例如：2，6綦二甲酸，1，4環己烷二羧酸，對 羥基苯甲酸，4，4聯苯二甲酸，乙二醇，1，2丙二醇 ，1，4 丁二醇，二甘醇，雙丙甘醇或（與）1，4環己 烷二甲醇。 對苯二甲酸與1，3丙二醇藉含鈦無機酯化反應催化 劑之助，直接進行酯化反應，鈦用量爲30至200 ppm，最好 爲50至lOOppm，該無機酯化反應催化劑內含有至少50摩爾％ Ti02^沈澱物，根據本發朋此種無機酯化反應催化劑 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐) ~ ：~~ 經濟部中央標準局員工消費合作社印製 ^03765 A7 __,__B7 ___ 五、發明説明（3 ) 內所含的鈦乃是以Ti〇2形狀而存在的鈦，而非以鈦的有機 « 酯化物形狀而存在的鈦。' 依照歐洲.專利申請第96 103 659.7 (相當於美國專利申 請第08/617, 562 )所述，由硫酸鈦熱分解而得的水合二氧化 鈦是適合在本發明內使用的，Ti〇2的含量爲50至99 %的二 氧化鈦與二氧化矽的共沈物，則特別適合於本發明。 此種共沈物曾在W095 - 18839與歐洲專利申請第716, 122A 號中被提及，但當時並非被用爲聚縮反應的催化劑。 依照本專利，要取得低含量丙烯醛與烯丙醇的聚對苯 二甲酸丙二醇酯，其關鍵在酯化反應結束後，與聚縮反應 開始前，必須使酯化反應催化劑失去作用或將其排除 (BLOCKING )，此時最好在聚縮反應開始時，加入含磷 的化合物，其磷的用量爲10至100 ppm，最好是20至60卩卩111 ，此種磷化合物，係指磷、氧化合物，如：磷酸、亞磷酸 、次磷酸、羧基磷酸以及類似的化合物，就此點而言，本 發明的生產方法基本上是與其他已知的方法不同的。 在預聚縮反應與聚縮反應中，要使用銻化合物爲催化 劑，銻含量爲100-300ppm，最好是200至250ppm，銻化合 物是常用的可溶於聚酯的銻類聚縮反應催化劑，例如醋酸 銻是，聚縮反應催化劑可以與磷化合物同時加入，但最好 不要如此，而在加完磷化合物之後，立即加入，尤其在對 於聚合物的透明度要求極高時，更要如此。 依其最終生產目的之所需，聚對苯二甲酸丙二醇酯可 以作成具有中性的，其透明藍白程度在CIELAB色値B*的-4.0 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ~' (請先閎讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 403765 A7 __, ___B7____ V. Description of the Invention (1) The present invention refers to the production of poly (trimethylene terephthalate) from terephthalic acid and 1,3 propylene glycol. Now, because 1,3 propylene glycol can be obtained in large quantities at low prices, polytrimethylene terephthalate will be a promising plastic in the future. It has a long-chain molecular structure and most of its properties are in polyterephthalic acid. Between ethylene glycol ester and polybutylene terephthalate, it can be applied to the entire fiber and casting field. Patent documents have described the production of polytrimethylene terephthalate from dimethyl terephthalate with the help of commonly used catalysts (US Patent Nos. 2,465,319, 4,611,049, 5 , 340, 909 and German Patent: (OLS) No. 1,954, 527), and the only precedent for synthesizing polytrimethylene terephthalate from terephthalic acid is US Patent No. 5,340, 909 No., this method uses 1,3 propylene glycol and terephthalic acid without a catalyst or with the help of titanium-containing organic compounds or tin-containing organic compounds, the esterification reaction, and finally with the help of tin catalyst to complete the polycondensation. During the synthesis of polytrimethylene terephthalate, part of the acrolein and allyl alcohol obtained as a result of thermal decomposition are discharged with the polycondensation vapor (US Patent No. 4,611,049, No. No. 5, 459,229), while the other part is left in the polymer, both of which are extremely toxic (the maximum allowable concentration of acrolein working environment is 0.1 ppm) and will irritate the eyes and endocrine membranes. Therefore, the present invention aims to reduce the content of acrolein and allyl alcohol in polytrimethylene terephthalate, and in particular, to provide a method for making polytrimethylene terephthalate currently synthesized from terephthalic acid, The hope of reducing its acrolein and allyl alcohol content became possible. This paper size is in accordance with Chinese National Standard (CNS) A4 (2 丨 0 x 297 mm) (Please read the precautions on the back before filling this page) 403765 A7, ._ / _B7 ^ _ ^ _ 5. Description of the invention ( 2) The polytrimethylene terephthalate obtained according to the present invention has an acrolein content of not more than 5 ppm and an allyl alcohol content of not more than 3 ppm. The method is as follows: · (a) With a titanium content of 30 to 200 ppm is an inorganic esterification catalyst, which undergoes a direct esterification reaction, and the catalyst contains at least 50 mol% of 1102 precipitates. (b) After the esterification reaction, phosphorus and an oxide compound having a phosphorus content of 10 to 100 ppm are added to seal the activity of the esterification catalyst. (c) With the help of commonly used antimony-containing polycondensation catalysts, pre-polycondensation and polycondensation reactions are carried out. The amount of antimony used is 100 to 300 ppm. At the same time, colorants can be added as required. The above is an introduction to the present invention, but it should not be considered as a limitation on the present invention. All patents and publications cited in this description are not inconsistent with their original content. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) The raw materials of this patent are terephthalic acid and 1,3 propylene glycol, terephthalic acid commonly used in the production of polyesters. And 1,3 propylene glycol can also be partially replaced with other dicarboxylic acids or (and) other glycols, the content of which can reach 15 mol%, such as: 2,6 dicarboxylic acid, 1,4 cyclohexane dicarboxylic acid Acid, p-hydroxybenzoic acid, 4,4 diphthalic acid, ethylene glycol, 1,2 propylene glycol, 1,4 butanediol, diethylene glycol, dipropylene glycol or (with) 1,4 cyclohexanedi Methanol. Terephthalic acid and 1,3 propylene glycol are directly esterified with the aid of a titanium-containing inorganic esterification catalyst. The amount of titanium is 30 to 200 ppm, preferably 50 to 100 ppm. The inorganic esterification catalyst contains at least 50 mol% Ti02 ^ precipitate, according to Benfapon's inorganic esterification catalyst. The paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm). Printed ^ 03765 A7 __, __ B7 ___ V. Description of the Invention (3) The titanium contained in the invention (3) is titanium that exists in the shape of Ti02, rather than titanium that exists in the shape of an organic «ester of titanium. '' According to European Patent Application No. 96 103 659.7 (equivalent to U.S. Patent Application No. 08/617, 562), hydrated titanium dioxide obtained by thermal decomposition of titanium sulfate is suitable for use in the present invention, and the content of Ti0 A co-precipitate of 50 to 99% titanium dioxide and silicon dioxide is particularly suitable for the present invention. Such coprecipitates were mentioned in W095-18839 and European Patent Application No. 716, 122A, but were not used as catalysts for the polycondensation reaction at that time. According to this patent, in order to obtain polytrimethylene terephthalate with a low content of acrolein and allyl alcohol, the key point is that the esterification reaction catalyst must be rendered ineffective or disabled after the end of the esterification reaction and before the polycondensation reaction begins. BLOCKING. At this time, it is best to add a phosphorus-containing compound at the beginning of the polycondensation reaction. The amount of phosphorus used is 10 to 100 ppm, preferably 20 to 60 卩 卩 111. This phosphorus compound refers to phosphorus. Oxygen compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, carboxyphosphoric acid, and similar compounds. In this regard, the production method of the present invention is basically different from other known methods. In the pre-polycondensation reaction and the polycondensation reaction, an antimony compound is used as a catalyst, and the antimony content is 100-300 ppm, preferably 200 to 250 ppm. The antimony compound is a commonly used antimony polycondensation catalyst that is soluble in polyester, such as Antimony acetate is a polycondensation catalyst that can be added at the same time as the phosphorus compound, but it is best not to do so, but to add it immediately after the phosphorus compound is added, especially when the transparency of the polymer is extremely high. According to the needs of its final production purpose, polytrimethylene terephthalate can be made neutral, and its degree of transparency blue and white is in the CIELAB color 値 B * -4.0. This paper size is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) ~ '(Please read the precautions on the back before filling this page)
403765 A7 __,. .,___ B7 ____ 五、發明説明（4 ) 至+4.0之間者，爲此，則應在聚縮反應結束前的任何時 刻，最好在酯化反應開始時，或是聚縮反應結束之前，在 反應混合物內添加著色劑，所添加的著色劑最好是能溶於 聚酯的鈷化合物，如醋酸鈷是，其鈷的用量爲20至60 ppm， 最好爲30至50 ppm。 酯化反應，預聚縮反應以及聚縮反應所需溫度與壓力 與已知的方法並無不同，在融化聚縮與切片成粒狀後，亦 可視需要，進行固相聚縮，此時亦可添加一些常用的添加 劑，例如顏料、消光劑、潤滑劑、、交叉連接劑等、 以下的實施例，旨在舉例說明，而不是，亦不可解釋 爲對本發明之限制，凡是熟悉此項技術者也會知道對以上 所述欲作不違背本發明精神與範圍的改變，是可以容許的 〇 實施例 茲舉例說明依照本發明合成聚對苯二甲酸丙二醇酯， 例中聚對苯二甲酸丙二醇酯各項數値的測定方法如下： 固有黏度：係將聚酯溶於100毫升苯酚與1.2二氯苯的 經濟部中央標準局員工消费合作社印製 (請先閎讀背面之注意事項再填寫本頁) 混合物溶液（其重量爲3:2 )中，在攝氏25度的溫度下測之 〇 端羧基含量··採用光學滴定法測定之，其法爲將聚酯 溶於鄰甲酚與氯仿的混合液（重量比70:30 )中，加入溴百 里酚藍爲指示劑，然後用0,05N的氫氧化鉀的乙醇溶液，進 行滴定。 CIELAB色値：係將聚酯切片，置於一乾燥箱內，加溫 本紙張尺度適用t國國家標準（CNS ) A4規格（210X297公釐） 403765 A7 _B7_ 五、發明説明（5 ) 至攝氏150 ± 5度，予以結晶達一小時，然後測定之，測 定聚酯樣品的色値，要使用三原色比色計，藉三個光電池 之肋，以測定.其X, Y, Z値，在每一個光電池之前，各有一 個紅色、藍色或綠色濾色器，其結果按CIELAB方法，以下 開方程式測定之： b*= 200 · 丙烯醛與烯丙醇：自然溶解於聚酯內的游離丙烯醛與烯丙 醇，依下述方法測定其含量：將待測之聚酯，先用液氮冷 卻，然後碾磨之，並篩選直徑小於0.4mm者，用於分析測 定，取上述聚酯樣品2.0克，置於一個20毫升其中裝有隔膜 的瓶內，將瓶子密封，加溫至攝氏170度，達60分鐘，最 後，通過隔膜，自瓶內氣體空間，將聚酯樣品取出，以氣 體色層分離法測定丙烯醛與烯丙醇的含量。 經濟部中央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 比較實施例1一 4，與實施例5 — 7 由一份重量的對苯二甲酸與一定重量的1，3丙二醇 (1，3PD )(用量詳下表），做成漿料，然後與酯化催化劑 和在一起，如有需要的話，也可添加一些醋酸鈷著色劑， 於前一批酯化物內，在比較實施例3與4內，聚縮反應催 化劑’也加入其中，然後混合物被酯化至反應所生的水減 至一定量爲止（酯化度至少達98.8 % )。 在比較實施例1 ， 3與4中，於酯化反應結束後，立 即開始預聚縮；而在比較實施例2中，聚縮反應催化劑係 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨Ο X 297公釐） 403765 at ______________B7_ ___ 五、發明説明（6 ) 於預聚縮反應之前加入，惟在實施例5至7例中，則在酯 化反應結束後，先要加入磷酸，然後，在預聚縮反應開始 之前，再加入聚縮反應催化劑，在實施例7中，祗要加入 大約150 ppm 的銻，其餘的100 ppm的銻則在很晚的時候纔 加入。 在100至50毫巴的壓力（絕對）下，進行預聚縮反應 達四十分鐘左右後，開始聚縮，此時將眞空度降至小於1 毫巴，除了在比較實施例2與3中，聚縮反應溫度大約是 攝氏270度或是260度至270度外，其他各例的聚縮反應 溫度均爲攝氏257至265度，下面表列的聚縮反應時間， 與在一定條件下達到可能最大黏度所需的時間相當，換言 之，如果聚合·物達到這個黏度還繼續聚縮的話，則其黏度 就會因分解效應主導之故，而不增反減。 所得的聚對苯二甲酸丙二醇酯的其他條件與特性如下 ---：----------本！ (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作杜印裝 例 號 1,3 丙二醇 酯化催化劑 mm w 聚縮催化劑 聚縮 時間 聚對苯二甲酸丙二醇酯 重量 (份） 種類 鈦缝 ppm 站缝 ppm mm ppm 種類 鈦或 銻含量 ppm 分鐘 固有 黏度 dL/G 端羧基 含量 mq/KG 丙烯醛 含量 ppm 烯丙醇 含量 ppm 色値 b* 1 0.567 TiO, SiO, 50 - - - - 171 0.926 14 10 1.7 10.4 2 0.641 Ti〇2 150 - - Ti〇2 130 120 0.802 23 >10 - 3.2 3 0.656 Ti(OBu)4 75 - - SbAC3 200 67 0.890 10 40 3.8 10.7 4 0.567 TiO„ Si〇? 50 - - SbAC3 200 113 0.918 14 11 1.4 8.8 5 0.567 TiO, SiO? 50 20 40 SbAC3 200 163 0.919 17 5 1.7 5.9 6 0.567 Ti〇„ SiO, 50 40 40 SbAC3 250 162 0.912 19 4 2.0 -0.5 7 0.567 TiO, Si〇, 50 40 60 SbAC3 250 153 0.635 16 3 2.4 -1.2 本紙張又度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 403765 at . B7 五、發明説明（7 ) 備註：Ti02 : Si02指二氧鈦化與二氧化鈔的共沈物’其 中Ti02佔80摩爾％，德國AKZO公司提供 Ti02指含童量約爲2 %的鈉與約6 %的水的水合 二氧化鈦，德國SACHTLEBEN CHEMIE公司提 供403765 A7 __ ,.., ___ B7 ____ 5. The description of the invention (4) to +4.0, for this purpose, it should be at any time before the end of the polycondensation reaction, preferably at the beginning of the esterification reaction, or Before the end of the polycondensation reaction, a colorant is added to the reaction mixture. The coloring agent added is preferably a cobalt compound that is soluble in polyester, such as cobalt acetate, and the amount of cobalt is 20 to 60 ppm, preferably 30. To 50 ppm. The temperature and pressure required for esterification, pre-polycondensation, and polycondensation are not different from known methods. After melting and polycondensing and slicing into granules, solid phase polycondensation can also be performed as required. Add some commonly used additives, such as pigments, matting agents, lubricants, cross-linking agents, etc. The following examples are intended to illustrate, but are not, and should not be interpreted to limit the present invention. It will be understood that it is permissible to make changes to the above without departing from the spirit and scope of the present invention. Examples are provided to illustrate the synthesis of polytrimethylene terephthalate in accordance with the present invention. The determination method of the term 値 is as follows: Intrinsic viscosity: It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs in which polyester is dissolved in 100 ml of phenol and 1.2 dichlorobenzene (please read the precautions on the back before filling this page) The content of the 0-terminal carboxyl group in a mixture solution (its weight is 3: 2) measured at a temperature of 25 degrees Celsius is determined by an optical titration method, in which the polyester is dissolved in A mixture of phenol and chloroform (70:30 weight ratio) was added bromine thymol blue as an indicator, and then an ethanol solution of potassium hydroxide 0,05N, carry out titration. CIELAB color tincture: The polyester chips are placed in a drying box, and the paper is heated to the national standard (CNS) A4 size (210X297 mm) 403765 A7 _B7_ V. Description of the invention (5) to 150 ° C ± 5 degrees, crystallize for one hour, and then measure it. To determine the color of the polyester sample, use the three primary colorimeter to borrow the ribs of three photovoltaic cells to determine the X, Y, and Z 値 in each one. Before the photovoltaic cell, each has a red, blue or green color filter. The results are measured according to the CIELAB method with the following open equation: b * = 200 · Acrolein and allyl alcohol: Free acrolein naturally dissolved in polyester With allyl alcohol, determine its content according to the following method: the polyester to be tested is cooled with liquid nitrogen, then milled, and those with a diameter less than 0.4 mm are used for analysis and determination, and the above polyester sample 2.0 is taken G, placed in a 20 ml bottle with a septum, sealed the bottle, warmed to 170 degrees Celsius for 60 minutes, and finally, through the septum, the polyester sample was taken out of the gas space in the bottle with a gas color Determination of acrolein and ene by layer separation Alcohol content. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) Comparative Examples 1 to 4 and Examples 5 to 7 consist of one part of terephthalic acid and a certain weight of 1,3 propylene glycol (1,3PD) (the amount is detailed in the table below), made into a slurry, and then mixed with the esterification catalyst, if necessary, you can also add some cobalt acetate colorant to the previous batch of esterification In Comparative Examples 3 and 4, a polycondensation reaction catalyst 'was also added thereto, and then the mixture was esterified until the water produced by the reaction was reduced to a certain amount (the degree of esterification reached at least 98.8%). In Comparative Examples 1, 3 and 4, pre-polycondensation was started immediately after the end of the esterification reaction; while in Comparative Example 2, the polycondensation catalyst was based on the Chinese paper standard (CNS) A4 specification ( 2 丨 〇 X 297 mm) 403765 at ______________B7_ ___ V. Description of the invention (6) Added before the pre-polycondensation reaction, but in Examples 5 to 7, after the esterification reaction is completed, phosphoric acid must be added first. Then, a polycondensation catalyst was added before the pre-polycondensation reaction was started. In Example 7, the antimony was added with about 150 ppm of antimony, and the remaining 100 ppm of antimony was added very late. At a pressure of 100 to 50 mbar (absolute), the pre-polycondensation reaction is carried out for about forty minutes, and then the polycondensation starts. At this time, the porosity is reduced to less than 1 mbar, except in Comparative Examples 2 and 3. The temperature of the polycondensation reaction is about 270 degrees Celsius or 260 degrees to 270 degrees Celsius. The polycondensation reaction temperature of the other cases is 257 to 265 degrees Celsius. The polycondensation reaction time listed in the table below is reached under certain conditions It may take the same time as the maximum viscosity. In other words, if the polymer and the polymer continue to condense after reaching this viscosity, the viscosity will be dominated by the decomposition effect without increasing or decreasing. Other conditions and characteristics of the obtained polytrimethylene terephthalate are as follows: --------------- this! (Please read the precautions on the back before filling this page) Order the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed equipment example 1,3 Propylene glycol esterification catalyst mm w Polycondensation catalyst Polycondensation time Polytrimethylene terephthalate Weight (Parts) Type titanium seam ppm Station seam ppm mm ppm Type titanium or antimony content ppm Min intrinsic viscosity dL / G terminal carboxyl content mq / KG acrolein content ppm allyl alcohol content ppm color 値 b * 1 0.567 TiO, SiO, 50 ----171 0.926 14 10 1.7 10.4 2 0.641 Ti〇2 150--Ti〇2 130 120 0.802 23 > 10-3.2 3 0.656 Ti (OBu) 4 75--SbAC3 200 67 0.890 10 40 3.8 10.7 4 0.567 TiO „Si〇? 50--SbAC3 200 113 0.918 14 11 1.4 8.8 5 0.567 TiO, SiO? 50 20 40 SbAC3 200 163 0.919 17 5 1.7 5.9 6 0.567 Ti〇„ SiO, 50 40 40 SbAC3 250 162 0.912 19 4 2.0 -0.5 7 0.567 TiO, Si〇, 50 40 60 SbAC3 250 153 0.635 16 3 2.4 -1.2 This paper is again applicable to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 403765 at. B7 V. Description of Invention (7) Remarks: T i02: Si02 refers to the co-precipitate of titanium dioxide and banknote dioxide, of which Ti02 accounts for 80 mol%. German AKZO company provides Ti02 refers to hydrated titanium dioxide containing about 2% sodium and about 6% water. Provided by SACHTLEBEN CHEMIE
Ti(〇Bu)4指四丁基氧鈦 SbAC3指醋酸銻 如上表所示，四丁基氧鈦（比較實施例3 )會使產品 的色澤微黃，丙烯醛與浠丙醇的含量偏高，此外，根據本 發明，其酯化反應時間也比使用二氧代鈦沈澱物作催化劑 時的酯化反應時間爲長，就本發明所使用的催化劑而言’ 二氧化鈦與二氧化矽共沈物，具有較高的催化活性’但對 聚合物（在未使用著色劑時），要比使用純二氧化鈦沈澱 物（比較實物例2 )時，容易褪色多了，不過，褪色可由 添加適量的著色劑加以矯正，如此，也可使所生產的聚酯 其色値b*小於+0.5 (參考實例6與7 )。 依照本發明，不管是使用那一種聚縮反應催化劑，所 獲得的聚合物，其烯丙醇的含量則是令人滿意的，雖然其 丙烯醛的含量比使用四丁基氧鈦時低，但最低也不過10 ppm (見比較實施例1，2與4.)，仍嫌偏高，爲使聚酯 的丙烯醒含量不超過5 ppm起見，依照本發明，即須在聚縮 之前，加入一種磷、氧化合物，將Ti02基的酯化催化劑的 活性，完全加以封住（參看實施例5與比較實施例4 )， 並要在聚縮催化劑中，選用不含鈦者。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先聞讀背面之注意事項再填寫本頁)Ti (〇Bu) 4 refers to tetrabutyltitanium oxide SbAC3 refers to antimony acetate As shown in the table above, tetrabutyltitanium oxide (Comparative Example 3) will make the color of the product slightly yellow, and the content of acrolein and gadopropanol will be higher In addition, according to the present invention, the esterification reaction time is also longer than the esterification reaction time when a titanium dioxo precipitate is used as a catalyst. As far as the catalyst used in the present invention is concerned, the co-precipitated titanium dioxide and silicon dioxide , Has a higher catalytic activity ', but for polymers (when no colorant is used), it is easier to fade than when using pure titanium dioxide precipitate (comparative example 2), but the discoloration can be added by adding an appropriate amount of coloring agent Corrected so that the color b * of the polyester produced can also be less than +0.5 (refer to Examples 6 and 7). According to the present invention, no matter which kind of polycondensation catalyst is used, the polymer obtained has an allyl alcohol content that is satisfactory. Although its acrolein content is lower than that when using tetrabutyltitanium oxide, The minimum is not more than 10 ppm (see Comparative Examples 1, 2 and 4.), which is still too high. In order to prevent the propylene content of polyester from exceeding 5 ppm, according to the present invention, it must be added before the polycondensation. A phosphorus and oxygen compound that completely seals the activity of a Ti02-based esterification catalyst (see Example 5 and Comparative Example 4), and selects a titanium-free catalyst in the polycondensation catalyst. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)