4 67 887 A7 B7 五、發明説明（1 ) 發昍背暑 聯笨二酚類（dipheno丨s)為非常有用的化學品，尤其 是四-第三丁基聯苯二酚類，被廣泛應用於殺蟲劑、化學 合成中間物、共聚高分子及抗氧化劑等。例如由2, 6 -二-第三丁基酚所合成的四-第三丁基聯苯二酚，是動植物脂 肪、油品、汽油、潤滑油、及橡膠組成物的安定劑。而且 *經由四烷基聯苯二酚脫烷基而得4,4'-聯苯二酚，更是 許多特殊聚縮合高分子、共聚合高分子產品（如液晶高分 子）之必要單體原料。 經濟部中央標準局—工消費合作社印製 USP 4,487,977揭示一種製造四烷基聯苯二酚之方法 ，係利用二烷基酚經由金屬或髙濃度鹼金屬觸媒，於通氧 情況下先反應成四烷基聯對笨醌（tetra alkyl diphenoquinone)之後，再以氫化觸媒於高溫高歷條件下 進行氫化反應，將四烷基聯對苯醌邀原成高纯度的四烷基 聯苯二酚類。此方法不但需以高溫高壓將四烷基聯對苯醌 氫化成四烷基聯苯二酚類，又由於反應過程中不使用溶劑 ，而在反應完成後需K溶劑進行溶解，過漶去除氫化觸媒 後再結晶，不但製程繁雜且產率並不高，故仍有其缺點。 另外，USPs 4,354,P47; 4,354,048; 4,205,187; 4,085,124及4,096,190所揭示者皆靥於此類製法。 USP 3,562,338揭示K兩階段方式製造四烷基聯苯二 酚之方法，第一階段先使二烷基酚於鹼金屬氫氧化物及通 氧反應情況下，轉化成四烷基聯對苯醌，第二階段再添加 部份二烷基酚在絕氧情況下與四烷基聯對苯醌反應，直至 1 5 5 79 (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（2! 0 X 297公釐） 467987 A7 B7 經濟部中央榇準局員工消費合作社印聚 五、發明説明（2 ) 大部份形成四烷基聯苯二酚為止。此方法之效率不佳》且 有反應熱不易散去及高溫氧氣爆炸之虞，且反應後觸媒之 處理及未反應單體之回收均有問題。（JSPs 3,210,384; 3,306,874; 3,306,875及3,631,208亦揭示與上述反應過 程相闞反應部份；而USP 4,482,754則从連續製程進行上 述反應過程之相關程序。 USPs 4,085,124及4,096,190揭示一種四烷基聯苯二 酚之製法，係於含酴金屬氫氧化物或胺類或金屬錯合物觸 媒之水溶液系統中|使二烷基酚進行偶合反應，所得產物 包含有四烷基聯笨二酚，四烷基聯對笨醌及高分子產物， 因而必爾使用特別的分離程序。 USP 4,238,627揭示一種四烷基聯苯二酚之製法，係 使用各種不同觸媒，在髙壓氧及高溫條件下•不使用溶劑 進行二烷基酚的氧化偁合。由於此製法不使用溶劑，因此 對產物、觸媒及雜質之分雔處理等增加很大的困難度。尤 其觸媒與反應物不在同一栢，因而難K提高二烷基酚之轉 化率。 USP 4,847,434則掲示一種四烷基聯苯二酚之製法， 係使用鹼金屬氫氧化物、四級銨塩類相轉移觸媒及過氧化 氫水溶液，使二烷基酚在水溶液中進行氧化偁合反應*最 後產物必需經異丙醇再结晶* K移除未反應之二烷基酚。 日本特開昭61-200935掲示一種聯苯二酚之製法，係 在鹼金屬氫氧化物存在下，在第三丁醇中，使二烷基酚在 通入空氣條件下偶合成四烷基聯笨二酚，其間需利用減壓 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 2 1 5 5 79 (請先閲讀背面之注意事項再填寫本頁) Γ裝— 訂— 条 i ί — -------- 8 8 7 6 44 67 887 A7 B7 V. Description of the invention (1) The dipheno 丨 s are very useful chemicals, especially tetra-tert-butylbiphenyls, which are widely used Used in pesticides, chemical synthesis intermediates, copolymers and antioxidants. For example, tetra-tert-butylbiphenyldiol synthesized from 2,6-di-tert-butylphenol is a stabilizer for animal and vegetable fats, oils, gasoline, lubricants, and rubber compositions. And * 4,4'-biphenol is obtained through dealkylation of tetraalkylbiphenol, which is an essential monomer raw material for many special polycondensation polymers and copolymerized polymer products (such as liquid crystal polymers). . USP 4,487,977 printed by the Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives discloses a method for manufacturing tetraalkylbiphenyls, which uses dialkylphenols through a metal or rhenium concentration alkali metal catalyst to react into After the tetraalkyl diphenoquinone, the hydrogenation reaction is performed under a high temperature and high temperature conditions using a hydrogenation catalyst, and the tetraalkyl diphenoquinone is invited to be converted into a high-purity tetraalkyl diphenol. class. This method not only requires the hydrogenation of tetraalkylbi-p-benzoquinone to tetraalkylbiphenyldiols at high temperature and pressure, but also does not use a solvent during the reaction, but requires K solvent to dissolve after the reaction is completed. Recrystallization after catalyst, not only the process is complicated and the yield is not high, so it still has its shortcomings. In addition, USPs 4,354, P47; 4,354,048; 4,205,187; 4,085,124 and 4,096,190 are all known from such methods. USP 3,562,338 discloses a two-stage method for producing tetraalkylbiphenyldiol. In the first stage, the dialkylphenol is converted into tetraalkylbiphenylquinone under the reaction of an alkali metal hydroxide and oxygen, In the second stage, some dialkylphenols are added to react with tetraalkylbi-paraquinone under anaerobic conditions, up to 1 5 5 79 (please read the notes on the back before filling this page) This paper size is applicable to China Standard {CNS) A4 specification (2! 0 X 297 mm) 467987 A7 B7 Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) Most of the tetraalkylbiphenyls have been formed. The efficiency of this method is not good ", and the reaction heat may not be easily dissipated and the high-temperature oxygen may explode, and the treatment of the catalyst after the reaction and the recovery of unreacted monomers have problems. (JSPs 3,210,384; 3,306,874; 3,306,875 and 3,631,208 also disclose the reaction part that is related to the above-mentioned reaction process; and USP 4,482,754 carries out the relevant procedures of the above-mentioned reaction process from a continuous process. USPs 4,085,124 and 4,096,190 disclose a kind of tetraalkylbiphenyl Preparation method: It is in an aqueous solution system containing rhenium metal hydroxide or amines or metal complex catalysts. The dialkylphenol is subjected to a coupling reaction, and the obtained product contains tetraalkyldibenzyl diphenol and tetraalkyldiamine. For benquinone and polymer products, Biel uses a special separation procedure. USP 4,238,627 discloses a method for the preparation of tetraalkylbiphenols, which uses various catalysts under high pressure oxygen and high temperature conditions. • No solvents are used. Oxidative coupling of dialkylphenols. Since this method does not use a solvent, it is difficult to treat products, catalysts, and impurities. This is particularly difficult because the catalyst and the reactants are not in the same cypress. Improve the conversion rate of dialkylphenols. USP 4,847,434 shows a method for preparing tetraalkylbiphenols, which uses alkali metal hydroxide and quaternary ammonium phosphonium phase transfer. Catalyst and aqueous hydrogen peroxide solution to make oxidative coupling reaction of dialkylphenol in aqueous solution * The final product must be recrystallized by isopropanol * K to remove unreacted dialkylphenol. Japanese Patent Application Laid-Open No. 61-200935 Shown is a method for the preparation of biphenol, which is based on the coupling of dialkylphenol with tertiary butanol in the presence of an alkali metal hydroxide in tertiary butanol. The dimensions of this paper are in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 2 1 5 5 79 (Please read the precautions on the back before filling this page) Γ 装 — 订 — 条 i ί — ---- ---- 8 8 7 6 4
B 明説明S 發鋪 T蒸五 酿 基 烷二 體 單 之 應」 反 未 及 醇 丁 三 第 出 鋪 物 形 固 得 所 媒約 觭僅 化率 基化 烷轉 脫之 入酚 加基 中烷 液 二 漶之 於法 再製 , 此 媒。 觸應 除反 漶化 , 基 解烷 溶脫 醚行 笨進 K 接 再直 烷 四 造 製 度 純 高 率 效 髙 Μ 種 1 供 提 係 的 百 之 明 發 Ja本 明 發 供法 。 提方 法係之 方的物 之目合 物一化 合另酚 化之二 酚明苯 二發聯 苯本基 聯 烷 基 四 造 製 度 純 髙 、 率 效 髙 以 種 在 法 應 反 段 階 兩 Μ 括 包 法 方 之 離 分 及 晶 長 核 成 接 直 並 應 反 行 it㈤ 中概 劑明 溶發 括條 包氧 - 通 法及 製中 穎劑 新溶 之於 騎， 二 下 苯在 聯存 基媒 烷觸 四性 種 阚 1 在 闞 ， 有酚 僳基 明烷 發 二 本使 閉 ， 密率 壓速 高拌 溫攪 高及 於率 } 速 (b溫 ; 降 酚制 二 控 苯 } C 聯 ί 基及 烷 ； 四應 成反 合化 偶轉 化行 氧進 ’ 0 下繼 件.下 而 晶 结 核 成 中 劑 溶 在 中 統。 糸酚 閉 二 密苯 該聯 在基 酚烷 二 四 笨之 聯度 基純 烷 高 四得 使可 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印裝 明 說 细 詳 明 0 包 法 方 造 製 穎 新 之 酚二 苯 聯 基 烷 四 CHt- 種 一 示 揭 明 發 本 氧密 通壓 在高 中溫 劑高 溶於 於} b ， ( 下 丨 在酚 存 二 媒苯 觸聯 性基 鹼垸 在四 - 成 酚合 基偁 烷化 二 氧 使 - — 下 (a件 括條B indicates that the application of S-fat and T-pentamyl alkane dimers is not as good as that of the butadiene-butadiene-based product, so that only the conversion rate of the alkylated alkane is transferred to the phenol plus alkyl alkane. Liquid Erzhi was made by law, this medium. In response to the dephosphorylation reaction, the alkyl alkoxide dissolves and de-etherifies the benzene, K, and then alkane to produce four high-efficiency, pure, high-efficiency 种 M species 1 supply and extraction systems. The method of formulating the object of the formula is a compound of another phenol, bisphenol, benzene, benzene, biphenyl, and dialkyl. The system is pure, efficient, and effective. The separation of the French side and the growth of the crystal nucleus are straight and should be reversed. The intermediate solution is clear dissolved, and the oxygen is contained. Contact with the tetrad species 阚 1 In 阚, there are two phenol sulfonylbenzines which are closed, and the density and pressure are high and the temperature is high and the temperature is high. The rate is high (b temperature; phenol reduction by benzene control). The quaternary reaction should be converted into an oxygenated couple and the oxygen will be transferred to the next 0's. The next step is to crystallize the nodules into the intermediate system. High-grade pure alkanes are available (please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, detailed and detailed descriptions 0 Four CHt-species one reveals the oxygen tight pressure High Temperature agent in a high dissolved} b, (Shu phenol under two storage media benzene touch-linkable group in the four base embankment - Cheng alkoxy group bonded to the phenolic oxygen to make di - - at (a bar member comprising
及接苯 率直聯 速而基 溫，烷 憐晶四 之結之 中核度 統成純 系中高 應劑得 反溶 ， 制在離 控酚分 } 二 酚 (C苯基 及聯烷 ; 基二 應烷之 反四應 化使反 轉，未 行率與 進速濟 下拌過 閉棵 K 本纸張尺度適用中國國家標準（CNS > A4規格（210X297公釐） 3 1 5 5 79 kBlQBl A7 B.7 五、發明説明（4 ) 二酚。 詳言之，本發明掲示一種四烷基聯苯二酚 *包括U)使二烷基酚，在鹸性觸媒存在下， 通氧條件下，於901CK下之溫度常壓進行氧化 產生四院基驗每二酷（tetraalkyi diphenol) 對苯醌（t e t r* a a 1 k y 1 d i p h e η o q u i η ο n e ) ; ( b ) K 換糸統內之氣體，使氧含量控制在10% K下， 壓進行轉化反應，而使（a)步驟中未反應之二 烷基聯對苯醌再轉化成四烷基聯苯二酚；（c) ，將攪拌速率控制在150rpmK下，及降溫速率 鐘5七以下| Μ使四烷基聯苯二酚自溶劑中逐 ，而未反應之二烷基酚則仍溶於溶劑中，待溫 ，再經由簡單的過瀘分離出结晶固體，再Κ少 後，烘乾，可製得高純度之四烷基聯笨二酚。 經濟部中央標準局員工消費合作社印製 之新穎製法 於溶劑中在 偶合反應， 及四烷基聯 惰性氣體置 再Μ高溫高 烷基酚與四 轉化完畢後 控制在每分 漸成核長晶 度降至室溫 量溶劑清洗 產物”四烷 之垸基，其 、正丙基、 及己基等。 (請先閱讀背面之注意事項再填寫本頁) 本發明方法中所用之起始物”二烷基酚”及 基聯笨二酚"中之”烷基”意指含1至6個碳原子 可為直鏈或分枝者。焼基實例例如甲基、乙基 異丙基、正丁基、第二丁基、第三丁基、戊基 Κ第三丁基尤佳。 二烷基酚中之烷基可在酚環上之任何位置，但較好在 2及6位置。 四烷基聯苯二酚上四烷基之位置係對應於二烷基酚之 烷基位置，例如當二烷基酚係2,6 -二烷基酚時，對應之四 烷基聯苯二酚可為3, 3’，5,5’-四烷基聯苯二酚。 1 5 5 7 9 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 46 Τ8δΤ Α7 r B7 五、發明説明（5 ) 本發明中所用之鹼性觸媒係作為二烷基酚氧化偶合之 觸媒。該鹼性觸媒包含鹼金雇氧化物如氧化鈉、氧化鉀； 鹼金屬氫氧化物如氫氧化鈉、氫氧化鉀；鹼金属碳酸塩如 碳酸納、碳酸鉀；鹼金屬醇塩如異丙醇納、異丙醇鉀、第 三丁酵納、窠三丁醇鉀；及鹼金屬芳醇塩如酚納塩。該等 鹼性觸媒可單獨或組合使用。鹼性觸媒之用量並無限制， 但通常對每莫耳二烷基酚使用約0.1至2莫耳之範圍，更好 為0.01至1其耳，最好為0.05至0.5萁耳之範圍。鹼性觸媒 可直接以固體加入反應系統中，亦可配成水溶液加入反應 糸統中。 經濟部中央標準局員工消費合作社印製 (請先聞讀背面之注意事項再填寫本頁) 本發明方法中所用之溶劑為可溶解起始物及鹼性觸媒 並有利於四烷基聯笨二酚结晶之溶劑。溶劑實例例如醇類 如甲醇、乙醇、丙醇、異丙醇、正丁醇、異丁醇；烴類如 己烷；鹵化烴類如二氯甲烷、三氯甲烷；芳族烴類如苯、 甲笨；酯類如乙酸乙酿；酚類如鼢、間-甲酚及對甲酚。 其中尤以酵類較佳。溶劑之用量並無特別限制*只要可使 起始物及觸媒溶解即可。但通常為二垸基酚重量之50 %至 300¾之間，更好為100至200¾之間。 本發明方法中，係K (a)及（b)步驟之不同條件進行 連績反應。（a)步驟之反應溫度為50至90¾之範圍，且需 在通氧條件下進行反應。通氧可通人純氧或含氧之氣體如 空氣等。通入之氧氣係作為二烷基酚偁合成四垸基聯苯二 酚之氧化劑。氧氣使用量為對每莫耳二烷基酚使用0.25至 2. 5莫耳，更好為0.5至1.5莫耳。 本紙張尺度適用中國國家標準（CNS ) A4規格（2 ί Ο X 297公逄） 5 1 55 7 9 Λ7 46 7 88 7 B7 五、發明説明（6 ) (請先閱讀背面之注意事項再填寫本頁) 本發明方法中，（b)步驟係在高溫高壓條件下進行反 應，且（b)步驟中需先Μ惰性氣體置換U)步驟中之氧氣， 並控制氧氣含量在0至10¾之間，更好為0.5〜5¾ 。反應 溫度須高於四烷基聯苯二酚之熔點溫度*但通常為180至 260Ό間，®好為180至24010之間。反應壓力為溶劑在反 應溫度下之飽和蒸汽壓力。 本發明方法中，步驟（c)之成核長晶步驟|係藉由控 制降溫速率及降低攪拌速率而使產物進行成核長晶。降溫 速率宜控制在每分鐘5¾ Μ下|且搜拌速率宣控制在低於 lSOrpm。在降至室溫後，可直接過濾结晶並K所用溶劑清 洗|而得高純度之四烷基聯笨二.酿晶體。 本發明方法中，步驟（b)所用之惰性氣體可為例如氦 氣、氖氣、氩氣、氮氣等，其中Μ氮氣較佳。步驟（b)中 惰性氣體置換後*可Μ氣相層析儀測定反應器中氧氣殘存 量，而決定停止通入惰性氣體之時間。 本發明將Κ下列實施例進一步說明本發明，但不因此 限制本發明之範園。 經濟部中央標準局員工消費合作社印製 管施例1 2,6-:-M^£TSS&(2,6-di-tert-butylphenol， 2,6-DTBP)206.4g(1.0莫耳）溶於含有氫氧化鉀2.78g(0.05 莫耳）及異丁醇206s的高壓反應釜中*蕷熱攪拌昇溫到70 它，於反應釜氣體入口 ，徐徐導入每分鐘lOOc.c.流量的 氧氣，使用渦輪葉片型式攪拌棒轉速500rpin，反應釜氣體 出口處，先K水吸收帶出的異丁醇後，再排至大氣中，此 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇X：297公漤） 6 1 5 57 9 467887 Λ7 B7 五、發明説明（7 ) 通氣反應持缅反應2小時後，停止氧氣導入至Μ氮氣置換 密封，釜中氣氣含量為3.6%左右，再昇溫到180Ό持鑕反 應1.5小時後，Κ每分鐘31C的降溫速率降溫》轉速調降為 lOOrpm Μ利四-第三丁基聯笨二酚成核長晶，待降至室溫 後再過漶清洗，所得產品以7〇·〇烘乾過夜* MHPLC分析純 度高達99.85¾ ，熔點為189¾ (DSC)，而2,6-二-第三丁基 酚的轉化率高達93.8%左右。 窗掄例2 2,6 -二-第三丁基酚206.4s (1.0莫耳}、5%氫氧化 鉀水溶液22.4g(0.1莫耳）、異丙醇309g置入高壓反應釜 中，預熱搜拌昇溫到80¾，徐徐導入每分鐘100c.c.流量 的氧氣，渦輪葉片型式搅拌棒轉速500rpm，持續反應6.5 小時後，停止氧氣導入並K氮氣置換密封*釜中氧氣含量 為3.5%左右，昇溫至200¾持績反應2.5小時後，K每分 鐘4¾的降溫速率降溫•轉速調降為lOOfPffi Μ利產物成核 長晶•待降至室溫再過濾清洗，所得產物K70t烘乾過夜 * M HPLC分析純度高達99.81¾ |熔點為189¾ (DSC)，而 2,6 -二-第三丁基酚的轉化率高達96.5%左右。 l:h較例1 將2,6-二-第三丁基酚206.48(1.0莫耳）、50%氫氧 化鉀水溶液5.56g(0.05莫耳）及異丁醇309s置人1公升玻 璃反應釜中，攪拌並水浴加熱昇溫至8010 ，徐徐導入每分 鐘200c.c.流量的氧氣，氣體透過冷凝管釋故入大氣中， 反應約4小時後*停止供應氧氣，並Μ氮氣置換玻璃釜中 (請先閱讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作社印製 ------------,* 裝----^--訂------Κ ^----J*i1------- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 7 15 579 4 67 887 Λ7 Β7 五、發明説明（8 ) 的氧氣，K電熱包替代水浴鍋，約100分鐘逐漸昇溫至200 t *同時豳出反應釜中含水的異丁醇後，溫度維持在200 t：，開始減壓蒸餵未反應的2,6-二-第三丁基酚，負壓200 t 〇 r r持續約1 5分鐘，低速攪拌降溫*待溫度達到1 0 0 10左 右·注入大i純水並強力攪拌，Κ分散懸浮產物*然而尚 有部份结塊現象》所得泥漿狀產物經過溥、清洗程序•並 分析得產物純度約91.4¾左右*其中含有未反應2,6 -二-第三丁基聯苯二酚5. 26¾及3,3’，5,5·-四-第三丁基聯對 苯醌3.34 % ，而二-第三丁基酚的轉化率則為63.4¾左右 〇 啻施例3 經濟部中央標準局員工消費合作社印製 (請先間讀背面之注意事項再填寫本頁) 2,S -二-第三丁基酚103,2s(0.5莫耳）、50%氫氧化鉀 水溶液5.6s (0.05莫耳）、間-及對-甲酚混合物（60/40) 309ε置入高壓反應釜中，預熱攪拌昇溫至90¾ ，徐徐導入 每分鐘50c.c.流量的氧氣，使用渦輪葉片型式搅拌棒轉速 500γρπ.-反應釜氣體出口處，先以水吸附帶出的間-及對-甲酚混合物後，再排至大氣中•持續反應5.5小時後，停 止氧氣導人並以氮氣置換密封|釜中氧氣含量為1.6¾ 左 右，再昇溫至21〇υ持缅反應3.5小時後，K每分鐘3¾的 降溫速率降溫，轉速調降為lOOrpmM利產物成核長晶，待 降至室溫過漶，並Μ間、對-甲酚溫合物及9 0 t熱水清洗 ，所得產物M70〜80t之間烘乾過夜，MHPLC分析純度高 達99.9%，熔點為186.410$(：)，而二-第三丁基酚的轉 化率高達97.8%左右。- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 8 1 5 5 79 A7 4 67 887 B7 五、發明説明（9 ) g觖例4 2,6-二-第三丁基酚206.48(1.0莫耳）、49.6%氫氧化 納水溶液4.032s(0.05莫耳）、異丁醇206s置人高壓反應釜 中，預熱攪拌昇溫到60t：，徐徐導入每分鐘75c.c.流量的 氧氣，渦輪棄片型式攪拌棒轉速5 00 r pm |反應釜氣體出D 處，經水吸附帶出的異丁醇*持鱭反應7小哼後，停止氧 氣専入並Μ氮氣置換密封，釜中氧氣含量為2.3% 左右， 再昇溫至180t：持續反應2小時後•以每分鐘4¾的降溫速 率降溫•轉速調降為lOOrpmK利產物成核長晶，待降到室 溫過溏清洗|所得產物以70〜80¾之間烘乾過夜，經HPLC 分析純度高達99.81% ，熔點為187.51 (DSC)，而二-第三 丁基鼢的轉化率高達95.6%左右。 (請先閲讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作杜印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 9 1 5 57 9And the rate of benzene is directly linked to the base temperature, and the nucleus of the alkane crystal four becomes a pure medium high-reaction agent to be reversely dissolved. It is produced in the isolated phenol fraction} diphenol (C phenyl and dialkyl; The reverse of the four-response makes the reversal, the non-performing rate and the speed of mixing closed tree K paper size applicable to Chinese national standards (CNS > A4 specifications (210X297 mm) 3 1 5 5 79 kBlQBl A7 B. 7. V. Description of the invention (4) Diphenol. In particular, the present invention shows a tetraalkylbiphenol * including U) Dialkylphenol, in the presence of a catalyst, under the condition of oxygen, under Oxidation at 901CK under normal pressure produces tetraalkyi diphenol (tetr * aa 1 ky 1 diphe η oqui η ο ne); (b) K changes the gas in the system, so that The oxygen content is controlled at 10% K, and the conversion reaction is performed under pressure, so that the unreacted dialkyl-p-benzoquinone in step (a) is converted into tetraalkylbiphenyldiol; (c), the stirring rate is controlled At 150 rpmK, and the cooling rate is below 5-7 | Μ makes tetraalkylbiphenols from the solvent, but unreacted dialkyl It is still dissolved in the solvent, and after being warmed, the crystalline solid is separated through simple passivation, and then dried after a small amount of K, and a high-purity tetraalkylbiphenyldiol can be prepared. Consumption by employees of the Central Standards Bureau of the Ministry of Economic Affairs The new method printed by the cooperative is used in a coupling reaction in a solvent, and the tetraalkyl-linked inert gas is placed at a high temperature and the high-alkylphenol is converted to a gradual nucleation degree. The product "tetraalkanoyl, its n-propyl, and hexyl, etc. (Please read the notes on the back before filling out this page) The starting materials used in the method of the present invention" dialkylphenols "and acetylbenzyl "Alkyl" in diphenol " means a group containing 1 to 6 carbon atoms which may be linear or branched. Examples of fluorenyl groups such as methyl, ethyl isopropyl, n-butyl, second butyl, Tertiary butyl and pentyl K tertiary butyl are particularly preferred. The alkyl group in the dialkylphenol may be at any position on the phenol ring, but preferably at the 2 and 6 positions. The position of the alkyl group corresponds to the alkyl position of the dialkylphenol. For example, when the dialkylphenol is 2,6-dialkylphenol, The corresponding tetraalkylbiphenyldiol can be 3,3 ', 5,5'-tetraalkylbiphenol. 1 5 5 7 9 This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) ) 46 Τ8δΤ A7 r B7 V. Description of the invention (5) The basic catalyst used in the present invention is a catalyst for oxidative coupling of dialkylphenols. The basic catalyst contains alkali metal oxides such as sodium oxide, oxidation Potassium; Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal alcohols such as sodium isopropoxide, potassium isopropoxide, third isocyanate, sodium Potassium butoxide; and alkali metal aromatic alcohols, such as sodium phenoxide. These alkaline catalysts can be used alone or in combination. The amount of the alkaline catalyst is not limited, but it is generally used in the range of about 0.1 to 2 moles per mole of dialkylphenol, more preferably 0.01 to 1 mole, and most preferably 0.05 to 0.5 moles. The alkaline catalyst can be directly added to the reaction system as a solid, or it can be formulated as an aqueous solution to be added to the reaction system. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The solvent used in the method of the present invention is soluble in starting materials and basic catalysts and is conducive to tetraalkylbenzene Solvent for diphenol crystals. Examples of solvents are, for example, alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol; hydrocarbons such as hexane; halogenated hydrocarbons such as dichloromethane, chloroform; aromatic hydrocarbons such as benzene, Methylbenzyl; esters such as ethyl acetate; phenols such as pyrene, m-cresol and p-cresol. Among them, yeast is better. The amount of the solvent is not particularly limited as long as the starting material and the catalyst can be dissolved. However, it is usually between 50% and 300¾, more preferably between 100 and 200¾. In the method of the present invention, successive reactions are performed under different conditions of steps K (a) and (b). The reaction temperature in step (a) is in the range of 50 to 90¾, and the reaction needs to be carried out under oxygen-filled conditions. Oxygen can pass through pure oxygen or oxygen-containing gas such as air. The introduced oxygen is used as an oxidizing agent for the synthesis of tetrafluorenylbiphenyldiol from dialkylphenols. The amount of oxygen used is 0.25 to 2.5 moles per mole of dialkylphenol, more preferably 0.5 to 1.5 moles. The size of this paper applies Chinese National Standard (CNS) A4 (2 ί Ο X 297 cm) 5 1 55 7 9 Λ7 46 7 88 7 B7 V. Description of the invention (6) (Please read the precautions on the back before filling in this Page) In the method of the present invention, step (b) is carried out under high temperature and pressure conditions, and step (b) requires the inert gas to replace the oxygen in step U), and the oxygen content is controlled between 0 and 10¾, More preferably, it is 0.5 to 5¾. The reaction temperature must be higher than the melting point temperature of the tetraalkylbiphenol. However, it is usually between 180 and 260 ° C, and preferably between 180 and 24010. The reaction pressure is the saturated vapor pressure of the solvent at the reaction temperature. In the method of the present invention, the step of nucleating and growing the crystals in step (c) is performed by controlling the cooling rate and reducing the stirring rate to nucleate and grow the product. The cooling rate should be controlled at 5¾ M per minute | and the search and mixing rate should be controlled below 1SOrpm. After falling to room temperature, the crystals can be directly filtered and washed with the solvent used in K | to obtain a high-purity tetraalkylbiben. Crystal. In the method of the present invention, the inert gas used in step (b) may be, for example, helium, neon, argon, nitrogen, etc., among which M nitrogen is preferred. After the replacement of the inert gas in step (b), the remaining gas in the reactor can be measured by a gas chromatograph, and the time for stopping the inert gas can be determined. The present invention will further illustrate the present invention by the following examples, but does not limit the scope of the present invention. Example 1 Printed tube of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 2,6-:-M ^ £ TSS & (2,6-di-tert-butylphenol, 2,6-DTBP) 206.4g (1.0 mole) In a high-pressure reaction kettle containing 2.78 g (0.05 mol) of potassium hydroxide and 206s of isobutanol *, heat up to 70 with hot stirring, and slowly introduce oxygen at a flow rate of 100 c.c. per minute at the gas inlet of the reactor, use Turbine blade type stirring rod rotates at 500rpin, and at the gas outlet of the reactor, the isobutanol taken out by K water is absorbed first, and then discharged to the atmosphere. This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇X : 297 cm) 6 1 5 57 9 467887 Λ7 B7 V. Description of the invention (7) After the aeration reaction was carried out for 2 hours, the introduction of oxygen to the nitrogen gas was stopped and the seal was closed. The gas content in the kettle was about 3.6%, and then the temperature was increased. After 1.5 hours of reaction at 180 ° C, the cooling rate of K at 31C per minute was reduced. The speed was adjusted to 100 rpm. Metylene tetra-tert-butylbibenzol nucleated crystals were grown. After the temperature was lowered to room temperature, they were rinsed. The obtained product was dried overnight at 70 · 0. The purity by MHPLC analysis was as high as 99.85¾ and the melting point was 189¾ (DSC). 2,6-di - tert-butyl phenol conversion rate as high as 93.8%. Case 2 Example 2,6.4-Di-tert-butylphenol 206.4s (1.0 mole), 22.4 g (0.1 mole) of 5% potassium hydroxide aqueous solution, 309 g of isopropanol were placed in a high-pressure reactor and preheated The temperature of the mixture was increased to 80¾, and the oxygen flow rate of 100 c.c. per minute was slowly introduced. The turbine blade type stirring rod was rotated at 500 rpm. After the reaction continued for 6.5 hours, the oxygen introduction was stopped and the K nitrogen was replaced to seal the oxygen content of the kettle. After heating up to 200¾ for 2.5 hours, the cooling rate of K was reduced to 4¾ per minute. • The speed was adjusted to 100fPffi. The product was nucleated and grown in crystals. • After cooling to room temperature, it was filtered and washed. The resulting product was dried at K70t overnight. M HPLC Analytical purity is as high as 99.81¾ | Melting point is 189¾ (DSC), and the conversion of 2,6-di-tertiary-butylphenol is as high as about 96.5%. L: h Comparative Example 1 2,6-di-tertiary-butyl Phenol 206.48 (1.0 mole), 50% potassium hydroxide aqueous solution 5.56g (0.05 mole) and isobutanol 309s were placed in a 1 liter glass reaction kettle, stirred and heated in a water bath to 8010, and slowly introduced 200c.c per minute The flow of oxygen, the gas is released into the atmosphere through the condensate tube, and after about 4 hours of reaction * the supply of oxygen is stopped, and Μ Nitrogen Replacement Glass Kettle (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ------------, * 装 ---- ^- -Order ------ Κ ^ ---- J * i1 ------- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 7 15 579 4 67 887 Λ7 Β7 5 2. Description of the invention (8) Oxygen, K electric heating bag instead of water bath, gradually warmed to 200 t in about 100 minutes * At the same time, after the isobutanol containing water in the reactor was decanted, the temperature was maintained at 200 t: Unreacted 2,6-di-third butyl phenol, 200 t rr negative pressure for about 15 minutes, low temperature stirring to cool down * until the temperature reaches about 10 0 10 · Inject large pure water and stir vigorously, Κ Disperse suspended products * However, there is still some agglomeration phenomenon.> The mud-like product obtained is subjected to a 程序, washing procedure and analysis. The purity of the product is about 91.4¾. * It contains unreacted 2,6-di-tert-butylbiphenyl diphenyl Phenol 5.26¾ and 3,3 ', 5,5 · -tetra-tertiary-butyl-para-benzoquinone 3.34%, while the conversion of di-tertiary-butylphenol is about 63.4¾. Example 3 Economy Member of the Central Standards Bureau Printed by a consumer cooperative (please read the precautions on the back before filling this page) 2, S-Di-tertiary-butylphenol 103.2s (0.5 mol), 50% potassium hydroxide aqueous solution 5.6s (0.05 mol ), M- and p-cresol mixture (60/40) 309ε was placed in a high pressure reaction kettle, preheated and stirred to 90¾, slowly introduced oxygen at a flow rate of 50c.c. per minute, using a turbine blade type stirring rod at a speed of 500γρπ .-The gas outlet of the reactor is first absorbed by the water-and p-cresol mixture, and then discharged to the atmosphere. After the reaction continues for 5.5 hours, stop oxygen introduction and replace the seal with nitrogen | Oxygen in the kettle The content is about 1.6¾, and then it is heated up to 21 ℃. After the Burma reaction for 3.5 hours, the temperature of K is reduced to 3¾ per minute, and the speed is adjusted to 100rpm. The product is nucleated and grows. It was washed with m-, p-cresol warm compound and 90 t hot water, and the obtained product was dried overnight between M70 ~ 80t. The purity by MHPLC analysis was as high as 99.9%, the melting point was 186.410 $ (:), and di-third butyl The conversion rate of phenol is as high as 97.8%. -This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 8 1 5 5 79 A7 4 67 887 B7 V. Description of the invention (9) g Example 4 2,6-Di-tert-butylphenol 206.48 (1.0 mol), 49.6% sodium hydroxide aqueous solution 4.032s (0.05 mol), isobutanol 206s were placed in a high-pressure reaction kettle, preheated and stirred to warm up to 60t :, and slowly introduced a flow rate of 75c.c. per minute Oxygen, turbine disc-type type stirring rod speed 5 00 r pm | Reactor gas outlet D, isobutanol carried out by water adsorption * holding the reaction after 7 hum, stop the oxygen inflow and replace the seal with M nitrogen The oxygen content in the medium is about 2.3%, and then the temperature is raised to 180t: After continuing the reaction for 2 hours • The temperature is reduced at a rate of 4¾ per minute • The speed is adjusted to 100 rpm. The product was dried at 70 ~ 80¾ overnight. The purity was 99.81% by HPLC analysis, the melting point was 187.51 (DSC), and the conversion of di-tert-butylphosphonium was as high as 95.6%. (Please read the precautions on the back before filling out this page} Printed by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for China National Standard (CNS) A4 (210X297 mm) 9 1 5 57 9