1238818 A7 B7 五、發明説明（j 技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明關於一種製備雙酚A丨2，2 -雙（4 一經基 本基）丙院}之改良方法’詳曰之’本發明關於一^種可靠 地製備雙酚A之方法，其係在以含硫的胺化合物部份改質 的酸型離子交換樹脂作爲觸媒存在下進行酣與酮之縮合反 應，而由於丙酮中甲醇不純物之因素，經由硫醇化合物之 添加至該反應系統中可同時抑制催化活性之衰減。 背景技術 熟知雙酚A係作爲環氧樹脂或工程塑膠（如聚碳酸酯 樹脂及聚芳撐樹脂）之起始原料的重要化合物，及因此它 的需要性有逐年地明顯擴增之傾向。 雙酚A係在酸性觸媒存在下及可在以硫化合物作爲共 觸媒之情形下，藉由過量的酚與丙酮之縮合反應而製備。 經濟部智慧財產局員工消費合作社印製 迄今，已使用無機酸（如硫酸及氯化氫）作爲酸性觸 媒而被用於反應中，然而，近年來已著重於陽離子交換樹 脂之應用，其已被引進產業用途方面（參閱英國專利GB 842209、849565 及 883391) ° 另一方面，已知欲作爲共觸媒之適合的硫化合物包括 具有或未具有取代基（如甲基硫醇、乙基硫醇及硫代二元 醇）之烷基硫醇化合物（參閱美國專利2 3 5 9 2 4 2及 2775620)，該硫醇具有提高反應速率及同時提高 選擇性之功能，例如在雙酚A之製法中，形成的反應副產 物2 -（2 -羥基苯基）一 2 -（4 一羥基苯基）一丙烷 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4 - 1238818 A7 _____B7____ 五、發明説明（会 (請先閲讀背面之注意事項再填寫本頁} (O’P’ -異構物）爲主成分，及除其之外者爲參酚與 多酚’特別是當使用雙酚A作爲聚碳酸酯樹脂或聚芳撐之 起始原料時，需要將上述副產物的含量最小化，及要求非 常純與沒有著色作用，依此，可使用硫醇以提高反應速率 、抑制副產物的形成及提高選擇性之方式達成。 近年來，使用各種酸型改質的離子交換樹脂作爲觸媒 ，其中含硫基團被引入它的硫酸基團之部份中以代替使用 前述陽離子交換樹脂與硫醇化合物之組合。 經濟部智慧財產局員工消費合作社印製 已知，作爲前述酸型改質的離子交換樹脂之一者可爲 以含硫的胺化合物部份改質的酸型離子交換樹脂。然而在 此情形中，當在以含硫的胺化合物部份改質的前述酸型離 子交換樹脂構成的觸媒存在下，藉酚與酮進行縮合反應而 製備雙酚A時，由於丙酮中的甲醇不純物其將會產生觸媒 活性衰減之問題。爲了解決上述問題，已提出一種抑制觸 媒衰減之方法，其係讓少量的水存在於反應用之起始原料 中（參閱日本專利申請公開號1 7 2 2 4 1 / 1 9 9 4 ( 平成 6 年），175898/1998 (平成 10 年）， 251179/1998 (平成 10 年），及 251180/1998(平成10年），雖然如此，由 於觸媒之衰減會藉由水再度發生，前述方法通常無法令人 滿意，因而使抑制觸媒衰減之效果無法有效地運用。 另一方面，已提出一種方法，係用於將反應用的起始 原料進行精製處理，使起始原料中的雜質化合物含量減少 至低於0 · 1重量％，該化合物爲如式·· R - X所示，其 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " 一 " -5- 1238818 A7 B7 五、發明説明（全 中R爲烷基、烯基、環烷基或環烯基，及X爲〇Η、鹵素 原子、羧酸酯基、硫酸酯基或磺酸酯基。 f請先閲讀背面之注意事項再填寫本頁} 雖然如此，由於其負有對作爲起始原料之酚與酮進行 精製處理之義務，剛剛述及的方法通常亦無法令人滿意， 依此需增加其精製步驟。 發明之掲露 在此情況下，本發明之一般目的係提供一種穩定地製 造高轉化率的雙酚Α之方法，其係藉在以含硫的胺化合物 部份改質的酸型離子交換樹脂觸媒之存在下，進行酚與酮 之縮合反應，同時抑制由於丙酮中甲醇不純物引起的催化 活性之衰減作用。 本發明之其它目的將由下述說明書內容淸楚揭示。 經濟部智慧財產局員工消費合作社印製 在此情況下，爲了達到上述目的，本發明人集聚了嚴 密的、大規模的硏究與調查，結果已發現本發明目的可藉 使用以含硫的胺化合物部份改質的酸型離子交換樹脂作爲 觸媒及其具有改質率在特定範圍內，及亦藉添加硫醇化合 物至反應系統中製備。本發明係以前述發現與資料爲基礎 而完成者。 詳言之，本發明提供一種製備雙酚A之方法，其係在 以含硫的胺化合物部份改質的酸型離子交換樹脂作爲觸媒 存在下’進行酚與酮之縮合反應，其特徵爲在丙酮中的甲 醇濃度以重量計爲4 0 0至7 0 0 0 p p m範圍之情況中 ，使用具有改質率爲1 5至5 Omo 1 %範圍的前述離子 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " -- -6 - 1238818 A7 -----— _B7 五、發明説明（4 (請先閲讀背面之注意事項再填寫本頁) 父換樹脂’及亦藉添加硫醇化合物至反應系統中製備。用 於本文中的術語，，改質率，，係指在酸型離子交換樹脂中磺 酸基的改質莫耳率，該改質係藉含硫的胺化合物達成的。 實施本發明之聶佳丨苗1 根據本發明之方法係用於製備雙酚A，其係在以含硫 的胺化合物部份改質的酸型離子交換樹脂作爲觸媒存在下 ’進行與酮之縮合反應，該作爲上述改質的酸型離子交 換樹脂之基質的酸型離子交換樹脂不特別受限制，惟可選 用迄今習用上作爲雙酚A之製備用的觸媒之離子交換樹脂 。因此’從催化活性等觀點來看，強酸性的磺酸型離子交 換樹脂特別合適。 前述磺酸型離子交換樹脂不特別受限制，惟其限制條 件爲帶有磺酸基團的強酸性離子交換樹脂，舉例說明其可 爲磺化苯乙烯/二乙烯基苯共聚物、磺化與交聯的苯乙烯 聚合物、酚甲醛/磺酸樹脂及苯甲醛/磺酸樹脂等。 經濟部智慧財產局員工消費合作社印製 另一方面，欲用於部份改質該酸型離子交換樹脂之含 硫的胺化合物不特別受限制，但可適當地及視情況地選用 可用於改質酸型離子交換樹脂之已熟知的化合物。 上述含硫的胺化合物實例包括毓基烷基吡啶類，例如 3 -锍基甲基吡啶、3 -（ 2 -酼基乙基）吡啶及4 一（ 2 -酼基乙基）吡啶；毓基烷基胺類，例如2 -锍基乙基 胺、3 -酼基丙基胺及4 -毓基丁基胺；噻唑烷類，例如 噻唑烷、2 ，2 —二甲基噻唑烷、2 —甲基一 2 —苯基噻 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1238818 A7 __B7 五、發明説明（含 (請先閲讀背面之注意事項再填寫本頁) 唑烷及3 -甲基噻唑烷；及胺基硫代酚類，例如4 -胺基 硫代酚，之中以4 一（ 2 -巯基乙基）吡啶、2 -毓基乙 基胺及2，2 -二甲基噻唑烷爲較佳。 任何該等含硫的胺化合物可爲游離形式，或爲酸性物 質（例如氫氯酸）之加成鹽形式，或四級銨鹽。 藉使用含硫的胺化合物部份改質上述作爲基質的酸型 離子交換樹脂之方法不特別受限制，但可選用已熟知的方 法。 例如，作爲基質的樹脂可藉使酸型離子交換樹脂及含 硫的胺化合物彼此反應而經改質，較佳爲在水性溶劑（例 如水）中進行，以達到所需的改質率，反應可在常溫或加 熱條件下進行，藉由該反應，作爲離子交換基團之磺酸基 與在含硫的胺化合物中的胺基反應，因而藉由被引入部份 離子交換基團之含硫基部份改質離子交換樹脂。 經濟部智慧財產局員工消費合作社印製 於根據本發明之方法中，在丙酮中的甲醇濃度以重量 計爲4 0 0至7 0 0 0 p pm範圍之情況中，使用具有改 質率爲1 5至5 Omo 1 %範圍的改質的酸型離子交換樹 脂。 本發明人已發現下述情形，作爲酚與酮的縮合反應觸 媒其使用以含硫的胺化合物部份改質的酸型離子交換樹脂 之例中，在前述樹脂中之未反應部份中的磺酸基團扮演觸 媒，而造成丙酮中存在的甲醇不純物與在前述樹脂中的殘 餘的含硫的胺化合物之酼基反應，因而降低了觸媒之催化 活性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐1 " -8 - 1238818 A7 _ _B7__ 五、發明説明（6) (請先閲讀背面之注意事項再填寫本頁) 詳言之，其能夠抑制催化活性之衰減及因而延長觸媒 之使用壽命，其在本發明中藉添加少量的硫醇化合物至反 應系統中，而使硫醇化合物與存在於丙酮中之不純物甲醇 反應及因而抑制甲醇與在改質的酸型離子交換樹脂中的含 硫的胺化合物之巯基間的反應。 前述硫醇化合物之實例包括具有1至10個碳原子的 烷基硫醇，例如甲基硫醇、乙基硫醇、η -丙基硫醇、異 丙基硫醇、η -丁基硫醇、s e c -丁基硫醇、t e r t -丁基硫醇、戊基硫醇、己基硫醇、庚基硫醇、辛基硫醇 、壬基硫醇、癸基硫醇等等，硫醇化合物之中以各具有1 至3個碳原子的烷基硫醇爲較佳。 欲添加至反應系統之硫醇化合物的含量爲1 / 2 0至 1/500莫耳比，較佳爲1/50至1/400莫耳比 ，以丙酮爲基準。 經濟部智慧財產局員工消費合作社印製 視作爲起始原料之丙酮中的甲醇濃度、丙酮與酚間的 反應狀況、在作爲觸媒之改質的酸型離子交換樹脂中的衰 減程度而定，上述含量可選擇性地變化，例如，在高濃度 的甲醇或觸媒嚴重衰減之情況下，該含量可增加。 於本發明中，如上所引述者，該硫醇化合物之添加藉 硫醇化合物之催化效果不僅對延長觸媒之使用壽命及亦在 增進形成雙酚A之反應速率上係有效的。 此外，本發明中可使用具有水含量以重量計爲約 5〇0至5000ppm的起始原料。 一般，作爲起始原料之試劑級或工業用的酚以重量計 i紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9 - 1238818 A7 B7 五、發明説明（7) 爲具有5 0 0至1 〇 〇 〇 P Pm水量，同樣地’作爲起始 原料之丙酮以重量計爲具有1 〇 〇 〇至3 〇 〇 0 p pm水 (請先閲讀背面之注意事項再填寫本頁) 量。 於根據本發明之方法中，過量的酚與未反應的丙酮可 被回收及循環使用，而爲了達到前述的水含量其需要大規 模的精製處理。在酚與丙酮之間的反應中’水以與最終雙 酚A之等莫耳含量釋出，例如，以莫耳比爲1 : 10之丙 酮與酚間的反應對改質率爲2 0%、5 0%及7 0%之水 濃度分別升高至約40 0 Op pm、約9 00 0 Ppm及 約1 3 0 0 0 P P m，也就是說，在各起始原料中之水含 量以重量計爲約5 0 0至2 0 0 0 p pm (由超出前述含 量之反應所釋出的水含量）的情形中，對反應行爲幾乎不 會造成影響。 事實上，添加0 . 0 5至0 · 2 %的水對抑制由甲醇 造成的影響幾乎不會展現出操作效果。然而，含於反應系 統中的水抑制了標的雙酚A的形成，及在起始原料中含約 0 . 4 %水含量將造成催化活性之大幅度衰減。 經濟部智慧財產局員工消費合作社印製 用於根據本發明雙酚A之製法中的酚對丙酮之比例不 特別受限制，而就精製該最終雙酚A之容易性、經濟效益 等因素之觀點來看，該未反應的丙酮含量較佳爲儘可能的 低，依此，使用超過其化學計量之過量的酚係有利地。 因此，酚通常使用3至3 0莫耳之量，較佳爲5至 2 0莫耳，以每一莫耳的酮計。 在雙酚A之製造中，除了反應液體具有不合理的高黏 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ' -10- 1238818 A7 B7 五、發明説明（a) 度或反應係在低溫下進行而產生固化使操作進行困難之情 形外，一般是不需要反應溶劑。 (請先閲讀背面之注意事項再填寫本頁) 在酚與酮間之縮合反應中，適合的連續反應固定床系 統其中酚與酮在反應塔中爲連續地供給及反應，該反應塔 塡充以含硫的胺化合物部份改質的酸型離子交換樹脂，在 此情形下，單一反應器與串聯或並聯配置的複式反應器兩 者皆爲適合的。 於工業規模方面，特別適合地是採用配設有至少二個 反應塔串聯的連續多階式反應固定床系統，其中各反應塔 塡充有酸型離子交換樹脂。 下文中，將說明連續反應固定床系統之反應條件。 首先，丙酮/酚的莫耳比一般選在1/3 0至1/3 之範圍，較佳爲1 / 2 0至1 / 5。當莫耳比低於 1/3 0時，恐有發生不合乎常理之低反應速率之虞，而 當莫耳比例大於1 / 3時，則有導致形成過量不純物的傾 向，及會降低對雙酚A的選擇性。 經濟部智慧財產局員工消費合作社印製 本發明中，對用於將酚、丙酮及該硫醇化合物供入反 應器之方法沒有限制，較佳地，丙酮及硫醇化合物各獨立 地供給各個反應器。 另外，反應溫度一般選在4 0至1 5 0°C之範圍，較 佳爲5 5至1 0 0 °C。當反應溫度低於4 0 °C時，會產生 不合乎常理的低反應速率及會產生極高黏度的反應液體， 因而恐有發生固化反應之虞，反之，當反應溫度高於 1 5 0 °C時，使得反應難以控制、對雙酚A ( p，p ’ 一 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ；297公釐） Γ Λ 1238818 A7 B7 五、發明説明（9) 異構物）之選擇性衰減及產生改質的酸型離子交換樹脂觸 媒之另外的分解及衰減作用。 (請先閲讀背面之注意事項再填寫本頁) LHSV (液體每小時空間速度）一般選在〇 · 2至 3〇hr_1之範圍，較佳爲〇 · 5至20hi* 一丄。 於根據本發明之方法中，由反應塔排出的反應混合物 可藉由熟知方法進行後處理，以收集標的雙酚A。以下將 以一後處理實例說明，首先，在結晶前進行反應混合物之 濃縮，濃縮條件不特別受限制，惟通常包括1 3 0至 1 70t：之溫度範圍及1 3至53kPa之壓力範圍的條 件。當溫度低於1 3 0 °C時，必要條件爲高度真空，而當 溫度高於1 7 0 °C時，則會造成不純物含量的增加或造成 反應產物的著色作用。在經濃縮的殘餘液體中雙酚A的濃 度於2 5至4 0重量％範圍係有利的。當其濃度低於2 5 重量％時，結果造成低的雙酚A回收率，當其濃度高於 4 0重量％時，結果造成在結晶後漿液傳送困難。 經濟部智慧財產局員工消費合作社印製 來自經濃縮的殘餘液體之雙酚A與酚加成物的結晶作 用通常係藉真空冷卻結晶方法進行，其步驟包含在減壓下 利用水蒸發作用的潛熱冷卻，在前述方法中’結晶處理通 常在包括4 0至7 0°C之溫度範圍與3至1 3 k P a之壓 力範圍的條件下進行，其藉將約3至2 0重量％水加入經 濃縮的殘餘液體中。當欲添加的水量低於3重量％時’會 造成熱移除容量不足，而當水量高於2 〇重量％時’會不 適當地造成雙酚A的溶解流失量增加’更且，當結晶溫度 低於4 0 °C時，恐有造成增加結晶液體黏度或結晶液體固 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 1238818 A7 ______B7 五、發明説明（ib 化之虞，而當結晶溫度高於7 0 t時，會不適當地造成雙 酣A之溶解流失量的增加。 (請先閲讀背面之注意事項再填寫本頁) 接著，以上述方式結晶的雙酚A與酚加成物藉熟知方 法分離，及利用酚進行淸潔處理，然後在包括溫度一般選 在1 30至200 °C範圍（較佳爲1 50至1 80°C)及 壓力選在3至2 0 k P a範圍之條件下，將已進行淸潔處 理之加成物分離成爲雙酚A與酚。 從分離處理所獲得的存在於雙酚A中的殘餘酚，其可 藉汽提方法或類似方法實質上完全地被移除，依此可獲得 高品質的雙酚A。 下文中，本發明將以相關的實施例及比較例詳盡地說 明，然而其將不會限制本發明。 實例1 經濟部智慧財產局員工消費合作社印製 內徑爲1 2mm與高度爲1 2 0 0mm之堆積床形式 反應器，其塡充有以2 〇 m ο 1 %計2 -毓基乙基胺改質 的磺酸型離子交換樹脂作爲觸媒（製自三菱化學工業股份 有限公司，商品名” Diaion SK— 104H” ），其與 水以含量6 9 . 3毫升（m L )量呈膨潤狀態。兩組反應 器爲串聯連接。 接著，以2 7 7 m L / H r流速將酚供給第一階段反 應器，同時分別獨立地將含有以重量計爲5 0 0 p pm甲 醇之丙酮及莫耳比爲1/4 0 0 (以丙酮爲基準）的乙基 硫醇，以流速1 5 · 6 m L / H r供給第一及第二階段反 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 546 -13- 1238818 Α7 Β7 五、發明説明（Λ 應器，以在反應溫度維持於7 5 °C下進行反應。 (請先閲讀背面之注意事項再填寫本頁) 依此’該反應混合物以時間終止進行分析，以測得酚 對雙酚A之轉化率，其結果如表1所示。 重複實例1之步驟，除了此例係使用以2 5 m ο 1 % 計2 ’ 2 -二甲基噻唑烷改質上述相同的磺酸型離子交換 樹脂作爲觸媒’及另使用含有以重量計爲1 〇 〇 〇 p prn 甲醇的丙酮及莫耳比爲1/2 0 0 (以丙酮爲基準）的乙 基硫醇。 其結果如表1所示。 重複實例1之步驟，除了此例係使用以2 5 m ο 1 % 計2 ’ 2 -二甲基噻唑烷改質上述相同的磺酸型離子交換 樹脂作爲觸媒’及另使用含有以重量計爲5 〇 〇 〇 p pm 經濟部智慧財產局員工消費合作社印製 甲醇的丙酮及莫耳比爲1/1 〇 〇 (以丙酮爲基準）的乙 基硫醇。 其結果如表1所示。 實例4 重複貫例1之步驟》除了此例係使用以4 5 in ο 1 % 計2 ’ 2 -二甲基噻唑烷改質上述相同的磺酸型離子交換 樹脂作爲觸媒，及另使用含有以重量計爲5 0 〇 〇 p pm 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ；297公釐） 54? -14- 1238818 A7 B7 五、發明説明（止 甲醇的丙酮及莫耳比爲1/5 0 (以丙酮爲基準）的乙基 硫醇。 (請先閲讀背面之注意事項再填寫本頁) 其結果如表1所示。 奮例5 重複實例1之步驟，除了此例係使用以3 0 m 〇 1 % 計4 -（ 2〜巯基乙基）吡啶改質上述相同的磺酸型離子 交換樹脂作爲觸媒，及另使用含有以重量計爲1 〇 〇 〇 ppm甲醇的丙酮及莫耳比爲1/2 0 0 (以丙酮爲基準 )的乙基硫醇。 其結果如表1所示。 於實例1至5中，可獲得令人滿意的結果其包括對雙 酚A之選擇性爲至少9 3 %。 比較例1 經濟部智慧財產局員工消費合作社印製 重複實例1之步驟，除了此例係使用以1 0 m 〇 1 % 計2 -巯基乙基胺改質上述相同的磺酸型離子交換樹脂作 爲觸媒，及另使用含有以重量計爲1 〇 〇 〇 p pm甲_的 丙酮。 其結果如表1所示。 比較例2 重複實例1之步驟，除了此例係使用含有以重量計爲 5000ppm甲醇的丙酮。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -15- 1238818 Α7 Β7 五、發明説明（也 其結果如表i所示。 比較仞I 3 (請先閲讀背面之注意事項再填寫本頁} 重複實例1之步驟，除了此例使用以2 5 m 〇 1 %計 2 ’ 2 -二甲基噻唑烷改質上述相同的磺酸型離子交換樹 脂作爲觸媒’及另使用含有以重量計爲1 〇 〇 〇 〇 p pm 甲醇的丙酮。 其結果如表1所示。 比較仞ί 4 重複實例1之步驟，除了此例使用以7 m 〇 1 %計4 -（2 -毓基乙基）吡啶改質上述相同的磺酸型離子交換 樹脂作爲觸媒，及另使用含有以重量計爲4 0 〇 〇 p pm 甲醇的丙酮。 其結果如表1所示。 比較例5 經濟部智慧財產局員工消費合作社印製 重複實例1之步驟，除了此例使用以1 6 m 〇 1 %旨丨 2，2 -二甲基噻唑烷改質上述相同的磺酸型離子交換棱f 脂作爲觸媒，及另使用含有以重量計爲2 0 0 〇 0 p pm 甲醇的丙酮及莫耳比爲1/4 0 0 (以丙酮爲基準）的乙 基硫醇。 其結果如表1所示。1238818 A7 B7 V. Description of the invention (j Technical field (please read the notes on the back before filling this page) The present invention relates to an improved method for preparing bisphenol A 丨 2,2-bis (4 once basic base) The invention relates to a method for reliably preparing bisphenol A, which is carried out in the presence of a sulfur-containing amine compound partially modified acid-type ion exchange resin as a catalyst for the condensation of fluorene and ketone. Reaction, and due to the impurity of methanol in acetone, the addition of a thiol compound to the reaction system can simultaneously suppress the attenuation of catalytic activity. BACKGROUND ART Bisphenol A is well known as an epoxy resin or engineering plastic (such as polycarbonate resin). And polyarylene resin) are important starting materials for the raw materials, and therefore its demand tends to significantly increase year by year. Bisphenol A is in the presence of acid catalysts and can be used in sulfur catalysts as co-catalysts. In some cases, it is prepared by the condensation reaction of excess phenol and acetone. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs So far, inorganic acids such as sulfuric acid and hydrogen chloride have been used as acidity However, in recent years, emphasis has been placed on the application of cation exchange resins, which have been introduced into industrial applications (see British patents GB 842209, 849565 and 883391) ° On the other hand, it is known to be used as a co-contact Suitable sulfur compounds include alkyl mercaptan compounds with or without substituents (such as methyl mercaptan, ethyl mercaptan, and thioglycols) (see US Patents 2 3 5 9 2 4 2 and 2775620). ), The thiol has the function of increasing the reaction rate and at the same time increasing the selectivity, for example, in the production method of bisphenol A, a reaction by-product formed by 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) The size of a propane paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -4-1238818 A7 _____B7____ V. Description of the invention (meeting (please read the precautions on the back before filling this page) (O'P '- Isomers) as the main component, and the others are ginseng phenols and polyphenols. Especially when bisphenol A is used as the starting material of polycarbonate resin or polyarylene, the content of the above by-products needs to be adjusted. Minimized and very demanding With no coloring effect, thiols can be used to increase the reaction rate, inhibit the formation of by-products, and increase the selectivity. In recent years, various acid-modified ion exchange resins have been used as catalysts, among which sulfur The group was introduced into the part of its sulfuric acid group instead of using the combination of the aforementioned cation exchange resin and thiol compound. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, known as the aforementioned acid type modified ion exchange resin One of them may be an acid-type ion exchange resin partially modified with a sulfur-containing amine compound. However, in this case, when the contact formed by the aforementioned acid-type ion exchange resin partially modified with a sulfur-containing amine compound is used. In the presence of a vehicle, when the bisphenol A is prepared by the condensation reaction of phenol and ketone, the problem of catalyst activity degradation will occur due to the impure methanol in acetone. In order to solve the above problems, a method for suppressing catalyst decay has been proposed, which allows a small amount of water to be present in the starting materials for the reaction (see Japanese Patent Application Publication No. 1 7 2 2 4 1/1 9 9 4 (Heisei 6 years), 175898/1998 (Heisei 10), 251179/1998 (Heisei 10), and 251180/1998 (Heisei 10). However, because catalyst decay will occur again through water, the above methods are usually It is unsatisfactory, so that the effect of suppressing the attenuation of the catalyst cannot be effectively used. On the other hand, a method has been proposed for purifying the starting material for the reaction so that the content of impurity compounds in the starting material Reduced to less than 0. 1% by weight, the compound is as shown in the formula: R-X, and its paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) " 一 " -5- 1238818 A7 B7 V. Description of the invention (all of R is alkyl, alkenyl, cycloalkyl or cycloalkenyl, and X is 〇Η, halogen atom, carboxylate, sulfate or sulfonate. F please Read the notes on the back before filling out this } Nevertheless, because of its obligation to refine phenols and ketones as starting materials, the methods just mentioned are usually unsatisfactory, and the purification steps need to be increased accordingly. The invention disclosed in this case The general purpose of the present invention is to provide a method for stably producing bisphenol A with a high conversion rate, which is carried out in the presence of an acid-type ion exchange resin catalyst partially modified with a sulfur-containing amine compound. The condensation reaction of phenol and ketone, while suppressing the attenuation of the catalytic activity caused by the impure methanol in acetone. Other objects of the present invention will be revealed clearly in the following description. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in this case In order to achieve the above purpose, the present inventors have gathered rigorous and large-scale investigations and investigations. As a result, it has been found that the purpose of the present invention can be obtained by using an acid-type ion exchange resin partially modified with a sulfur-containing amine compound as a catalyst. It has a modification rate within a specific range, and is also prepared by adding a thiol compound to the reaction system. The present invention is based on the foregoing findings and In detail, the present invention provides a method for preparing bisphenol A, which is carried out in the presence of a phenol with a sulfur-containing amine compound partially modified acid-type ion exchange resin as a catalyst. A condensation reaction of ketones, characterized in that in the case where the methanol concentration in acetone is in the range of 400 to 7 000 ppm by weight, the foregoing ionomer having a modification rate in the range of 15 to 5 Omo 1% is used. Paper size applies to China National Standard (CNS) A4 specification (210X297 mm) "--6-1238818 A7 ------- _B7 V. Description of the invention (4 (Please read the precautions on the back before filling this page) ) Parent exchange resin 'and also prepared by adding thiol compounds to the reaction system. As used herein, the term, modification rate, refers to the modification mole rate of the sulfonic acid group in the acid-type ion exchange resin, which modification is achieved by a sulfur-containing amine compound. Nie Jia Miao 1 practicing the present invention 1 The method according to the present invention is used to prepare bisphenol A, which is performed with a ketone in the presence of an acid-type ion exchange resin partially modified with a sulfur-containing amine compound as a catalyst. For the condensation reaction, the acid-type ion-exchange resin which is the matrix of the modified acid-type ion-exchange resin is not particularly limited, but an ion-exchange resin which has been conventionally used as a catalyst for the preparation of bisphenol A can be selected. Therefore, from the viewpoint of catalytic activity and the like, a strongly acidic sulfonic acid ion exchange resin is particularly suitable. The aforementioned sulfonic acid-type ion exchange resin is not particularly limited, but its limitation is a strongly acidic ion exchange resin with a sulfonic acid group. For example, it can be a sulfonated styrene / divinylbenzene copolymer, sulfonated and crosslinked Styrene polymer, phenol formaldehyde / sulfonic acid resin and benzaldehyde / sulfonic acid resin. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. On the other hand, the sulfur-containing amine compounds intended to be used to partially modify the acid-type ion exchange resin are not particularly limited, but can be used appropriately and as appropriate. Well-known compounds of quality acid type ion exchange resins. Examples of the above sulfur-containing amine compounds include fluorenylalkylpyridines, such as 3-fluorenylmethylpyridine, 3- (2-fluorenylethyl) pyridine, and 4-mono (2-fluorenylethyl) pyridine; fluorenyl Alkylamines, such as 2-fluorenylethylamine, 3-fluorenylpropylamine, and 4-fluorenylbutylamine; thiazolidines, such as thiazolidine, 2,2-dimethylthiazolidine, 2- Methyl-2-Phenylthiazine This paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1238818 A7 __B7 V. Description of the invention (including (please read the precautions on the back before filling this page) 3-methylthiazolidine; and aminothiophenols, such as 4-aminothiophenols, among which 4-mono (2-mercaptoethyl) pyridine, 2-mercaptoethylamine, and 2,2- Dimethylthiazolidine is preferred. Any such sulfur-containing amine compound may be in free form, or in the form of an addition salt of an acidic substance (such as hydrochloric acid), or a quaternary ammonium salt. By using a sulfur-containing amine The method of partially modifying the compound as the matrix of the acid-type ion exchange resin described above is not particularly limited, but a well-known method may be selected. The resin as the matrix can be modified by reacting the acid-type ion exchange resin and the sulfur-containing amine compound with each other, preferably in an aqueous solvent (such as water) to achieve the desired modification rate. It is carried out under normal temperature or heating conditions. By this reaction, the sulfonic acid group as an ion exchange group reacts with the amine group in the sulfur-containing amine compound, so the sulfur-containing group is introduced into a part of the ion exchange group. In the method according to the present invention, in the case where the concentration of methanol in acetone is in the range of 400 to 7 00 p pm, A modified acid-type ion exchange resin having a modification rate ranging from 15 to 5 Omo 1% was used. The present inventors have found that, as a condensation reaction catalyst for a phenol and a ketone, it is used a sulfur-containing amine compound In the example of a partially modified acid-type ion exchange resin, the sulfonic acid group in the unreacted portion of the resin acts as a catalyst, causing the methanol impurities in acetone and the residual Sulfur The fluorene-based reaction of the compound reduces the catalytic activity of the catalyst. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm1 " -8-1238818 A7 _ __B7__ V. Description of the invention (6) (please Read the precautions on the back before filling this page.) In detail, it can inhibit the degradation of catalytic activity and thus extend the life of the catalyst. In the present invention, a small amount of thiol compound is added to the reaction system, so that The thiol compound reacts with the impurity methanol present in acetone and thus suppresses the reaction between the methanol and the mercapto group of the sulfur-containing amine compound in the modified acid-type ion exchange resin. Examples of the aforementioned thiol compound include an alkyl mercaptan having 1 to 10 carbon atoms, such as methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan , Sec-butyl mercaptan, tert-butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, etc. Of these, alkylthiols each having 1 to 3 carbon atoms are preferred. The content of the thiol compound to be added to the reaction system is 1/20 to 1/500 mole ratio, preferably 1/50 to 1/400 mole ratio, based on acetone. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, depending on the methanol concentration in acetone as the starting material, the reaction between acetone and phenol, and the degree of attenuation in the acid-type ion exchange resin modified as a catalyst, The above-mentioned content may be selectively changed, for example, in the case of a high concentration of methanol or a catalyst that is severely attenuated, the content may be increased. In the present invention, as mentioned above, the addition of the thiol compound by virtue of the catalytic effect of the thiol compound is not only effective in extending the life of the catalyst but also in increasing the reaction rate of forming bisphenol A. Further, a starting material having a water content of about 5,000 to 5000 ppm by weight may be used in the present invention. Generally, the reagent grade or industrial phenols used as starting materials are based on the weight of paper. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9-1238818 A7 B7 5. The invention description (7) The amount of water from 0 to 100,000 P Pm, similarly 'acetone as starting material has 10,000 to 3,000 p pm water by weight (please read the precautions on the back before filling this page) the amount. In the method according to the present invention, excess phenol and unreacted acetone can be recovered and recycled, and in order to achieve the aforementioned water content, it requires a large-scale refining treatment. In the reaction between phenol and acetone, 'water is released at a molar content equal to the final bisphenol A. For example, the reaction between acetone and phenol at a molar ratio of 1:10 is 20%. , 50% and 70% of the water concentration increased to about 40 0 Op pm, about 9 00 0 Ppm and about 13 0 0 PP m, that is, the water content in each starting material In the case of about 50,000 to 20,000 p pm by weight (amount of water released by the reaction exceeding the foregoing content), the reaction behavior is hardly affected. In fact, the addition of 0.05 to 0.2% water has little effect on the suppression of the effects caused by methanol. However, the water contained in the reaction system inhibits the formation of the target bisphenol A, and the water content of about 0.4% in the starting material will cause a significant attenuation of the catalytic activity. The ratio of phenol to acetone printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for use in the production method of bisphenol A according to the present invention is not particularly limited, but from the viewpoint of the ease, economic benefits and other factors of refining the final bisphenol A In view of this, the unreacted acetone content is preferably as low as possible, and accordingly, it is advantageous to use an excess of phenol based on its stoichiometry. Therefore, phenol is usually used in an amount of 3 to 30 moles, preferably 5 to 20 moles, based on each mole of ketones. In the manufacture of bisphenol A, except that the reaction liquid has an unreasonably high viscosity, the paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) '-10- 1238818 A7 B7 V. Description of the invention (a) Degree or The reaction is generally carried out at a low temperature and curing is difficult to perform. Generally, a reaction solvent is not required. (Please read the precautions on the back before filling this page) In the condensation reaction between phenol and ketone, a suitable continuous reaction fixed bed system in which phenol and ketone are continuously supplied and reacted in the reaction tower, the reaction tower is charged An acid-type ion exchange resin partially modified with a sulfur-containing amine compound. In this case, both a single reactor and a multiple reactor arranged in series or in parallel are suitable. In terms of industrial scale, it is particularly suitable to use a continuous multi-stage reaction fixed bed system equipped with at least two reaction towers connected in series, wherein each reaction tower 塡 is filled with an acid-type ion exchange resin. Hereinafter, the reaction conditions of the continuous reaction fixed bed system will be explained. First, the molar ratio of acetone / phenol is generally selected in the range of 1/3 0 to 1/3, and preferably 1/20 to 1/5. When the molar ratio is lower than 1/3 0, an unreasonably low reaction rate may occur, and when the molar ratio is larger than 1/3, there is a tendency to cause excessive impurities to be formed, and it will reduce the Selectivity of phenol A. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the present invention, there is no limitation on the method for supplying phenol, acetone, and the thiol compound into the reactor. Preferably, acetone and thiol compound are independently supplied to each reaction Device. In addition, the reaction temperature is generally selected in the range of 40 to 150 ° C, and more preferably 55 to 100 ° C. When the reaction temperature is lower than 40 ° C, an unreasonably low reaction rate and an extremely high-viscosity reaction liquid may be generated, so there is a risk of curing reaction. On the contrary, when the reaction temperature is higher than 150 ° At C, it makes the reaction difficult to control. For bisphenol A (p, p '-11-this paper size applies Chinese National Standard (CNS) A4 specifications (210 ×; 297 mm). Γ Λ 1238818 A7 B7 V. Description of the invention ( 9) Selective attenuation of isomers) and additional decomposition and attenuation of modified acid-type ion exchange resin catalysts. (Please read the precautions on the back before filling this page) LHSV (Liquid Hourly Space Velocity) is generally selected in the range of 0.2 to 30hr_1, preferably 0.5 to 20hi *. In the method according to the present invention, the reaction mixture discharged from the reaction tower may be worked up by a well-known method to collect the target bisphenol A. The following is an example of a post-treatment. First, the reaction mixture is concentrated before crystallization. The concentration conditions are not particularly limited, but usually include conditions in the temperature range of 130 to 70 t: and the pressure range of 13 to 53 kPa. . When the temperature is lower than 130 ° C, a high vacuum is necessary. When the temperature is higher than 170 ° C, the content of impurities is increased or the reaction product is colored. It is advantageous that the concentration of bisphenol A in the concentrated residual liquid is in the range of 25 to 40% by weight. When its concentration is lower than 25% by weight, it results in a low recovery rate of bisphenol A, and when its concentration is higher than 40% by weight, it results in difficulty in transporting the slurry after crystallization. The crystallization of bisphenol A and phenol adducts from concentrated residual liquid printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is usually performed by a vacuum cooling crystallization method, which includes the use of latent heat of water evaporation under reduced pressure. Cooling, in the aforementioned method, the crystallization treatment is usually performed under conditions including a temperature range of 40 to 70 ° C and a pressure range of 3 to 13 kPa, by adding about 3 to 20% by weight of water Concentrated residual liquid. When the amount of water to be added is less than 3% by weight, 'the heat removal capacity will be insufficient, and when the amount of water is more than 20% by weight,' the dissolution loss of bisphenol A will be inappropriately increased '; When the temperature is lower than 40 ° C, it may cause the increase of the viscosity of the crystalline liquid or the crystalline liquid solid paper. The Chinese national standard (CNS) A4 specification (210X297 mm) is applicable. -12- 1238818 A7 ______B7 V. Description of the invention (ib There is a risk that when the crystallization temperature is higher than 70 t, the dissolution loss of Shuangya A will be inappropriately increased. (Please read the precautions on the back before filling this page) Then, the Shuanghua crystallized in the above manner Phenol A and phenol adducts are separated by well-known methods, and cleaned with phenol, and then the temperature is generally selected in the range of 1 30 to 200 ° C (preferably 1 50 to 180 ° C) and the pressure is selected in In the range of 3 to 20 k P a, the adduct that has been subjected to the cleaning treatment is separated into bisphenol A and phenol. The residual phenol present in the bisphenol A obtained from the separation treatment can be steamed. The extraction method or similar method is substantially completely removed, so that Obtain high-quality bisphenol A. In the following, the present invention will be described in detail with related examples and comparative examples, but it will not limit the present invention. Example 1 The inner diameter printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is A packed bed reactor with a height of 12 mm and a height of 12 mm is filled with a 2-sulfenylethylamine modified sulfonic acid ion exchange resin based on 200 m ο 1% as a catalyst (made from Mitsubishi Chemical Industry Co., Ltd., trade name "Diaion SK-104H"), is swollen with water at a content of 69.3 milliliters (m L). The two sets of reactors are connected in series. Next, 2 7 7 The m L / H r flow rate feeds the phenol to the first-stage reactor, while independently containing acetone with a weight of 500 p pm methanol and a molar ratio of 1/4 0 0 (based on acetone). Ethyl mercaptan, supplied at a flow rate of 15 · 6 m L / H r for the first and second stage anti-paper sizes. Applicable to China National Standard (CNS) A4 specifications (210X297 mm) 546 -13- 1238818 Α7 Β7 V. Description of the invention (Λ reactor to carry out the reaction at a reaction temperature maintained at 7 5 ° C (Please read the precautions on the back before filling this page.) Based on this, the reaction mixture was analyzed at the end of time to measure the conversion of phenol to bisphenol A. The results are shown in Table 1. Repeat the steps of Example 1. In addition to this example, the same sulfonic acid type ion exchange resin as the catalyst was modified by using 2 '2 -dimethylthiazolidine at 25 m ο 1% as a catalyst' and another containing 1 〇〇〇 by weight p prn Methanol has an acetone and a molar ratio of 1/2 0 0 (based on acetone) ethyl mercaptan. The results are shown in Table 1. The procedure of Example 1 was repeated, except that in this example, the same sulfonic acid ion exchange resin as the catalyst was modified by using 2 '2 -dimethylthiazolidine based on 25 m ο 1%, and it was used by weight. For 5,000p pm, the acetone and molar ratio of methanol to ethyl mercaptan with a molar ratio of 1/1 (based on acetone) were printed for the consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The results are shown in Table 1. Example 4 The procedure of Example 1 was repeated except that in this example, the same sulfonic acid ion-exchange resin as the catalyst was modified using 2 '2-dimethylthiazolidine as 4 5 in ο 1%, and another containing 50,000p pm by weight This paper standard is applicable to Chinese National Standard (CNS) A4 (21〇 ×; 297mm) 54? -14-1238818 A7 B7 V. Description of the invention Ethyl mercaptan with an ear ratio of 1/5 0 (based on acetone). (Please read the notes on the back before filling out this page.) The results are shown in Table 1. Example 5 Repeat the steps of Example 1 except that In this example, the same sulfonic acid ion-exchange resin modified with 4-(2 ~ mercaptoethyl) pyridine in terms of 30 m 〇1% was used as the catalyst, and the content of the sulfonic acid-type ion exchange resin was 1000 ppm by weight. Methanol has an acetone and a molar ratio of 1/2 0 0 (based on acetone). The results are shown in Table 1. In Examples 1 to 5, satisfactory results were obtained. The selectivity of bisphenol A is at least 93%. Comparative Example 1 Repeated example 1 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition to this example, the same sulfonic acid type ion exchange resin modified as above using 2-mercaptoethylamine as a catalyst at 10 m 〇1% was used as the catalyst, and the content of the sulfonic acid ion-exchange resin containing 10000 p by weight was used. The results are shown in Table 1. Comparative Example 2 The procedure of Example 1 was repeated, except that this example used acetone containing 5000 ppm of methanol by weight. This paper is in accordance with China National Standard (CNS) A4 (210X 297mm) -15- 1238818 Α7 Β7 V. Description of the invention (also the results are shown in Table i. Comparison 仞 I 3 (Please read the precautions on the back before filling out this page) Repeat the steps in Example 1 except This example uses 2 '2 -dimethylthiazolidine modified at 25 m 〇1% as the catalyst of the same sulfonic acid type ion exchange resin as described above and another containing 10000 p pm by weight Methanol in acetone. The results are shown in Table 1. Comparative Example 4 The procedure of Example 1 was repeated, except that this example was modified with the same sulfonic acid as described above using 4- (2-methylethyl) pyridine at 7 mol%. Acid-type ion exchange resins as catalysts, and The result is shown in Table 1. Comparative Example 5 The procedure of Example 1 was repeated by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that this example uses 16 m 〇1% purpose.丨 2,2-Dithiazolidine is used to modify the same sulfonic acid ion-exchange edge f lipid as the catalyst, and acetone and mole ratio containing 20.0 00 p pm methanol are used separately. 1/4 0 0 (based on acetone) ethyl mercaptan. The results are shown in Table 1.
於比較例1至4中’在操作8 0 0小時後，對雙酚A 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） •16 1238818 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（也 的選擇性減至9 0 %或更低，及伴隨著轉化率之下降。 表1 - 1 經改質的酸型離子交換樹月旨 丙酮中的甲醇濃 硫醇化合物 含硫的胺化合物 改質率 度(Cone.) (以丙酮爲基準， (mol%) 似重量計,ppm) 莫耳比） 實例1 2-疏基乙基胺 20 500 1/400 實例2 2,2-二甲基噻唑烷 25 1000 1/200 實例3 2,2-二甲基噻唑烷 25 5000 1/100 實例4 2,2-二甲基噻哩院 45 5000 1/50 實例5 4-(2-毓基乙基)吼啶 30 1000 1/200 比較例1 2-疏基乙基胺 10 1000 0 (Comp’tive) 比較例2 2-疏基乙基胺 20 5000 0 比較例3 2,2-二甲基噻唑烷 25 10000 0 比較例4 4-(2-疏基乙基)D比D定 7 4000 0 比較例5 2,2-二甲基噻唑烷 16 20000 1/400 註：C o m p ’ t i V e ··比較的，C ο n c. ·•濃度 ； ^ 一 .tr~ (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 1238818 Α7 Β7 五、發明説明（仏 表1 — 2 酚之轉化率(％) 第一階段反應 第二階段反應 反應開始 400Hrs 後 800Hrs 後 反應開始 400Hrs 後 800Hrs 後 實例1 13.2 12.1 10.7 15.8 14.0 12.2 實例2 12.9 12.5 11.3 15.7 14.6 13.6 實例3 13.6 12.8 11.2 16.1 14.6 13.7 實例4 11.1 9.8 8.7 13.2 12.9 11.5 實例5 14.2 12.5 10.8 17.8 16.2 14.0 比較例1 12.1 7.2 2.3 14.3 9.6 4.8 (Comp’tive) 比較例2 12.5 7.5 2.7 15.3 11.2 6.8 比較例3 12.2 5.8 1.0 15.0 8.2 2.1 比較例4 12.0 5.1 1.2 14.8 9.2 3.1 比較例5 12.6 6.8 2.1 15.4 10.3 4.4 註：C o m p ’ t i v e ··比較的 —„—.---------- (請先閲讀背面之注意事項再填寫本頁) 訂 f 經濟部智慧財產局員工消費合作社印製 產業利用忡 根據本發明，可穩定地製造具高轉化率之雙酚A ’同 時可抑制由於丙酮中甲醇不純物所引起的觸媒哀減，其在 製備雙酚A之方法中添加硫醇化合物，使用以含硫的胺化 合物部份改質的酸型離子交換樹脂作爲觸媒進行酚與丙酮 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 1238818 A7 B7 五、發明説明（也 間的縮合反應 (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（210X297公釐）In Comparative Examples 1 to 4, 'After 8000 hours of operation, the paper size of the bisphenol A applies Chinese National Standard (CNS) A4 specifications (210 × 297 mm) • 16 1238818 A7 B7 Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 5. Description of the invention (also selectivity decreased to 90% or lower, and accompanied by a decrease in conversion. Table 1-1 Modified acid-type ion exchange tree methanol concentrated thiol in acetone Compound sulfur-containing amine compound modification rate (Cone.) (Based on acetone, (mol%) like weight, ppm) mole ratio) Example 1 2-Pyroethylamine 20 500 1/400 Example 2 2,2-dimethylthiazolidine 25 1000 1/200 Example 3 2,2-dimethylthiazolidine 25 5000 1/100 Example 4 2,2-dimethylthiazolium 45 5000 1/50 Example 5 4 -(2-Yetylethyl) pyridine 30 1000 1/200 Comparative Example 1 2-Pyroethylamine 10 1000 0 (Comp'tive) Comparative Example 2 2-Pyroethylamine 20 5000 0 Comparative Example 3 2,2-Dimethylthiazolidine 25 10000 0 Comparative Example 4 4- (2-Pyroethyl) D Ratio D D 74000 0 Comparative Example 5 2,2-Dimethylthiazolidine 16 20000 1/400 Note : Comp 'ti V e · In comparison, C ο n c. · • Concentration; ^ .tr ~ (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 1238818 Α7 Β7 V. Description of the invention (仏 Table 1 — 2 Phenol conversion rate (%) First stage reaction Second stage reaction start 400Hrs after 800Hrs After 400Hrs start After 400Hrs After example 1 13.2 12.1 10.7 15.8 14.0 12.2 Example 2 12.9 12.5 11.3 15.7 14.6 13.6 Example 3 13.6 12.8 11.2 16.1 14.6 13.7 Example 4 11.1 9.8 8.7 13.2 12.9 11.5 Example 5 14.2 12.5 10.8 17.8 16.2 14.0 Comparative Example 1 12.1 7.2 2.3 14.3 9.6 4.8 (Comp'tive) Comparative Example 2 12.5 7.5 2.7 15.3 11.2 6.8 Comparative Example 3 12.2 5.8 1.0 15.0 8.2 2.1 Comparative Example 4 12.0 5.1 1.2 14.8 9.2 3.1 Comparative Example 5 12.6 6.8 2.1 15.4 10.3 4.4 Note: C omp 'tive ·· Comparison --------------- ---- (Please read the precautions on the back before filling this page) Order f Use of the printing industry by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 忡 According to the present invention, it can be manufactured stably The high conversion rate of bisphenol A can also inhibit the catalyst degradation caused by the impure methanol in acetone. In the method for preparing bisphenol A, a thiol compound is added, and a sulfur-containing amine compound partially modified Acid type ion exchange resin as catalyst for phenol and acetone. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -18-1238818 A7 B7 V. Description of the invention (also the condensation reaction (please read the back first) Please pay attention to this page, please fill in this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210X297 mm)