572939572939
HOAr: ΗΟ^ ΗΟ-0 Ηφ (精先閱讀背面之注意事項再填寫本頁) ·· 經濟部智慧財產局員工消货合作社印製 HB D P為反應型芳磷系難燃劑，適合於鍵結環氧樹脂 等單體，聚合反應後成品可維持其物性、化性並具耐^ 性，為未來環保產品之趨勢。 有關羥基反應型芳磷系難燃劑合成方法，例如美國 專利第 5,506,3 13 號（ 1996 年）與第 5,278,212 號（1994 年），均提出產品為混合物，主成份比例偏低，未明示純 化方式或以鹽酸水清洗產品。該等美國前案主要内容在 顯示羥基芳磷系難燃劑在應用後，減緩成品在化性、物 性的變化。 另外·，本案發明人之美國專利第6，124,492號（2000 年）揭露有關[雙-(3-第三丁基-4-羥基苯基_2,4_二-第三丁 基苯基）間苯二酚二鄰酸酯之製法]，成功的提供一種具有 咼轉化率與高選擇性之生產方法，來製造雙_(3-第三丁基 -4-¾基苯基-2，4-二-第三丁基苯基）間苯二g分二鄰酸酯。 本纸怅尺度過用中國國家標準（CNS)/V1規格（210 x 297公沒） ϋ H · I I n ϋ -I n —i ϋ n I n ϋ I ϋ n n ϋ ϋ ϋ n n ϋ 572939 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 A7 五、發明說明（2 【發明之概述】 本發日月i El 心曰的，主要在提供一種含羥基丙二酚芳磷 酉旨製浩古、、土 ^ ^ ' ’可以提高單一產品的純度、具有反應再 見丨生氣心步驟簡化與純化步騾具環保概念等諸多優 ”占本發明〈製造方法提供了擴量生產的可行性。 本發明之制；主士 ， 〃 表k万法，可以用來製備含羥基丙二酚芳 粦酉曰（簡％ Η B D P )。本發明之製造方法大致包括下列 步騍·（ 1)將丙二酚，適量的氯化磷醯與適量的氯化鎂當 觸媒，進仃加熱第一階段酯化反應，得到單取代為主要 中間產物；（2)蒸餾回收未反應的氯化磷醯，再加入適量 的鄰位含垸基酚類化合物與有機鹼，繼續進行加熱第二 階段酯化反應；（3)第二階段酯化反應結束後，再加入適 量的第二丁基對苯二酚進行加熱第三階段酯化反應；以 及（4)當反應結束後，加入有機溶劑，先過濾有機鹼的鹽 酸鹽，再以少量氨氣置換殘存鹽酸鹽為氯化銨，過滤氣 化銨’減壓蒸餾有機溶劑，即可得Η B d Ρ系列化合物。 本發明之製造方法中，過量之氯化磷醯其較佳係為 丙一酚莫耳數之四至八倍。適量之氯化鎂觸媒使用量其 較佳係為氯化磷醯重量的O.i至1〇%，更佳係為氯化磷 酿重量之0.4%。 本發明之製造方法中，其中第一階段酯化的加熱溫 度較佳係為60〜120°C ’更佳係為丨⑼〜丨1〇t。第二、主 階段酯化的加熱溫度較佳係為1 00〜1 5，更佳係為 120〜130〇C 0 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 x 297公釐） 衣--------訂---------線4^ (請先閱讀背面之注意事項再填寫本頁} 五、發明說明（多） 本發明之製造方法中，其中三階段酯化反應結束是 才曰反應產物經31P核磁共振光譜確定。 本發明之製造方法中’其中步驟⑺之有機驗較佳係 選自包括三乙基胺或扯啶族群中之一者或兩者，其用量 為丙二酚1〜2倍當量。其中步驟（4)之有機溶劑較佳係 選自包括甲苯、二甲苯、乙酸乙酯、或乙酸丁酯族群中 之一者或數者。 一般而T，本發明之製造方锋按最適條件製備，部 刀產PP轉化率以丙一紛計算鬲達理論値1⑼％，選擇性在 80%以上。 【發明之較佳具體實施例説明】 本發明之製造方法將氯化磷醯、丙二紛與氯化鎂一 次加入反應槽内，反應溶液溫度加熱反應4小時後，蒸 出過量的氯化磷醯；續加入鄰位含烷基酚類化合物與有 機驗，在加熱反應2小時；再加入第三丁基對苯二酚， 加熱反應2小時；三階段酯化反應均以3!p核磁共振光譜 儀檢測完全作用。產品溶於有機溶劑後，先過濾有機鹼 的鹽酸鹽，再以少量氨氣將殘存有機鹼鹽酸鹽置換成氯 化銨，過濾氯化銨蒸餾回收有機溶劑，即可得到Η B D Ρ系列化合物。 根據本發明，含羥基丙二酚芳磷酯（簡稱Η B D Ρ ) 之製備在單爸下進行，首先將丙二龄，過量的氯化磷醯 及微量的催化劑氣化鍰同時加入反應槽内，反應槽上置 本紙張尺_家標準（CNS)A4規格⑵G χ 297公发）—^ 572939 Λ7 B7 五 、發明說明（f·) 冷凝管及溫度探針，冷凝管上接導氣管，可將鹽酸導入 中和槽。 第一階段加熱溫度在60〜12(rc，常壓下進行酯化反 應’王要生成單取代物（11=1)及少量雙取代物（㈣），如下 述方程式（1);較佳的溫度控制為1〇〇〜11(rc，溫度過高 反應釋出的大量鹽酸氣會把氯化磷醯帶離反應槽，·約4 ^時後，進行過量氣化磷醯回收的減壓（30〜40mmHg) ，餾；約2·5小時後氣化磷不再蒸出後；回復室溫加入當 量含鄰位烷基酚類化合物與二倍當量有機鹼進行第二階 段酯化反應，·如下述方程式（2);溫度控制在1〇〇〜15〇Ό， 較佳為120〜130°C二小時；續加入當量第三丁基對苯二 酚，進行第三階段酯化反應，如下述方程式（3);溫度控 制在100〜150°C，較佳為120〜13(TC二小時；三階段酯化 反應元成後，分別以31 p核磁共振光譜儀測試確定其反應 終點。 當反應完成後，產物溶於有機溶劑中，回復室溫先 過濾有機鹼的鹽酸鹽，再以少量氨氣將未析出的有機驗 鹽酸鹽置換為氣化銨，過濾氣化銨蒸餾回收有機溶劑， 即可得到Η B D P產品。全程反應以丙二酚為計算基礎， 轉化率高達理論値100%，選擇性在80%以上。 0 (I) Ρ〇α3 + ΗΟ^Η^ΟΗ 1!2 (cat\ Cl-P- △ ClHOAr: ΗΟ ^ ΗΟ-0 Ηφ (Read the notes on the back first and then fill out this page) ·· The HB DP printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a reactive aromatic phosphorus flame retardant, suitable for bonding The monomers such as epoxy resin can maintain their physical properties, chemical properties and resistance after polymerization, which is the trend of environmentally friendly products in the future. Regarding the synthesis method of hydroxyl-reactive aromatic phosphorus-based flame retardants, for example, U.S. Patent Nos. 5,506,3 13 (1996) and 5,278,212 (1994) have proposed that the product is a mixture with a low proportion of main components, which has not been explicitly purified. Wash the product with water or hydrochloric acid. The main content of these previous U.S. cases is to show that after the application of hydroxyaromatic phosphorus flame retardants, it slows down the changes in the chemical and physical properties of the finished products. In addition, U.S. Patent No. 6,124,492 (2000) of the inventor of the present case discloses [bis- (3-third-butyl-4-hydroxyphenyl_2,4-di-third-butylphenyl) Production method of resorcinol diphthalate], has successfully provided a production method with fluorene conversion and high selectivity to produce bis (3-thirdbutyl-4-¾ylphenyl-2,4 -Di-tert-butylphenyl) isophthalic acid g-di-phthalate. This paper has been scaled to the Chinese National Standard (CNS) / V1 specifications (210 x 297). Ϋ H · II n ϋ -I n —i ϋ n I n ϋ I ϋ nn ϋ ϋ ϋ nn ϋ 572939 Wisdom of the Ministry of Economic Affairs A7 printed by the Consumer Cooperative of the Property Bureau V. Invention Description (2 [Summary of the Invention] This article describes the eleventh day of the eleventh month, mainly to provide a kind of hydroxymalonol-containing phosphorous phospholipids to make Haogu, ^ ^ '' It can improve the purity of a single product, have a goodbye reaction, simplification of angry steps, and purification steps with environmental protection concepts, etc. 'account for the present invention <the manufacturing method provides the feasibility of expanded production. The system of the present invention; master The method can be used to prepare hydroxypropionol-containing aromatic compounds (Simplified% Η BDP). The manufacturing method of the present invention generally includes the following steps: (1) the glycerol is chlorinated in an appropriate amount Phosphorium phosphonium and a suitable amount of magnesium chloride are used as catalysts, and the first stage of the esterification reaction is heated to obtain mono-substitution as the main intermediate product; (2) Unreacted phosphorus phosphonium chloride is recovered by distillation, and an appropriate amount of ortho-containing phosphonium groups is added Phenolic compounds and organic bases, continue Carry out the second-stage esterification reaction by heating; (3) After the second-stage esterification reaction is completed, add an appropriate amount of second butyl hydroquinone for the third-stage esterification reaction by heating; and (4) after the reaction is completed Add organic solvents, first filter the hydrochloride of the organic base, then replace the remaining hydrochloride with ammonium chloride with a small amount of ammonia gas, and filter the gasified ammonium to distill the organic solvent under reduced pressure to obtain the ΗB d P series compounds. In the manufacturing method of the present invention, the excess phosphorus phosphonium chloride is preferably four to eight times the molar number of glycerol. The proper amount of magnesium chloride catalyst used is preferably from Oi to 1 by weight of the phosphorus phosphonium chloride. 〇%, more preferably 0.4% by weight of the phosphorus chloride brewing. In the manufacturing method of the present invention, the heating temperature of the first-stage esterification is preferably 60 ~ 120 ° C 'more preferably is 丨 ⑼ ~ 丨10t. Second, the heating temperature of the main stage of esterification is preferably 100 ~ 15, more preferably 120 ~ 130 ° C. 0 This paper size is applicable to China National Standard (CNS) A4 specification (2) 0 x 297 mm) clothing -------- order --------- line 4 ^ (Please read the precautions on the back before filling this page} Explanation of the invention (multi) In the manufacturing method of the present invention, the reaction product is determined by 31P nuclear magnetic resonance spectrum before the completion of the three-stage esterification reaction. In the manufacturing method of the present invention, the organic test of step ⑺ is preferably selected from Including one or both of triethylamine or pyridine groups, the amount of which is 1 to 2 equivalents of glycerol. The organic solvent in step (4) is preferably selected from the group consisting of toluene, xylene, and ethyl acetate. Either one or more of the esters or butyl acetate groups. Generally, T, the manufacturing side of the present invention is prepared under the optimal conditions, and the conversion rate of PP produced by the knife is calculated based on the calculation of the theory, reaching 1%, the selectivity Above 80%. [Description of the preferred embodiment of the invention] The manufacturing method of the present invention adds phosphorus rhenium chloride, propylene dichloride and magnesium chloride into the reaction tank at one time. After the reaction solution is heated and reacted for 4 hours, excess phosphorus rhenium chloride is distilled off; Continue to add ortho-position alkylphenol compounds and organic test, and react for 2 hours under heating; then add a third butyl hydroquinone and heat for 2 hours; all three-stage esterification reactions are detected by 3! P nuclear magnetic resonance spectrometer Fully functional. After the product is dissolved in an organic solvent, first filter the hydrochloride of the organic base, then replace the remaining organic base hydrochloride with ammonium chloride with a small amount of ammonia, and then filter the ammonium chloride to recover the organic solvent by distillation. Compounds. According to the present invention, the preparation of hydroxy-containing glycerol aryl phosphonate (abbreviated as "BD PB") is carried out under a single parent. First, malonic acid, excess phosphorus chloride, and a small amount of catalyst gasification, are simultaneously added to the reaction tank. ， The paper ruler is placed on the reaction tank _ Home Standard (CNS) A4 size ⑵G χ 297 public hair) — 572939 Λ7 B7 V. Description of the invention (f ·) Condensation tube and temperature probe, the condensing tube is connected to the air pipe, but Hydrochloric acid was introduced into the neutralization tank. The first stage heating temperature is 60 ~ 12 (rc, the esterification reaction is performed under normal pressure. 'Wang wants to generate mono-substituents (11 = 1) and a small amount of di-substituents (㈣), as shown in the following equation (1); better The temperature is controlled to 100 ~ 11 (rc. A large amount of hydrochloric acid gas released by the reaction at too high temperature will take the phosphorus chloride thallium away from the reaction tank. After about 4 hours, the pressure reduction of the excess gasification of phosphorus thallium ( 30 ~ 40mmHg), distillation; after about 2.5 hours after the vaporized phosphorus is no longer distilled out; return to room temperature and add an equivalent amount of an ortho-alkylphenol compound and double equivalent organic base for the second-stage esterification reaction, · As shown in the following equation (2); the temperature is controlled at 100 ~ 150 ° C, preferably 120 ~ 130 ° C for two hours; the equivalent of the third butyl hydroquinone is continuously added to carry out the third-stage esterification reaction, as follows The equation (3) is described; the temperature is controlled at 100 ~ 150 ° C, preferably 120 ~ 13 (TC for two hours; after the three-stage esterification reaction is completed, the reaction end point is determined by 31 p nuclear magnetic resonance spectrometer test. When the reaction After the completion, the product was dissolved in an organic solvent, and the hydrochloric acid salt of the organic base was filtered first at room temperature. The produced organic test hydrochloride is replaced with vaporized ammonium, and the organic solvent is recovered by filtering and vaporizing the vaporized ammonium to obtain the Η BDP product. The whole reaction is based on the calculation of glycerol, and the conversion rate is as high as 値 100%. Above 80%. 0 (I) Ρ〇α3 + ΗΟ ^ Η ^ ΟΗ 1! 2 (cat \ Cl-P- △ Cl
CIJCIJ
Cl + HCl(g) 1=1,2 本纸張尺度適用中E 0家標準（CNS)A:丨規恪（210 x 297公沒） 572939 Λ： 五、發明說明（< ) 〇^〇+©*〇十-。+ HOAr—N ^ CI-P-Cl」η . △Cl + HCl (g) 1 = 1,2 E 0 standards (CNS) A: 丨 compliant (210 x 297) 572939 Λ: 5. Description of the invention (<) 〇 ^ 〇 + © * 〇 十-. + HOAr—N ^ CI-P-Cl ″ η. △
Ohr 〇〇^H〇K>fL.a + R3WHCI I — fl 〇Arn HOAr: HO^+- HO^) H〇^ R3N ： Qi Et3N.·:.·:Ohr 〇〇 ^ H〇K> fL.a + R3WHCI I — fl 〇Arn HOAr: HO ^ +-HO ^) H〇 ^ R3N: Qi Et3N. ·: .. ::
(3)C IP- OAr OAr· 〇H Ο n OI-I △ R3N 9 0 -γ^ΗΟ-^Ο-Ρ- 0*<PH〇-〇-P- -O^-OH 0 仓 〇Arn 訂 經 濟 部 智 .¾ 財 產 局 員 X 消 合 社 印 製 + R3N*HCl 為方便更進一步説明起見，將列舉以下實施例作更 具體的説明。 以下實施例為本發明之具體説明，但不會因此而限丨, 定本發明的範圍。 | 線 實施例一 第一階段酯化反應實驗，如方程式（1)。秤取114克 (〇」〇5莫耳）丙二酚，61·4克（〇·4莫耳）氣化磷醯及〇·24 克催化劑氣化鎂，同時加入25〇毫升雙頸反應瓶中，反 應瓶上万分別接一冷凝管及溫度探針，冷凝管溫度維 。(：，該冷凝管上方接一導氣管至中和槽。 反應液升溫至約65°C左右開始反應，溫度維持在1〇〇 _______7 本紙張尺度適用中國0家標準（CNS)A4規絡（210x 297公沒） 經濟部智慧財產局員工消費合作社印製 572939 五、發明說明（6 ) C至110 C <間，約一小時後鹽酸產生之速度趨緩。四小 時後將冷凝官轉換為蒸餾裝置，維持 o°c冷凝，升溫至 15〇C ’ 2小時後再減壓蒸餾（30〜40mmHg) 30分鐘， 回覆立/m取樣進行3 1 p核磁共振光譜儀檢測，由相對積分 値換算產物重理論値為22·6克，而實際反應所得為22 5 克，可證明轉化率為100%。 實施例二〜七 反應步騾同實施例一，固、定丙二酚反應當量數，改 變氣化磷醯與催化劑氯化鎂用量，以探討選擇性與轉化 率’其反應劑量、31Ρ光譜積分値與轉化率，如表一所示。 表一、第一階段酯化反應結果 實施例 氣化鱗酿（克） 丙二齡（克） 氯化鎂（克） 31P光譜積分値 轉化率 (n=l:n=2) (%) 一 61.4 11.4 0.24 97:3 約100 二 46.0 11.4 0.18 97:3 約100 三 30.7 11.4 0.12 96:4 約100 四 23.0 11.4 0.09 73:27 約100 五 15.4 11.4 0.06 50:50 約100 六 61.4 11.4 0.06 97:3 約63 七 46.0 11.4 0.46 95:5 約 100 ^ 實施例八 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐〉 --------訂--------- (請先閱讀背面之注意事項再填寫本頁) 572939 表二、第二階段酯化反應結果 A7 一 -------- B7 五、發明說明（7 ) 第二階段醋化反應實驗，如方程式⑺。繼續實施例 —所獲得第-階段中間體，按相對積分値計算添加2,4_ 二-第三丁基酚18.8克（0.091莫耳）與啶15 8克（〇 2 莫耳）；冷凝管以水冷凝，反應溫度維持在12〇〜13〇ό: 小時，取樣以31Ρ核磁共振光譜儀檢測，已完全反應，其 中90%以上選擇性為二取代產物，如表二。 實施例九〜十五 第二階段酯化反應實驗如實施例八，僅改變反應溫 度、制酸劑（使用三乙基胺為20.2克）與反應劑為2,6-二-甲基酚11.1克（0.091莫耳）或2,6-二-第三丁基酚18.8 克（0.091莫耳），結果如表二。 實施例 反應劑 制酸劑（溶劑） 反應溫度 反應時間 (小時） 轉化率 (%) 選擇性 (%) 八 2,4二丁基酚 巧匕咬（無） 120°C 2 100 95 九 2,4二丁基酚 呼匕咬（無） 100°C 4 95 85 十 2,6二甲基酚 碎匕咬（無） 120°C 1 100 80 十一 2,6二甲基酚 碎匕症（無） 100°C 0.5 100 93 十二 2,6二丁基酚 吡啶（無） 150°C 8 45 50 十三 2,4二丁基酚 三乙基胺(甲 苯） 25°C 16 100 85 十四 2,4二丁基酚 三乙基胺(乙酸 25°C 16 100 88 ^紙張尺度綱中酬紐準（CNS)A4l見格⑵0 X 297公釐） --------^--------- (請先閱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 A7 ___ B7 乙酯） 十五 2,6二甲基盼 三乙基胺(二氯 25〇C 8 95 78 甲烷） ---- ---- 572939 五、發明說明（汉） 實施例十六 第三階段酯化反應，如方程式（3)。繼續實施例八與 例十一，添加第三丁基對苯二酚I5·77克（0·095莫耳）， 反應溫度維持在120〜13 0°c二小時，取樣以31p核磁共振 光譜儀檢測，已完全反應成三取代的H B D P產物。將 產品溶於75克甲苯中，在室溫下過濾扯啶鹽酸鹽，蒸餘 回收甲苯後，得初產物Η B D P。將初產物分別溶於甲 苯（75克）、乙酸乙酯（70克）等溶劑，通入少量氨氣， 約5分鐘後氯化銨生成，過濾氣化銨，回收溶劑，分測 各項數據，得產品測試値，如表三。 -------------^^衣--------奸--------- (請先閱讀背面之注音？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表三、產品測試値 顏色 溶劑 磷含量 (%) 氣含量 (ppm) 羥基値 (meq/g) 選擇性 實施例八 淡黃色 甲苯 5.95 1550 1.79 84 績反應 淡黃色 乙酸乙酯 5.92 390 1.76 85 實施例十一 淡黃色 甲苯 7.12 1680 2.03 81 續反應 淡黃色 乙酸乙酯 7.15 75 2.06 81 註：選擇性係由G P C定出η=1的含量 10 572939 Λ7 B7 五、發明說明（？ 絲上所陳，本創作無論就目的、手段及功效，在在 均·㉝其迴兴於習知技術之特徵，為「含羥基丙 二酚芳 鱗醋製備法」之-大突破。惟應注意的是，上述諸多實 犯例僅係為了便於説明而舉例而已，本發明所主張之權 利範圍自應以申請專利範圍所述為準，而非僅限於上述 實施例。 --------II---------線 (請先閱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)A-l規格（210x 297公釐）(3) C IP- OAr OAr. 〇H Ο n OI-I △ R3N 9 0 -γ ^ ΗΟ- ^ Ο-Ρ- 0 * < PH〇-〇-P- -O ^ -OH 0 Warehouse 〇Arn Ordered by the Ministry of Economic Affairs. ¾ Printed by X Bureau of Property Bureau + R3N * HCl For the convenience of further explanation, the following examples will be enumerated for more specific description. The following embodiments are specific descriptions of the present invention, but are not limited thereby, and define the scope of the present invention. | Example 1 The first stage esterification reaction experiment, such as equation (1). Weigh 114 grams (〇.05 mol) of glycerol, 61.4 grams (0.4 mol) of gaseous phosphatium and 0.24 grams of catalyst gaseous magnesium, while adding a 25 ml double-necked reaction bottle In the reaction bottle, a condensate tube and a temperature probe are connected to the upper part of the reaction flask, and the temperature of the condensate tube is maintained. (: An air duct is connected above the condensing tube to the neutralization tank. The reaction solution is heated to about 65 ° C to start the reaction, and the temperature is maintained at 100_______7 This paper standard applies to China's 0 standard (CNS) A4 profile (210x 297) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 572939 V. Description of the invention (6) Between C and 110 C < The rate of hydrochloric acid production will slow down after about one hour. The condensation officer will be changed after four hours It is a distillation device, maintaining o ° c condensation, heating to 150 ° C. 2 hours, and then distilling under reduced pressure (30 ~ 40mmHg) for 30 minutes, and responding to standing / m sampling for 3 1 p nuclear magnetic resonance spectrometer detection, converted by relative integral 値The theoretical weight of the product is 22.6 grams, and the actual reaction yield is 22.5 grams, which can prove that the conversion rate is 100%. Examples 2 to 7 The reaction steps are the same as in Example 1. The reaction equivalents of solid and stilbene are Change the amount of vaporized phosphorous phosphonium and catalyst magnesium chloride to explore the selectivity and conversion rate, its reaction dose, 31P spectral integration, and conversion rate, as shown in Table 1. Table 1. Results of the first-stage esterification reaction Examples of gasification Scale Stuffing (g) (G) Magnesium chloride (g) 31P spectral integration 率 Conversion rate (n = l: n = 2) (%)-61.4 11.4 0.24 97: 3 about 100 2 46.0 11.4 0.18 97: 3 about 100 3 30.7 11.4 0.12 96: 4 about 100 four 23.0 11.4 0.09 73:27 about 100 five 15.4 11.4 0.06 50:50 about 100 six 61.4 11.4 0.06 97: 3 about 63 seven 46.0 11.4 0.46 95: 5 about 100 ^ Example 8 8 This paper size applies Chinese national standards ( CNS) A4 specification (210 x 297 mm) -------- Order --------- (Please read the precautions on the back before filling this page) 572939 Table II, second stage ester Results of the chemical reaction A7 I -------- B7 V. Description of the invention (7) The second-stage vinegarization reaction experiment, such as equation ⑺. Continue the example-the obtained intermediate stage-calculated by the relative integral 値Add 18.8 g (0.091 mol) of 2,4-di-tert-butylphenol and 15 8 g (02 mol) of pyridine; the condensation tube is condensed with water, and the reaction temperature is maintained between 120 and 13: hours, sampling Detection by 31P nuclear magnetic resonance spectrometer, the reaction has been completed, of which more than 90% of the selectivity is a disubstituted product, as shown in Table 2. Example 9 ~ 15 Second stage ester The reaction experiment is as in Example 8. Only the reaction temperature is changed, the antacid (20.2 g using triethylamine) and 11.1 g (0.091 mole) of 2,6-di-methylphenol as the reactant or 2,6- Di-tertiary butylphenol was 18.8 g (0.091 mol). The results are shown in Table II. Examples Reagents Antacids (solvents) Reaction temperature Reaction time (hours) Conversion rate (%) Selectivity (%) Eight 2,4 dibutylphenols (no) 120 ° C 2 100 95 Nine 2, 4 Dibutylphenol bite (no) 100 ° C 4 95 85 Ten 2,6 dimethylphenol bite (no) 120 ° C 1 100 80 Eleven 2,6 dimethylphenol bite ( None) 100 ° C 0.5 100 93 Twelve 2,6 dibutylphenol pyridine (none) 150 ° C 8 45 50 Thirteen 2,4 dibutylphenol triethylamine (toluene) 25 ° C 16 100 85 ten Tetra 2,4 dibutylphenol triethylamine (acetic acid 25 ° C 16 100 88 ^ Paper standard outline (CNS) A4l see grid 0 0 297 mm) -------- ^- -------- (Please read the notes on the back before filling this page) A7 ___ B7 ethyl ester printed by the Employee Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (Dichloro 25 ° C 8 95 78 methane) ---- ---- 572939 V. Description of the invention (Chinese) Example 16 The third stage of the esterification reaction is shown in equation (3). Continuing Example 8 and Example 11, adding 5.77 g of tert-butylhydroquinone I (0.095 mole), the reaction temperature was maintained at 120 ~ 130 ° C for two hours, and sampling was detected by 31p nuclear magnetic resonance spectrometer , Has completely reacted to the tri-substituted HBDP product. The product was dissolved in 75 g of toluene, and the pyridine hydrochloride was filtered at room temperature. The toluene was recovered by distillation to obtain the initial product Η B D P. The initial product was dissolved in solvents such as toluene (75 g), ethyl acetate (70 g), and a small amount of ammonia gas was passed in. About 5 minutes later, ammonium chloride was generated. The ammonium chloride was filtered, the solvent was recovered, and various data were measured. The product test is shown in Table 3. ------------- ^^ 衣 -------- 奸 --------- (Please read the phonetic on the back? Matters before filling out this page) Ministry of Economic Affairs Printed by the Intellectual Property Bureau Employees' Cooperatives Table III. Product Testing 値 Color Solvent Phosphorus Content (%) Gas Content (ppm) Hydroxyl 値 (meq / g) Selective Example 8 Light yellow toluene 5.95 1550 1.79 84 Ethyl ester 5.92 390 1.76 85 Example XI Light yellow toluene 7.12 1680 2.03 81 Continued reaction pale yellow ethyl acetate 7.15 75 2.06 81 Note: The selectivity is determined by GPC with the content of η = 1 10 572939 Λ7 B7 V. Description of the invention (? On the silk, the creation, regardless of the purpose, means and effect, is reminiscent of the characteristics of the known technology, and it is a major breakthrough in the "preparation method of hydroxymalonol-containing aromatic scale vinegar". However, it should be noted that the above-mentioned many actual cases are just examples for the convenience of explanation. The scope of the rights claimed in the present invention should be based on the scope of the patent application, and not limited to the above-mentioned embodiments. ---- II --------- line (please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperatives This paper is sized for China National Standard (CNS) A-l (210x 297 mm)