593246 __案號90133028_年月曰 修正___ 五、發明說明（1) 本發明係有關於一種製備磺酸鈉笨二甲酯醇的方法， 特別有關於一種可在製備磺酸鈉苯二甲酯醇過程中降低雙 丙二醇量（Dipropylene Glycol, DPG)的方法。 近二十年來全球各紡織纖維中以聚酯纖維的產能成長 最為快速。同樣地，與聚酯相關的共聚物研發也受到相當 的重視，世界上具有商業開發價值的酯類纖維，較熟悉的 有聚對苯二甲酸乙二酯（PET)和聚對笨二甲酸丁二g旨 (PBT )織維。 1 9 95年SHELL公司開始量產地毯用聚對笨二甲酸丙二 酯（Polypropylene Terephthalate,PTT)纖維，具有 NYLON纖维的回彈性優點，另外最大的特色是PTT纖維可常 壓染色而不需要導染劑•就環境保護及節約能源觀點來 看，PTT是新型聚酯纖維中相當具潛力的產品。如同PET的 研發進展，有關含有磺酸鹽苯基團的PTT共聚酯具有陽離 子可染型之特性。此種陽離子可染PTT (簡稱CD-PTT )若 與PTT搭配，可製造雙色調效果，開發出各種不同色調的 新紗種及新布種，提高聚酯織物的價位。另外，PTT織物 的吸濕性比PET織物差，導致抗靜電性及抗防污性也較 差。CD-PTT可降低PTT之此項缺點。 目前常用之商業化CD-PET之製備方法，通常是以5-磺 酸鈉苯二甲酸甲酯（簡稱MS )與大量乙二醇（EG )於催化 劑或添加劑下進行反應，而得到含各種混合物之乙二醇溶 液。再以此中間產物混合物與SPET聚合物進行共聚和反 應。該中間產物混合物已經有許多報導，例如日本專利 JP2000 1 361 78 (SANYO CHEM, 20 00 ) ·日本專利 593246 __案號 90133028_年月 日__ 五、發明说明（2) JP41 69 566 (TAAKEM0T0, 1 9 92 )，日本專利 JP5 81 5 776 (SUZUKI, 1953)等。上述方法之缺點在於若以丙二醇 (1, 3-propanediol ; 1，3-PDO )替代乙二醇（EG )時，反 應時間太長，且雙丙二醇 -0CH2CH2CH2OCH2CH2CH20,（dipropylene glycol ;DPG)的含 量太高，將導致纖維紡絲品質大幅下降。 另外Ho’echst公司（1 99 7年）報導，先將5 -磺基異苯 二酸（54111{〇15〇口111:1^131：1〇&(^(1;5-31?八）與鹼中和形成 鹽類，再分散於二醇溶劑中，然後加入催化劑反應。其缺 點為5-SIPA在溶劑中溶解度不佳，故需使用大量溶劑。較 早期的報導也有如美國專利3018272所教導，是以甲醇與 苯為溶劑。該方法在實用上會有環保的問題。 上述各種文獻，皆是針對CD-PET產物的研發，但對 CD-PTT則未有具雄報導β 负鑑於此，本發明提供一種合成CD_pTT的製程，可提 尚5 %酸納本二甲酸甲酿（§)之醋化率並能大幅減少中間 體化合物溶液之雙丙二醇（DPG)的含量，避免降低孅維 品質。 為了達成本發明，本發明之製偫磺酸鈉苯二甲酯醇 (如化學式I所示）593246 __Case No. 90133028_ Revised Month ___ V. Description of the invention (1) The present invention relates to a method for preparing sodium sulfonate dimethyl alcohol, especially to a method for preparing sodium sulfonate Method for reducing the amount of Dipropylene Glycol (DPG) in the methyl alcohol process. In the past two decades, the production capacity of polyester fibers among the world's textile fibers has grown fastest. Similarly, the development of polyester-related copolymers has also received considerable attention. The ester fibers of commercial development value in the world are more familiar with polyethylene terephthalate (PET) and polybutylene terephthalate. Two g purpose (PBT) weaving and maintaining. 1 In 1995, SHELL Company began mass production of Polypropylene Terephthalate (PTT) fibers for carpets. It has the resilience advantages of NYLON fibers, and the biggest feature is that PTT fibers can be dyed at normal pressure without the need. Dyeing agent • From the standpoint of environmental protection and energy saving, PTT is a promising product among new polyester fibers. As with the development of PET, PTT copolyesters containing sulfonate phenyl groups have the characteristics of cationic dyeability. This cationic dyeable PTT (abbreviated as CD-PTT), when combined with PTT, can create a two-tone effect, develop new yarn types and new cloth types in various shades, and increase the price of polyester fabrics. In addition, PTT fabrics are less hygroscopic than PET fabrics, resulting in poor antistatic and antifouling properties. CD-PTT can reduce this disadvantage of PTT. At present, the commonly used commercial CD-PET preparation method is usually a reaction of sodium 5-sulfonate methyl phthalate (MS) with a large amount of ethylene glycol (EG) under a catalyst or an additive to obtain various mixtures. Glycol solution. This intermediate product mixture is then copolymerized and reacted with the SPET polymer. There have been many reports of this intermediate product mixture, for example, Japanese Patent JP2000 1 361 78 (SANYO CHEM, 20 00) · Japanese Patent 593246 __Case No. 90133028_ Year Month Day__ V. Description of the Invention (2) JP41 69 566 (TAAKEM0T0 , 1 9 92), Japanese Patent JP 5 81 5 776 (SUZUKI, 1953) and the like. The disadvantage of the above method is that if propylene glycol (EG) is replaced by propylene glycol (1,3-propanediol; 1,3-PDO), the reaction time is too long, and the content of dipropylene glycol-0CH2CH2CH2OCH2CH2CH20, (dipropylene glycol; DPG) is too high. High, will lead to a significant decline in fiber spinning quality. In addition, Ho'echst Company (1977) reported that the 5-sulfoisophthalic acid (54111 {〇15〇 口 111: 1 ^ 131: 1〇 & (^ (1; 5-31? 八) Neutralize with alkali to form salts, re-disperse in diol solvent, and then add catalyst to react. Its disadvantage is that 5-SIPA has poor solubility in the solvent, so a large amount of solvent is needed. Earlier reports are also like US patent 3018272 It is taught that methanol and benzene are used as solvents. This method has practical environmental protection problems. The above-mentioned various documents are aimed at the development of CD-PET products, but CD-PTT has not been reported with a strong β negative view. Therefore, the present invention provides a process for synthesizing CD_pTT, which can improve the vinegarization rate of 5% acid sodium dicarboxylic acid methyl ester (§) and greatly reduce the content of dipropylene glycol (DPG) in the intermediate compound solution, thereby avoiding the reduction of dimensionality. Quality. In order to achieve the present invention, the sodium sulfonate dimethyl dimethyl alcohol of the present invention (as shown in Chemical Formula I)
593246 索號 90133028 年月曰 五、發明說明（3)593246 Call No. 90133028 Date of the fifth edition of the invention (3)
的方法，係將（A )磺酸納笨二甲酸酯（如化學式I I所示The method is to use (A) sodium benzoate dicarboxylate (as shown in Chemical Formula I I
，（8)1，3-丙二醇，（〇)1^((^)4以及（0)鹼金屬鹽類 混合之後•在140~220 °C溫度之間進行反應；其中B/A莫耳 比為2·0、40· 0 。 上述方法中，該磺酸鈉苯二甲酸酯係擇自5 -磺酸鈉異 苯二曱酸甲酯'5 -磺酸鈉異苯二甲酸乙酯、5 -磺酸鈉異苯 二甲酸丙酯及5-續酸納異笨二甲酸丁酯所組成之群組。而 TiOR中的R為-(CH2)nCH3，n則為卜7。上述鹼金屬鹽類為碳 酸鈉或醋酸鈉。 根據本發明之製備磺酸鈉苯二甲酷醇的方法，除了大 幅降低雙丙二醇（DPG )的含量之外，亦開發使用不同的 觸媒大幅提高MS的gg化率。 為了讓本發明之上述目的、特徵和優點更明顯易懂， 下文特舉出較佳實施例’並配合所附圖示，作詳細說明如 下_·, (8) 1,3-propanediol, (〇) 1 ^ ((^) 4 and (0) alkali metal salts after mixing • Reaction between 140 ~ 220 ° C; where B / A molar ratio 2 · 0, 40 · 0. In the above method, the sodium sulfonate phthalate is selected from methyl 5-sodium sulfonate isophthalate, methyl 5-sodium sulfonate isophthalate, The group consisting of 5-sodium sulfonate propyl isophthalate and 5-butanoic acid sodium isobutyryl dicarboxylate. The R in TiOR is-(CH2) nCH3, and n is bu 7. The above alkali metals The salts are sodium carbonate or sodium acetate. According to the method for preparing sodium xylitol sulfonate according to the present invention, in addition to greatly reducing the content of dipropylene glycol (DPG), different catalysts are also used to greatly increase the gg of MS In order to make the above-mentioned objects, features and advantages of the present invention more comprehensible, the following describes the preferred embodiments and the accompanying drawings for detailed description as follows.
第8頁 593246 _案號90133028__年月日 修正_ 五、發明說明（4) 實施例 實施例1Page 8 593246 _Case No. 90133028__ Year Month Day Amendment _ V. Description of the Invention (4) Example Example 1
將5-磺酸鈉笨二甲酸曱酯（ms)(178克，〇·6莫耳）與 1，3-丙二醇（450克，6·5莫耳）混合後，加入丁基鈦 (Tetrabutyloxyl Titanium; ΤΒΤ) (0·7 克，llOOppm)及 碳酸納（0·65克，10 0 0 ppm )，將所得之混合物加熱至反應溫 度130〜180 X：之間4小時，將此所得之混合物取樣以HPLC分 析·· HPLC(tnethanol，elution time, minute):2.1 (<1· 0%，DPG ) : 3. 24 (主產物）；6· 35(< 0· 2%，含DPG 之磺酸鈉苯二甲酯醇衍生物）。此混合物液體再逐漸減壓 下，將低沸點溶劑及化合物蒸餾出，存留於反應器内之產 品，以HPLC及1 HNMR分析及計算後，確定為磺酸鈉苯二甲 S旨醇化合物（如化學式I所示）。iHNMR(d广三氟醋酸， PPm): 了·57(3Η，磺酸鈉苯基）；4·15(4Η，CH20); 4·08(4Η，-CH202C·) ; 3·4(<1%，-CH20CH2-，DPG); 1· 88-1· 82(4H，-CH2-，1, 3-PDO 及DPG)。檢測釋出之甲酯 量分析結果顯示MS酯化率高於90 %。 實施例2 反應條件與實施例1相同，惟加入丁基鈦及醋酸鈉。 化率及DPG含量之結果如表1所示β 比較例1 將5-磺酸鈉苯二甲酸甲酯（MS)與1,3-丙二醇依實施 例1相同之莫耳比例混合後，加入20 0ppm之酷酸鋅或贈酸 鈣，將所得之混合物加熱至反應溫度130〜180 °C之間4小Tetrabutyloxyl Titanium (ms) (ms) (178 g, 0.6 mol) was mixed with 1,3-propanediol (450 g, 6.5 mol), and sodium sulfonate was added. ΤΒΤ) (0.7 g, 110 ppm) and sodium carbonate (0.65 g, 100 ppm), and the resulting mixture was heated to a reaction temperature of 130 to 180 X: 4 hours between, and the resulting mixture was sampled Analysis by HPLC · HPLC (tnethanol, elution time, minute): 2.1 (< 1.0%, DPG): 3. 24 (main product); 6. 35 (< 0.2%, sulfur containing DPG Sodium phthalate alcohol derivative). After the liquid of this mixture was gradually reduced in pressure, the low-boiling solvents and compounds were distilled off, and the products remaining in the reactor were analyzed and calculated by HPLC and 1 HNMR, and determined as the sodium sulfonate xylyl alcohol. Shown in Chemical Formula I). iHNMR (d-trifluoroacetic acid, PPm): 57 · (3Η, sodium sulfonate phenyl); 4 · 15 (4Η, CH20); 4 · 08 (4Η, -CH202C ·); 3 · 4 (< 1%, -CH20CH2-, DPG); 1. 88-1 · 82 (4H, -CH2-, 1, 3-PDO and DPG). Analysis of the amount of methyl esters released showed that the esterification rate of MS was higher than 90%. Example 2 The reaction conditions were the same as in Example 1, except that butyl titanium and sodium acetate were added. The results of chemical conversion rate and DPG content are shown in Table 1. Comparative Example 1 After mixing sodium 5-sulfonate methyl phthalate (MS) with 1,3-propanediol at the same molar ratio as in Example 1, 20 was added. 0ppm zinc cool acid or calcium donate, heat the resulting mixture to a reaction temperature between 130 ~ 180 ° C for 4 hours
593246 _案號90133028__年月日 修正__ 五、發明說明（5) 比較例2 反應條件與比較例1相同，惟以丁基欽取代醋酸鋅或 醋酸鈣。酯化率及DPG含量之結果如表1所示。 觸媒 添加劑 «料MS2酯化華 C酯化時間4小時） 中藺Η溶液Φ DPG含至（％ ) 霣施例1 丁基》 破酸撕 >90% <1.096 寅施例’2 丁基肽 睡駸肭 >9096 <1.0% 比K例1 睡ft鋅或 醱酸眄 無 <2096 比Κ例2 丁基鈦 無 >9056 5.0% 表1的數據顯示，比較例1及比較例2顯示，若僅單獨 使用丁基鈦或雖酸鋅（或醋酸約）為觸媒，無法同時達到 高酯化率以及低DPG含量，而實施例1及2同時使用丁基鈦 以及碳酸鈉或醋酸鈉，酯化率達85%以上，而DPG含量皆 低於1.0%，因而達成本發明之發明目的。即，根據本發 明之製備磺酸鈉苯二甲酯醇的方法，藉由使用鈦系觸媒及 添加劑碳酸鈉（或醋酸鈉），可提高酯化率，減少反應時 間，且所需之反應溫度較低，同時DPG含量也大幅減少， 可避免影響纖維產品的品質。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 β mraHi mm593246 _Case No. 90133028__Year Month Day Amendment __ V. Description of the Invention (5) Comparative Example 2 The reaction conditions were the same as those of Comparative Example 1, except that butyl acetate was used instead of zinc acetate or calcium acetate. The results of the esterification rate and DPG content are shown in Table 1. Catalyst additives «Material MS2 esterification Hua C esterification time 4 hours) Medium 蔺 Η solution Φ DPG content to (%) 霣 Example 1 Butyl" acid breaking > 90% < 1.096 Yin Example '2 Ding Base peptides > 9096 < 1.0% ratio K Example 1 < zinc or osmium acid < 2096 ratio & K Example 2 butyl titanium > 9056 5.0% The data in Table 1 shows that Comparative Example 1 and Comparative Example 2 shows that if only butyl titanium or zinc acid (or acetic acid) is used as a catalyst, high esterification rate and low DPG content cannot be achieved at the same time, while Examples 1 and 2 use both butyl titanium and carbonic acid. Sodium or sodium acetate has an esterification rate of more than 85% and a DPG content of less than 1.0%, thus achieving the purpose of the invention. That is, according to the method for preparing sodium dimethyl sulfonate according to the present invention, by using a titanium catalyst and an additive sodium carbonate (or sodium acetate), the esterification rate can be increased, the reaction time can be reduced, and the required reaction The temperature is lower and the DPG content is also greatly reduced, which can avoid affecting the quality of fiber products. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. The scope of protection shall be determined by the scope of the attached patent application. β mraHi mm