572788 A7 B7 五、發明説明（]) 技術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關雙酚類製造用酸性陽離子交換樹脂固定 床之製造方法，更詳細地說係有關，以含氮硫化合物使酸 性陽離子交換樹脂均勻地部分中和之雙酚類製造用酸性陽 離子交換樹脂固定床之製造方法。 背景技術 已知雙酚類，例如2，2 —雙（4 一羥苯基）丙烷（ 以下簡稱雙酚A )係爲，聚碳酸酯樹脂或聚丙烯酸酯樹脂 等工程塑料，或環氧樹脂等原料之重要化合物，且近來需 求大增，已知以該雙酚A爲首之雙酚類製法爲，以酸性陽 離子交換樹脂（以下亦簡稱爲離子交換樹脂）固定床爲觸 媒，使苯酚類及羥基化合物反應。又，此時爲了抑制例如 雙酚A產生異構體2 -（2 -羥苯基）一 2— (4 —羥苯 基）丙烷之副產物，已知可使用以含氮硫化合物使離子交 換樹脂均勻地部分中和之物作爲觸媒，且該中和法已有各 種提案。 經濟部智慧財產局8工消費合作社印製 例如，特公昭6 2 - 7 4 8號公bg所揭示，使離子交 換樹脂固定床中添加鹽酸之液體循環的方法，但，使用鹽 酸會有裝置腐蝕之問題。又，特開平8 — 4 0 9 6 1號公 報所揭示，中和劑之含氮硫化合物中添加芳香族磺酸類之 方法，雖然芳香族磺酸類無腐蝕問題，但，以水洗淨或以 苯酚取代離子交換樹脂時，會使酸中斷而變差，而對反應 開始時之製品品質有不良影響之問題。因此，’需求不須添 -4- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部智慧財產局員工消费合作社印製 572788 A7 一一 _____B7___ 五、發明説明（2 ) 加酸之中和方法。 發揭揭示 有鑑於此，本發明之目的爲，提供一種無需添加酸之 雙酉分類製造用陽離子交換樹脂固定床之製造方法。 經本發明者們專心硏究後發現，於將酸性陽離子交換 樹脂塡入反應器而形成固定床後，反應開始前以水洗淨， 再將流出之洗淨水中溶解含氮硫化合物而成之水溶液裝入 該反應器並循環時，可有效地達成本發明之目的，而完成 本發明。 即，本發明之要點如下所示。 1 . 一種雙酚類製造用酸性陽離子交換樹脂固定床之 製造方法，其特徵爲，以含氮硫化物使酸性陽離子交換樹 脂均勻地部分中和之雙酚類製造用酸性陽離子交換樹脂固 定床之製造方法中，係於將酸性陽離子交換樹脂塡入反應 器而形成固定床後，反應開始前以水洗淨’再將流出之洗 淨水中溶解含氮硫化物而成之水溶液裝入該反應器並循環 〇 2 ·如第1項所記載之雙酚類製造用酸性陽離子交換 樹脂固定床的製造方法’其中’酸性陽離子交換樹脂爲磺 酸型陽離子交換樹脂。 3 ·如第1或2項所記載之雙酚類製造用酸性陽離子 交換樹脂固定床的製造方法’其中’含氮硫化物爲騎4基太完 基胺類或噻唑烷類。 ‘ 本紙張尺度適用中國國家標準（CNS)八4規格（210x297公釐1 ^ (請先閲讀背面之注意事項再填寫本頁)572788 A7 B7 V. Description of the invention (]) Technical field (please read the notes on the back before filling this page) The present invention relates to a method for manufacturing an acidic cation exchange resin fixed bed for the manufacture of bisphenols. , A method for producing an acidic cation exchange resin fixed bed by using a nitrogen-containing sulfur compound to uniformly partially neutralize an acidic cation exchange resin. BACKGROUND ART Bisphenols are known, for example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) are engineering plastics such as polycarbonate resin or polyacrylate resin, or epoxy resin, etc. An important compound of raw materials, and the demand has recently increased greatly. It is known that the bisphenols produced by this bisphenol A method are based on acidic cation exchange resin (hereinafter also referred to as ion exchange resin) fixed bed as a catalyst to make phenols. And hydroxy compounds. In addition, at this time, in order to suppress, for example, the production of a by-product of the isomer 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane from bisphenol A, it is known to use an ion exchange with a nitrogen-containing sulfur compound. Resin is partially and neutrally used as a catalyst, and various proposals have been made for the neutralization method. Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, disclosed in JP 6 2-7 4 8 bg, a method for circulating a liquid containing hydrochloric acid added to a fixed bed of ion exchange resin. However, the use of hydrochloric acid will corrode the device. Problem. In addition, Japanese Patent Application Laid-Open No. 8-4 0 9 61 discloses that a method for adding an aromatic sulfonic acid to a nitrogen-sulfur compound of a neutralizing agent has no problem with the corrosion of the aromatic sulfonic acid. When phenol replaces the ion exchange resin, the acid is interrupted and deteriorated, which has a problem of adversely affecting the product quality at the beginning of the reaction. Therefore, 'No need to add -4- This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 572788 A7 One by one _____B7___ 5. Description of the invention (2) Add acid neutralization method. According to the disclosure, in view of this, an object of the present invention is to provide a method for producing a cation exchange resin fixed bed for the production of double fluorene classification without adding an acid. After intensive research, the inventors discovered that after the acidic cation exchange resin was poured into the reactor to form a fixed bed, it was washed with water before the reaction started, and the aqueous solution obtained by dissolving nitrogen-sulfur compounds was dissolved in the outflowing washing water. When loaded into the reactor and recycled, the purpose of the present invention can be effectively achieved, and the present invention can be completed. That is, the gist of the present invention is as follows. What is claimed is: 1. A method for manufacturing an acidic cation exchange resin fixed bed for the production of bisphenols, characterized in that the acidic cation exchange resin fixed bed for the production of bisphenols is uniformly and partially neutralized with a nitrogen-containing sulfide. In the manufacturing method, after the acidic cation exchange resin is poured into the reactor to form a fixed bed, it is washed with water before the reaction starts, and an aqueous solution prepared by dissolving nitrogen-containing sulfide in the outflowing washing water is charged into the reactor. Recycling 02-The method for producing an acidic cation exchange resin fixed bed for bisphenol production as described in item 1, wherein the "acid cation exchange resin is a sulfonic acid type cation exchange resin. 3. The method for producing an acidic cation exchange resin fixed bed for the production of bisphenols according to item 1 or 2 ', wherein the nitrogen-containing sulfide is a 4-base hexamethyleneamine or a thiazolidine. ‘This paper is sized for China National Standards (CNS) 8-4 (210x297 mm 1 ^ (Please read the notes on the back before filling this page)
572788 A7 B7 五、發明説明（3 ) 4 ·如第1至3項中任何一項所記載之雙酚類製造用 酸性陽離子交換樹脂固定床的製造方法，其中，雙酸類爲 2，2 -雙—（4 一羥苯基）丙烷。 發明實施之最佳形態 下面將詳細說明本發明。 本發明之雙酌類係由苯酸類及經基化合物反應而製得 〇 雙酚類係指，對羥基之對位須不具有取代基者。具體 例如' 苯酚、〇 -甲酚、m —甲酚、0 — t e r t — 丁基 苯酚、2，6 —二甲苯酚、2，6 -二—tert — 丁基 苯酚等烷基苯酚或〇 -氯苯酚、m -氯苯酚、2，6 -二 . 氯苯酚等鹵化苯酚。 羥基化合物之具體例如，丙酮、甲基乙基酮、甲基異 丁基酮、甲基- η -丙基酮、苯乙酮、環己酮等酮類或甲 醛水、乙醛、苯甲醛等醛類。 本發明較佳爲，以丙酮及苯酚爲原料製造雙酚Α。 作爲觸媒之酸性陽離子交換樹脂較佳爲磺酸系之物， 又作爲母體之樹脂如’苯乙烯-二乙烯基苯共聚合物系、 全氟乙烯共聚合物系、苯酚一甲醛聚合物系等，又以苯乙 希-二乙烯基苯共聚合物系爲佳。該樹脂可爲凝膠型或多 孔型’但，以交聯度例如2至8 %之較低者爲佳。將該酸 性陽離子交換樹脂塡入反應器中，可形成固定床。 本發明係於將酸性陽離子交換樹脂塡入反應器而形成 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 丨J,--------- (請先閱讀背面之注意事項再填寫本頁)572788 A7 B7 V. Description of the invention (3) 4 · The method for producing an acidic cation exchange resin fixed bed for the production of bisphenols according to any one of items 1 to 3, wherein the bisacids are 2, 2 -bis — (4-monohydroxyphenyl) propane. Best Mode for Carrying Out the Invention The present invention will be described in detail below. The bisphenols of the present invention are prepared by the reaction of benzoic acids and base compounds. Bisphenols refer to those which do not have a substituent at the para position of the hydroxyl group. Specific examples include alkylphenols such as' phenol, 0-cresol, m-cresol, 0-tert-butylphenol, 2,6-xylenol, 2,6-di-tert-butylphenol, or 0-chloro Halogenated phenols such as phenol, m-chlorophenol, and 2,6-di-chlorophenol. Specific examples of the hydroxy compound include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-η-propyl ketone, acetophenone, and cyclohexanone, or formaldehyde water, acetaldehyde, benzaldehyde, etc. Aldehydes. In the present invention, bisphenol A is preferably produced using acetone and phenol as raw materials. The acidic cation exchange resin as the catalyst is preferably a sulfonic acid-based resin, and the resin used as a precursor such as a 'styrene-divinylbenzene copolymer polymer system, a perfluoroethylene copolymer polymer system, and a phenol-formaldehyde polymer system. Etc. Preferably, a styrene-divinylbenzene copolymer is also used. The resin may be of a gel type or a porous type ', however, it is more preferable that the degree of crosslinking is, for example, 2 to 8% lower. This acidic cation exchange resin is poured into a reactor to form a fixed bed. The present invention is formed by injecting an acidic cation exchange resin into a reactor, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 丨 J, --------- (Please read the back (Please fill in this page again)
、1T ΦΤ 經濟部智慧財產局員工消費合作社印製 -6 - 572788 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 ) 固定床後，反應開始前以水洗淨，再將流出之洗淨水中溶 解含氮硫化物而成之水溶液裝入該反應器並循環時，以該 含氮硫化物使酸性陽離子交換樹脂均勻地部分中和。 以水洗淨時之水量較佳爲，水膨脹狀態之離子交換樹 脂容量的0 . 5至2倍。 接著將流出之洗淨水中溶解含氮硫化合物而成之水溶 液裝入反應器並循環。 上述含氮硫化合物如，2 - 基乙基胺、3 —锍基丁 基胺等锍基烷基胺類；2，2 -二甲基噻唑烷、2 -甲基 一 2 -乙基噻唑烷、環烷基噻唑烷、2 -甲基一 2 -苯基 噻唑烷、3 -甲基噻唑烷等噻唑烷類；1，4 -胺基苯硫 酚等胺基苯硫酚類；3 -锍基甲基吡啶、3 -毓基乙基吡 啶、4 -锍基乙基吡啶等毓基烷基吡啶類子，其中又以毓 基烷基胺類、噻唑烷類爲佳。該含氮硫化合物之水溶液濃 度較佳爲，溶解於洗淨水後爲1至1 0質量％，又，全部 使用量對酸性陽離子交換樹脂中之磺酸基較佳爲2至5 0 莫耳％，更佳爲5至3 0莫耳％。 至於含氮硫化合物水溶液之循環次數又以，使離子交 換樹脂達所希望之中和率爲佳。 該所希望中和率爲2至5 0%，又以5至3 0%爲佳 。中和率過低或過高時將無法充分發揮觸媒活性。 進行中和之溫度可爲室溫，或加溫爲3 0至1 0 0 °C 。超過1 0 0 °C時，會使離子交換樹脂脫離磺酸激烈化而 不佳。 — (請先閱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 ) A4規格（210X 297公釐） 572788 A7 ___B7 五、發明説明（5 ) 由本發明可推斷，洗淨水所含之酸具有效用。 下面將以實施例具體說明本發明，但非限於此例。 丨J. I ^----1 衣-- (請先閱讀背面之注意事項再填寫本頁) 〔實施例1〕 將水膨脹狀態之磺酸型陽離子交換樹脂（三菱化學公 司製，泰亞歐SK— 1 04) 50 c C塡入內於2 5mm ，長2 0 c m之玻璃柱後，使純水1 〇 〇 c c流過。將二 甲基噻唑啉1 · 4 g溶解於流出之水後，以3 0 〇 c c / h r方式裝入離子交換樹脂床，直使流出之液循環。經 1 2 0小時循環後，取出一半離子交換樹脂調查中和率。 結果如表1所示。又，中和率係利用下列式求取。 訂 中和率（％)=l〇〇x 中和處理樹脂之酸當量（m e q ·/g) _ 未處理樹脂之酸當量（m e q ·/g) _ 經濟部智慧財產局員工消費合作社印製 (式中，酸當量係使用氫氧化鈉水溶液以滴定法測定。） 〔比較例1〕 除了以純水取代流出之洗淨水外’其他同實施例1求 取離子交換樹脂之中和率。結果如表1所示。 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） -8- 572788 A7 B7 五、發明説明（6 ) 表1 中和率（％ ) 離子交換樹脂之取出位置 實施例1 比較例1 1(上流側） 25 99 2 17 0 3 20 0 4 18 0 5(下流側） 20 0 產業上利用可能性 本發明可提供一種無需添加酸之雙酚類製造用陽離子 交換樹脂固定床之製造方法。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐）1T ΦΤ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -6-572788 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) After fixing the bed, wash with water before the reaction begins, and then When an aqueous solution obtained by dissolving a nitrogen-containing sulfide in the flowing out washing water is charged into the reactor and circulated, the acidic cation exchange resin is partially and uniformly neutralized with the nitrogen-containing sulfide. The amount of water when washed with water is preferably 0.5 to 2 times the capacity of the ion-exchange resin in a water-swelled state. Next, an aqueous solution in which nitrogen-sulfur compounds are dissolved in the flowing out washing water is charged into the reactor and circulated. Examples of the nitrogen-containing sulfur compounds include fluorenyl alkylamines such as 2-ylethylamine and 3-fluorenylbutylamine; 2,2-dimethylthiazolidine, 2-methyl-2-ethylthiazolidine , Thiazolidines such as cycloalkylthiazolidine, 2-methyl-2-phenylthiazolidine, 3-methylthiazolidine; amine thiophenols such as 1,4-aminothiophenol; 3-； Carboxymethylpyridines such as methylmethylpyridine, 3-ethylethylpyridine, and 4-methylethylpyridine. Among them, ethylmethylpyridine and thiazolidine are preferred. The concentration of the aqueous solution of the nitrogen-containing sulfur compound is preferably 1 to 10% by mass after dissolving in the washing water, and the total amount used is preferably 2 to 50 moles for the sulfonic acid group in the acidic cation exchange resin. %, More preferably 5 to 30 mole%. As for the number of cycles of the nitrogen-containing sulfur compound aqueous solution, the ion exchange resin can achieve a desired neutralization rate. The desired neutralization rate is 2 to 50%, and more preferably 5 to 30%. When the neutralization rate is too low or too high, the catalyst activity cannot be fully exerted. The neutralization temperature may be room temperature, or the heating temperature may be 30 to 100 ° C. Exceeding 100 ° C will cause the ion exchange resin to become detached from the sulfonic acid and become inferior. — (Please read the notes on the back before filling this page) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 572788 A7 ___B7 V. Description of the invention (5) It can be inferred from the present invention that the washing water The acid contained is effective. Hereinafter, the present invention will be specifically described by examples, but is not limited to this example.丨 J. I ^ ---- 1 Clothing-(Please read the precautions on the back before filling in this page) [Example 1] Sulfonic acid cation exchange resin (made by Mitsubishi Chemical Corporation, Taiya Euro SK-1 04) 50 c C is poured into a glass column with a length of 20 cm and a length of 20 cm, and then 100 cc of pure water is passed through. After dissolving 1.4 g of dimethylthiazoline in the effluent water, it was charged into the ion exchange resin bed at 300 c c / h r, and the effluent liquid was circulated. After 120 hours of circulation, half of the ion exchange resin was taken out to investigate the neutralization rate. The results are shown in Table 1. The neutralization rate is determined by the following formula. Order neutralization rate (%) = 100 × acid equivalent (meq · / g) of neutralized resin _ acid equivalent (meq · / g) of untreated resin _ printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ( In the formula, the acid equivalent is measured by a titration method using an aqueous sodium hydroxide solution.) [Comparative Example 1] The ion exchange resin neutralization rate was determined in the same manner as in Example 1 except that pure water was used instead of the washing water flowing out. The results are shown in Table 1. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -8- 572788 A7 B7 V. Description of the invention (6) Table 1 Neutralization rate (%) Take-out position of ion exchange resin Example 1 Comparative example 1 1 (upstream side) 25 99 2 17 0 3 20 0 4 18 0 5 (downstream side) 20 0 Industrial utilization possibility The present invention can provide a cation exchange resin fixed bed for the manufacture of bisphenols without adding an acid method. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X29? Mm)