1250975 Α7 Β7 五、發明説明（1 ) 技術領域 本發明係關於一種如一般式（1 ) (請先閲讀背面之注意事項再填寫本頁) H ( C F R 1 c f 2 ) n C Η 2 Ο Η ( 1 ) (η=1 或 2。當 η = 1 時，Ri 表示 F 或 CF3。sn — 2時，R 1表示；F。）所表示的含氟之醇類之製造方法。 背景技術 關於 H (CF2CF2) nCH2〇H (n=l 、2) 的製造法，如特開昭5 4 - 1 5 4 7 Ο 7號公報及美國專 利2 5 5 9 6 2 8號中揭示，甲醇與四氟乙$希於自由基產 生劑的t -丁基辛基過氧化物存在下使其反應，得到 Η ( C F 2 C F 2 ) n C Η 2〇Η ( η最高爲1 2 )的短鏈 聚合物。 經濟部智慧財產局員工消費合作社印製 此方法中，因使用過剩量的甲醇，可望回收含於反應 粗製物之甲醇再利用。例如，如專利第3 0 2 8 0 4號公 報揭示含有甲醇再利用步驟之含氟醇類製造法。另一方面 ’反應粗製物中殘留成未分解的自由基產生劑狀態，或反 應中使用受酸劑時反應粗製物中殘留未反應之受酸劑等狀 態下，蒸餾短鏈聚合物混合物得到作爲目的之含氟之醇類 時，蒸發殘留部分、U V吸收成分等不純物含於回收之含 氟之醇類中。因此，例如設置作爲C D — R或d V D - R 等的基板上可藉激光將情報記入及/或讀取之記錄層，其 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -4- 1250975 A7 —_ __ B7 __ 五、發明説明（2) 所成之情報記錄媒體製造時的溶劑使用時，有著無法適用 於尚品質情報記錄媒體製造上之缺點。 (請先閲讀背面之注意事項再填寫本頁) 本發明的目的爲提供一種實際上不含不純物，又甲醇 可再利用的如一般式（1 ) H (CFR1CF2) nCH2〇H (1) (n=l或2。當η二1時，R1表示F或CF3。當n二 2時，R 1表示F。）所表示的含氟之醇類之製造方法。 發明的掲示 本發明係關於下述各項所示的含氟醇類的製造方法。 第1項一種含氟之醇類之製造方法，其特徵爲自由基 產生劑及受酸劑存在下，以甲醇及四氟乙烯或六氟丙烯作 爲啓始原料，製造如一般式（1 ) H (CFR1CF2) nCH2〇H (1) 經濟部智慧財產局員工消費合作社印製 (η二1或2。當n = l時，R1表示F或CF3。當n = 2時，R1表示F。）所表示的含氟之醇類之製造方法，其 含有如下述（i )至（v )步驟： (i )使甲醇與四氟乙烯或六氟丙烯進行反應的步驟 (i i )由所得之反應粗製物中除去受酸劑的反應生 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -5 - 1250975 94. 12. 1 6 a? B7 五、發明説明（3 ) 成物及未反應的受酸劑之步驟， (請先閲讀背面之注意事項再填寫本頁) (i i i )將經上（i i )步驟所處理的反應粗製物 導入蒸餾塔中，使甲醇與該反應粗製物中所殘存之自由基 產生劑同時由塔頂餾出，由塔底取出含有如一般式（1 ) 所示含氟醇類的殘底成分之步驟， (i v )由塔頂所得之餾出部分在回到反應器中再利 用之步驟，及 (v )純化前述殘底成分回收如一般式（1 )所示的 含氟醇類之步驟。 第2項一種HC F2CF2CH2〇H的製造方法，其 特徵爲於自由基產生劑及受酸劑的存在下，以甲醇及四氟 乙烯作爲啓始原料，並含有下述（i )至（v i )步驟： (i )使甲醇與四氟乙烯進行反應的步驟， (i i )由所得之反應粗製物中除去受酸劑的反應生 成物及受酸劑的殘留部分之步驟， 經濟部智慧財產局8工消費合作社印製 (i i i )將經上述（i i )步驟處理的反應粗製物 導入第一蒸餾塔中，使甲醇與該反應粗製物中殘留的自由 基產生劑同時由塔頂餾出，由塔底取出含有如一般式（2 H ( C F 2 C F 2 ) 1 C Η 2 Ο Η ( 2 ) (1 = 1至5的整數）所示含氟醇類的殘底成分之步驟， (1 v )由塔頂所得之餾出部分在回到反應器中再利 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -6- 1250975 A7 B7 五、發明説明（4) 用之步驟， (V )將前述步驟（i 1 1 )所得之殘留成分導入第 (請先閱讀背面之注意事項再填寫本頁) 二蒸餾塔中，由塔頂餾出H C F 2 C F 2 C Η 2〇Η，由塔 底取出含有一般式（2 )的1爲2以上的含氟醇類殘底部 分的步驟，及 (ν i )對於上述（ν )步驟中，將由塔頂餾出的η C F 2 C F 2 C Η 2〇Η ’與鹼基接觸後或於驗基存在下蒸 餾回收H C F 2 C F 2 C Η 2〇Η之步驟。 第3項對於第2項的方法，經（ν i )步驟的蒸餾回 收H C F 2 C F 2 C Η 2 〇 Η的方法，蒸餾含有 H C F 2 C F 2 C Η 2〇Η的成分將低沸點成分除去後，將 得到殘底成分的含H C F 2 C F 2CH2OH成分經再度蒸 餾回收H C F 2 C F 2 C Η 2〇Η的方法。 對於甲醇與四氟乙烯或六氟丙烯於自由基產生劑的存 在下使其反應之步驟中，對四氟乙烯或六氟丙燦而言使用 過量的甲醇。反應溫度爲4 0至1 4 0 °C程度，反應時間 爲3至1 2小時程度，反應壓力爲0 · 2至1 . 2 Μ P a 經濟部智慧財產局員工消費合作社印製 程度。反應可於如尚壓签的局壓反應备中進彳了。反應系中 可由氮氣、氬氣等惰性氣體取代爲佳。 作爲自由基產生劑，蒸餾時使用可共同與甲醇餾出者 。這些自由基產生劑僅可共同與甲醇餾出即可，既使於蒸 餾過程中會分解者亦可。 具體而言，可舉例出二- t -丁基過氧化物（沸點 1 〇 9至1 1 0 °C )(可由商品名”過丁基D ” （日本油 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -7- 1250975 Α7 Β7 五、發明説明（5) 月旨（股）製）獲得）、t 一 丁基過氧基一 2 —乙基乙酸鹽 (可由商品名”過丁基〇”（日本油脂（股）製）獲得） (請先閲讀背面之注意事項再填寫本頁) 、1：- 丁基過氧化基異丙基碳酸鹽（可由商品名”過丁基 I ” （日本油脂（股）製）獲得）等過氧化物爲佳。 自由基產生劑的使用量以每莫耳的四氟乙烯或六氟丙 烯而言，一般爲〇 · 005至ο · 1莫耳程度。 上述反應於受酸劑存在下進行。作爲受酸劑，可舉出 碳酸鈣、碳酸鎂、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀 等鹼性金屬或鹼性土金屬的碳酸鹽或碳酸氫鹽、氧化鈣、 氫氧化鈣、鹼石灰、碳酸鋇等。 受酸劑以不使反應系成強鹼性，且可截留產生於反應 時的H F等酸。 受酸劑的使用量，雖無特別限定，但每1莫耳的四氟 乙烯或六氟丙烯而言，僅爲0 . 0 0 1至0 . 1莫耳的程 度亦可。 甲醇與四氟乙烯或六氟丙烯的反應，一般以間歇式步 驟進行，但該反應後的步驟以間歇式步驟或連續步驟皆可 經濟部智慧財產局員工消費合作社印製 〇 如上述方法所得之反應粗製物，如圖1所示由反應器 導入蒸餾塔，欲使甲醇由塔頂餾出故加熱蒸餾塔。僅如上 述條件進行反應，雖一般反應粗製物中會殘留一部份未分 解的自由基產生劑，但本發明所使用的自由基產生劑係於 蒸餾後與甲醇同時被餾出之自由基產生劑，故曱醇的一般 蒸餾條件，例如蒸餾塔的壓力必須控制爲一 0 . 0 5至 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -8- 經濟部智慧財產局g(工消費合作社印製 1250975 94. 12. 1 6 A7 ___ B7 五、發明説明（6 ) 0 · IMP a程度（以表壓表示以下相同）下加熱蒸餾签 使其餾出，僅將甲醇於4 0至9 0 °C程度下進行餾出，於 反應粗製物中殘留的自由基產生劑可與甲醇同時餾出。因 此由反應粗製物可除去仍未分解的自由基產生劑。 本發明中僅可將殘存於反應粗製物的未分解自由基產 生劑由反應粗製物中除去即可，自由基產生劑亦可與甲基 同時餾出，或蒸餾過程中自由基產生劑被分解，其分解物 可與甲醇同時餾出亦可。因此，含有甲醇的蒸餾部分中亦 可含有未分解的自由基產生劑，亦可含有自由基產生劑的 分解物，或含有兩者亦可。例如上述所例舉的自由基產生 劑中，使用t -丁基過氧化物時，於蒸餾過程中幾乎無被 分解，t 一丁基過氧化物與甲醇同時餾出。 甲醇及四氟乙烯或六氟丙烯的反應粗製物中，雖有含 H F及水的情況，但這些於蒸餾塔的中段被濃縮。H F及 水被濃縮的層，如圖2所示可作爲測線餾分而由蒸餾塔取 出。測線餾分的溫度爲8 0至1 2 0 °C / 0 · 1 Μ P a程 本發明中，將反應粗製物導入蒸餾塔前，由反應粗製 物中除去C a F 2、N a F等的受酸劑的反應生成物及未反應 的受酸劑。此操作並無特別限定，僅爲受酸劑的反應生成 物及未反應的受酸劑由反應粗製物中除去的方法即可，例 如如圖1所示可使用離心分離機而有效率地除去。 由塔頂得到的餾分如圖1及2所示，回到反應器再利 用。該餾分中仍含有未分解的自由基產生劑時，自由基產 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)1250975 Α7 Β7 V. INSTRUCTION DESCRIPTION (1) TECHNICAL FIELD The present invention relates to a general formula (1) (please read the back note first and then fill in this page) H ( CFR 1 cf 2 ) n C Η 2 Ο Η ( 1) (η = 1 or 2. When η = 1, Ri represents F or CF3. When Sn 2, R 1 represents; F.) The method for producing the fluorine-containing alcohol represented by the formula. 2. Description of the Related Art A method for producing H (CF2CF2) nCH2〇H (n=l, 2) is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Methanol is reacted with tetrafluoroethylene in the presence of t-butyloctyl peroxide as a free radical generator to obtain hydrazine (CF 2 CF 2 ) n C Η 2〇Η (η up to 1 2 ) Short chain polymer. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. In this method, it is expected to recover the methanol contained in the crude reaction by using excess methanol. For example, Patent Publication No. 3082 0 discloses a method for producing a fluorine-containing alcohol containing a methanol reuse step. On the other hand, when the reaction crude material remains in the state of an undecomposed radical generator, or when an acid acceptor is used in the reaction, an unreacted acid acceptor remains in the reaction crude product, and the short-chain polymer mixture is distilled. In the case of the fluorine-containing alcohol of interest, the impurities such as the evaporation residual portion and the UV absorbing component are contained in the recovered fluorine-containing alcohol. Therefore, for example, a recording layer which can be recorded and/or read by laser on a substrate such as CD-R or dVD-R is provided, and the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X 297 mm). -4- 1250975 A7 —_ __ B7 __ V. INSTRUCTIONS (2) When the solvent used in the manufacture of the information recording medium is used, there is a disadvantage that it cannot be applied to the manufacture of the quality information recording medium. (Please read the note on the back and then fill out this page.) The object of the present invention is to provide a formula (1) H (CFR1CF2) nCH2〇H (1) (n) which is practically free of impurities and which can be reused in methanol. = 1 or 2. When η is 2, R1 represents F or CF3. When n is 2, R 1 represents a method for producing a fluorine-containing alcohol represented by F. DISCLOSURE OF THE INVENTION The present invention relates to a method for producing a fluorine-containing alcohol represented by the following items. Item 1 is a method for producing a fluorine-containing alcohol, characterized in that in the presence of a radical generating agent and an acid accepting agent, methanol, tetrafluoroethylene or hexafluoropropylene is used as a starting material to produce a general formula (1) H. (CFR1CF2) nCH2〇H (1) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing (η二1 or 2. When n = l, R1 means F or CF3. When n = 2, R1 means F.) A method for producing a fluorine-containing alcohol, which comprises the following steps (i) to (v): (i) a step (ii) of reacting methanol with tetrafluoroethylene or hexafluoropropylene, and a crude reaction product obtained therefrom In the case of removing the acid acceptor, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -5 - 1250975 94. 12. 1 6 a? B7 V. Invention description (3) Adult and not The step of reacting the acid acceptor, (please read the precautions on the back side and fill out this page) (iii) Introduce the crude reaction substance treated in the above step (ii) into the distillation column to make methanol and the reaction crude material. The remaining free radical generator is simultaneously distilled from the top of the column and taken out from the bottom of the column as shown in the general formula (1) a step of reacting the bottom component of the fluoroalcohol, (iv) a step of recovering the distillate portion obtained from the top of the column in the reactor, and (v) purifying the residue of the residue as shown in the general formula (1) The steps of the fluorine-containing alcohols. Item 2 is a method for producing HC F2CF2CH2〇H, characterized in that methanol and tetrafluoroethylene are used as starting materials in the presence of a radical generating agent and an acid accepting agent, and the following (i) to (vi) are contained. Step: (i) a step of reacting methanol with tetrafluoroethylene, (ii) a step of removing the reaction product of the acid acceptor and the residual portion of the acid acceptor from the obtained crude reaction product, Ministry of Economic Affairs Intellectual Property Bureau 8 (iii) introducing the reaction crude product treated in the above step (ii) into the first distillation column, and simultaneously distilling methanol and the residual radical generating agent remaining in the reaction crude product from the top of the column, The step of removing the bottom component containing the fluorine-containing alcohol represented by the general formula (2H(CF 2 CF 2 ) 1 C Η 2 Ο Η ( 2 ) (1 = 1 to 5), (1 v ) The distillate fraction obtained from the top of the column is returned to the reactor and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -6- 1250975 A7 B7 5. Inventive Note (4) Step, (V) introducing the residual component obtained in the aforementioned step (i 1 1 ) into the first (please read the back first) Precautions for refilling this page) In the second distillation column, HCF 2 CF 2 C Η 2〇Η is distilled from the top, and the fluorine-containing alcohol residue containing 1 or more of the general formula (2) is taken out from the bottom of the column. a partial step, and (ν i ), in the above (ν) step, HCF 2 CF is recovered by contacting the base with η CF 2 CF 2 C Η 2〇Η ' after distilling with the base or in the presence of a test group. Step 2 of 2 C Η 2〇Η. Item 3 For the method of item 2, the method of recovering HCF 2 CF 2 C Η 2 〇Η by distillation in the (ν i ) step, the distillation containing HCF 2 CF 2 C Η 2〇 After the low-boiling component is removed from the cerium component, the HCF 2 CF 2 CH 2 OH component containing the residual component is subjected to re-distillation to recover HCF 2 CF 2 C Η 2 。. For methanol and tetrafluoroethylene or hexafluoropropylene freely In the step of reacting in the presence of a base generator, an excess of methanol is used for tetrafluoroethylene or hexafluoropropyl. The reaction temperature is about 40 to 140 ° C, and the reaction time is 3 to 12 hours. Degree, reaction pressure is 0 · 2 to 1. 2 Μ P a Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing degree The reaction can be carried out in a pressure-reacting reaction such as a still press. The reaction system can be replaced by an inert gas such as nitrogen or argon. As a radical generating agent, it can be used together with a methanol distillate in distillation. The radical generating agent can be distilled only together with methanol, even if it is decomposed during the distillation. Specifically, bis-t-butyl peroxide (boiling point 1 〇9 to 110 ° C) can be exemplified (by the trade name "butyl butyl D"" (Japanese oil-based paper scale applies to Chinese national standards ( CNS ) A4 size (210X297 mm) -7- 1250975 Α7 Β7 V. Description of invention (5) (Made in the system), t-butylperoxy-2-ethylacetate (trade name) "Butyl butyl" (obtained from Japanese fats and oils)) (Please read the note on the back and fill out this page), 1:- Butyl peroxy isopropyl carbonate (can be traded under the trade name) It is preferred that a peroxide such as a base I" (obtained from Japanese fats and oils) is used. The amount of the radical generator to be used is generally from 005 005 to ο 1 mol per mil of tetrafluoroethylene or hexafluoropropene. The above reaction is carried out in the presence of an acid acceptor. Examples of the acid acceptor include alkali metal such as calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate, or carbonate or hydrogencarbonate of alkaline earth metal, calcium oxide, and calcium hydroxide. , soda lime, barium carbonate, and the like. The acid accepting agent does not cause the reaction to be strongly alkaline, and can retain an acid such as H F which is generated at the time of the reaction. The amount of the acid-receiving agent to be used is not particularly limited, but is preferably from 0. 0 0 to 0.1 mol per 1 mol of tetrafluoroethylene or hexafluoropropylene. The reaction of methanol with tetrafluoroethylene or hexafluoropropylene is generally carried out in a batch process, but the post-reaction steps can be carried out in batch or continuous steps by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives. The reaction crude product was introduced into a distillation column from the reactor as shown in Fig. 1, and the distillation column was heated to elute methanol from the top. The reaction is carried out only under the above conditions, and although a part of the undecomposed radical generating agent remains in the reaction crude product, the radical generating agent used in the present invention is a radical generated by distilling off with methanol after distillation. The general distillation conditions of sterols, such as the pressure of the distillation column, must be controlled to a value of 0. 05 to the paper scale applicable to the Chinese National Standard (CNS) Α 4 specifications (210X297 mm) -8- Ministry of Economic Affairs Intellectual Property Bureau g (Working Consumer Cooperatives Printed 1250975 94. 12. 1 6 A7 ___ B7 V. Inventive Note (6) 0 · IMP a degree (the same as the gauge pressure below) is heated to distill off the distillate, only methanol is used in 4 Distillation is carried out at a temperature of from 0 to 90 ° C, and the radical generator remaining in the crude reaction product can be simultaneously distilled off with methanol. Therefore, the radical generator which is still not decomposed can be removed from the reaction crude product. The undecomposed radical generating agent remaining in the reaction crude product may be removed from the reaction crude product, and the radical generating agent may be simultaneously distilled off with the methyl group, or the radical generating agent may be decomposed during the distillation, and the decomposition product thereof It may be distilled off simultaneously with methanol. Therefore, the distillation portion containing methanol may contain an undecomposed radical generating agent, may also contain a decomposition product of a radical generating agent, or may contain both. For example, the above-exemplified In the radical generator, when t-butyl peroxide is used, it is hardly decomposed during the distillation, and t-butyl peroxide is simultaneously distilled off with methanol. The reaction of methanol and tetrafluoroethylene or hexafluoropropylene In the crude product, although it contains HF and water, these are concentrated in the middle of the distillation column. The layer in which HF and water are concentrated can be taken out as a line fraction and taken out from the distillation column as shown in Fig. 2. The temperature of the line fraction is measured. 80 to 1 20 ° C / 0 · 1 Μ P a. In the present invention, before the crude reaction product is introduced into the distillation column, the acid accepting agent such as C a F 2 , N a F or the like is removed from the crude reaction product. The reaction product and the unreacted acid acceptor are not particularly limited, and only the reaction product of the acid acceptor and the unreacted acid acceptor may be removed from the reaction crude product, for example, as shown in FIG. It can be removed efficiently using a centrifugal separator. The fraction obtained in the top is returned to the reactor for reuse as shown in Figures 1 and 2. When the fraction still contains undecomposed free radical generator, the free-form paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) (Please read the notes on the back and fill out this page)
-9- 1250975 A7 B7 五、發明説明（7) 生劑亦可再利用。既使該餾分中含有自由基產生劑的分解 物的狀況，該餾分可直接回到反應器再利用。 (請先閱讀背面之注意事項再填寫本頁) 甲醇蒸餾後，由含有蒸餾釜中殘留含氟醇類混合物的 殘底成分中，以完全除去殘存自由基產生劑爲佳，但含於 殘底成分的自由基產生劑的量以1 0 0 0 m a s s p p m以下 程度，較佳爲5 0 mass ppm以下程度即可。 殘底成分由塔底取出，如圖1及圖2所示經蒸餾導入 純化步驟，除去存在於反應粗製物中的 H(CF2CF2)xCH2〇H(x表示3以上）、 H (CF (CF3) CF2) yCH2〇H (y 表示 2 以上） 等不純物，回收一般式（1 ) H (CFR1CF2.) nCH2〇H (1) (η 二 1 或 經濟部智慧財產局員工消費合作社印製 2。當η = 1時，R1表示F或CF3。當η = 2時，R1 表示F。）所表示的含氟之醇類。且，作爲原料使用四氟 乙烯時，因殘底成分中含有HCF2CH2〇H及 H ( C F 2 C F 2 ) 2 C Η 2〇Η，於純化步驟中由殘底成分 依 HCF2CH2〇H 及 H (CF2CF2) 2CH2〇H 的 順序分離亦可。 有關本發明方法，經上述純化步驟後，含有如一*般式 (1 ) H ( C F R 1 C F 2 ) n C Η 2 Ο Η ( 1 ) ( η及R 1與上述定義相同）所表示的含氟醇類之餾分，與驗 基接觸後，或於鹼基存在下經蒸餾回收亦可。經相關操作 後，可得到不純物含有量較少的一般式（1 )之含氟醇類 。此時，蒸餾塔的中段部分或蒸餾釜中直接添加驗基亦可 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） -10- 1250975 Α7 Β7 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) ，或蒸衝塔前設置處理槽（鹼基處理槽）亦可。設置驗基 處理槽時，對於該處理槽的操作條件雖無特別限定，但一 般於添加鹼基後，於2 0至1 5 〇 °C程度下以〇 . 5至3 小時程度接觸即可。使用甲醇及四氟乙烯作爲原料製造 H C F 2 C F 2 C. Η 2〇Η時，除去反應曱醇與四氟乙燃所 得之反應粗製物中的受酸劑，第一蒸餾塔中由塔頂離出甲 醇與殘存自由基產生劑，由塔底取出如一般式（2 ) H (CF2CF2) iCH2〇H (2) (1=1 至 5 的整數）所表示的殘底成分，其後導入含有一般式（2 ) 所表示的含氟醇類之殘底成分至第二蒸餾塔進行蒸餾，由 塔頂I留出H C F 2 C F 2 C Η 2 Ο Η，該態分與鹼基接觸後 或於鹼基存在下再蒸餾可回收HCF2CF2CH2〇H。 且由塔底可取出含有如一般式（2 )中1爲2以上之含氟 醇類的殘底成分。 經濟部智慧財產局員工消費合作社印製 作爲鹼基，以p K b爲2以下的鹼基爲佳。作爲如此 的鹼基，可舉出碳酸鈉、碳酸鉀等鹼金屬的碳酸鹽；碳酸 氫鈉、碳酸氫鉀等鹼金屬之碳酸氫鹽；甲醇鈉、乙醇鈉、 丙醇鈉、叔丁氧化鈉、乙醇鋰等鹼金屬醇鹽；氫氧化鈉、 氫氧化鎂、氫氧化鋰等鹼金屬的氫氧化物；氫氧化鈣、氫 氧化鎂、氫氧化鋇等鹼土族金屬之氫氧化物；氫氧化鋁、 鹼石灰等。這些鹼基可單獨使用，或組合2種以上使用亦 可。鹼基一般可使用甲醇等醇溶液。 鹼基的使用量可適宜地設定，但一般爲每重量1 k g 的與鹼基接觸之一般式（1 )含氟醇類而言爲〇 · 〇 5至 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -11 - 1250975 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（9) 1 . 0莫耳程度，較佳爲〇 . 1至〇 · 5莫耳程度。 以鹼基做處理時，依使用的鹼基種類可生成醇、 _ 反應生成物，作爲該反應生成物或鹼基的溶劑，將醇等低 沸點成分混入一般式（1 )的含氟醇類中。因此，欲得到 高純度的一般式（1 )含氟醇類，首先於第一階段的蒸㉒ 作’進行將一般式（1 )含氟醇類中分離去除低沸點成 分之醇、水等的蒸餾操作，再於第二階段中，以第一階P 的蒸餾操作中，作爲殘底成分而取得之含有一般式（丄） 含氟醇類的成分，進行蒸餾回收一般式（1 )的含氟醇類 爲佳。含有如此的蒸餾方法之本發明的一實施型態如圖3 所示。所謂如此的蒸餾方法，可得到無混入醇或水，實際 上不含不純物的一般式（1 )的含氟醇類。 又，改變如此二階段之蒸餾操作，依次蒸餾除去醇、 水等低沸點成分後’將一般式（1 )的含氟醇類可由蒸餾 塔的塔頂部或中段部進行回收。 本發明的方法，可採用任一種蒸態方法，但以二階段 的蒸I留方法可簡單且尚純度地回收~般式（1 )的含氟醇 類。-9- 1250975 A7 B7 V. INSTRUCTIONS (7) The green agent can also be reused. Even if the fraction contains a decomposition product of a radical generator, the fraction can be directly returned to the reactor for reuse. (Please read the precautions on the back and fill out this page.) After the methanol distillation, it is preferable to completely remove the residual radical generator from the residue containing the residual fluorine-containing alcohol mixture in the distillation still, but it is contained in the residue. The amount of the radical generating agent of the component may be about 1.0 mass ppm or less, preferably about 50 mass ppm or less. The bottom component is taken out from the bottom of the column, and is introduced into the purification step by distillation as shown in Figs. 1 and 2 to remove H(CF2CF2)xCH2〇H (x represents 3 or more) and H (CF (CF3)) present in the reaction crude product. CF2) yCH2〇H (y means 2 or more) and other impurities, and recover the general formula (1) H (CFR1CF2.) nCH2〇H (1) (η二1 or the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 2. When η When 1, 1, R1 represents F or CF3. When η = 2, R1 represents the fluorine-containing alcohol represented by F. Further, when tetrafluoroethylene is used as a raw material, HCF2CH2〇H and H(CF 2 CF 2 ) 2 C Η 2〇Η are contained in the residual component, and the residual component is HCF2CH2〇H and H (CF2CF2) in the purification step. The order of 2CH2〇H can also be separated. With respect to the method of the present invention, after the above purification step, the fluorine-containing compound represented by the formula (1) H (CFR 1 CF 2 ) n C Η 2 Ο Η ( 1 ) (η and R 1 are the same as defined above) The fraction of the alcohol may be recovered by distillation after contact with the test substrate or in the presence of a base. After the relevant operation, the fluorine-containing alcohol of the general formula (1) having a small impurity content can be obtained. At this time, the middle part of the distillation column or the addition of the test base directly in the distillation pot can also be applied to the Chinese National Standard (CNS) A4 specification (210x297 mm). -10- 1250975 Α7 Β7 5, invention description (8) (please Read the precautions on the back and fill out this page), or set the treatment tank (base treatment tank) in front of the steaming tower. When the assay processing tank is provided, the operating conditions of the treatment tank are not particularly limited, but generally, after adding the base, the contact may be carried out at a temperature of from 20 to 15 ° C for 5 to 3 hours. When HCF 2 CF 2 C. Η 2〇Η is produced by using methanol and tetrafluoroethylene as raw materials, the acid accepting agent in the crude reaction product obtained by reacting decyl alcohol and tetrafluoroethane is removed, and the first distillation column is separated from the top of the column. The methanol and the residual radical generating agent are taken out, and the residue component represented by the general formula (2) H (CF2CF2) iCH2〇H (2) (an integer of 1 = 1 to 5) is taken out from the bottom of the column, and then introduced into the residue. The residue of the fluorine-containing alcohol represented by the formula (2) is distilled to the second distillation column, and HCF 2 CF 2 C Η 2 Ο 留 is left from the top of the column I, and the state is in contact with the base or in the base. HCF2CF2CH2〇H can be recovered by re-distillation in the presence of a base. Further, a bottom component containing a fluorine-containing alcohol having 1 or more in 1 in the general formula (2) can be taken out from the bottom of the column. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. As bases, bases with a p K b of 2 or less are preferred. Examples of such a base include carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydrogencarbonates of alkali metals such as sodium hydrogencarbonate and potassium hydrogencarbonate; sodium methoxide, sodium ethoxide, sodium propoxide, and sodium t-butoxide. An alkali metal alkoxide such as lithium ethoxide; an alkali metal hydroxide such as sodium hydroxide, magnesium hydroxide or lithium hydroxide; a hydroxide of an alkaline earth metal such as calcium hydroxide, magnesium hydroxide or barium hydroxide; Aluminum, soda lime, etc. These bases may be used singly or in combination of two or more. As the base, an alcohol solution such as methanol can be generally used. The amount of base used can be appropriately set, but it is generally 1 kg per kg of base-contacting general formula (1) fluorine-containing alcohol, 〇·〇5 to the paper scale applicable to the Chinese National Standard (CNS) Α4 specifications (210X 297 mm) -11 - 1250975 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Print A7 B7 V. Invention Description (9) 1. 0 Mot, preferably 〇. 1 to 〇 · 5 Mo degree. When the base is used, an alcohol or a reaction product can be produced depending on the type of the base to be used, and a low boiling component such as an alcohol can be mixed into the fluorine-containing alcohol of the general formula (1) as a solvent of the reaction product or the base. in. Therefore, in order to obtain a high-purity fluorine-containing alcohol of the general formula (1), first, in the first stage of the vaporization 22, the alcohol, water, etc. of the low-boiling component are separated and removed from the fluorine-containing alcohol of the general formula (1). In the second operation, in the second stage, the component containing the general formula (fluorene) of the fluorine-containing alcohol obtained as the residual component in the first-stage P distillation operation is subjected to distillation to recover the general formula (1). Fluoroalcohols are preferred. An embodiment of the present invention containing such a distillation method is shown in FIG. By such a distillation method, it is possible to obtain a fluorine-containing alcohol of the general formula (1) which does not contain an alcohol or water and which does not substantially contain an impurity. Further, by changing the two-stage distillation operation and sequentially distilling off low-boiling components such as alcohol and water, the fluorine-containing alcohol of the general formula (1) can be recovered from the top or the middle portion of the distillation column. In the method of the present invention, any of the vaporized methods can be employed, but the fluorine-containing alcohol of the formula (1) can be recovered simply and in a pure manner by a two-stage steaming method.
本發明的製造方法可得到蒸發殘留成分爲5 0 mass ppm以下，較佳爲2 5 mass ppm以下，較佳爲丄〇 maSS ppm以下之一般式（1 )含氟醇類。 蒸發殘留成分可由以下求得。即，將含氟醇類於4〇 °C ’ 5 m m H g ( 0 · 6 6 5 k P a )下蒸發時測定經蒸 發時的殘留成分重量，對含氟醇類的m a s S p p m做 本紙張尺度適用中國國家標準（CMS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁}The production method of the present invention can obtain a general formula (1) fluorine-containing alcohol having an evaporation residual component of 50 mass ppm or less, preferably 25 mass ppm or less, preferably 丄〇 maSS ppm or less. The evaporation residual component can be obtained as follows. That is, when the fluorine-containing alcohol is evaporated at 4 ° C '5 mm H g (0 · 6 6 5 k P a ), the weight of the residual component at the time of evaporation is measured, and the mass of the fluorine-containing alcohol is mas S ppm. The paper scale applies to the Chinese National Standard (CMS) A4 specification (210X 297 mm) (please read the notes on the back and fill out this page)
-12- 1250975 A7 五、發明説明（" ~ -- 表示。 (請先閲讀背面之注意事項再填寫本頁) 本發明所得的-般式（1 )含氟醇類於2 ◦ 5 ”下 甲醇的U”光度爲0 _ 1…以下，較佳爲—0 . i abs以下’更佳爲—〇 . 2abs以下。甲醇中的Η 光度以1 m 1的—般式（丄）含氟醇類中加入3以工的 甲醇者作爲測定試料，作爲參考使用甲_行測定。 本發明製造方法所得之含氟醇類中所謂「實際上不含 不純物」意味著，（1)含氟醇類的蒸發殘留成分爲5〇 mass ppm以下，較佳爲2 5 mass ppm以下，更佳1 〇 mass ppm以下，及/或（i丄）甲醇中的1] v吸光度（ 2 0 5 n m )爲◦ . i a b s 以下，較佳—〇 _ 1 a b s 以下’更佳爲一〇 . 2abs以下。 經濟部智慧財產局員工消費合作社印製 基板上設置藉由激光可將情報記入及/或讀取的記錄 層所成之情報記錄媒體可由一般方法，即含有本發明一般 式（1 )含氟醇類的溶劑，較佳爲含有該含氟醇類之氟素 系溶劑中以溶解色素，將所得之溶液塗抹於基板上，再進 行媒’形成含有色素記錄層而製造出。作爲該色素，可 舉出菁系色素、酞菁系色素、吡喃鏺鹽系色素、硫代吡喃 鏺鹽系色素、三十碳烷系色素、葜系色素、靛吩系色素、 靛苯胺系色素、三苯基甲烷系色素、苯酮系色素、胺鑰系 色素、deinmonium系色素、金屬錯鹽系色素等。作爲基 板，可舉出聚碳酸鹽、聚甲基甲基丙烯酸鹽、環氧基樹脂 、非晶體構造聚烯烴、聚酯、聚氯化乙烯等塑膠、玻璃、 陶瓷等。且，以平面性的改善、接著力的提升、記錄層的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 1250975 Α7 Β7 五、發明説明（11) 變質防止等爲目的，亦可於記錄層與基板之間設置底漆層 ’或於記錄層的上面設置保護層亦可。 (請先閲讀背面之注意事項再填寫本頁) 本發明可容易製造出，於基板上設置藉由激光可將情 報記入及/或讀取的記錄層所成之情報記錄媒體（C D -R、DVD - R等光碟等）、底片的感光體等製造上爲佳 ’實際上不含不純物之H C F 2 C. F 2 C Η 2〇Η、 Η ( C F 2 C F 2 ) 2 C Η 2 〇 Ή 及 H C F ( C F 3 ) 2 C F 2 C Η 2〇Η，且可有效地利用經回 收的含有甲醇之餾分及含於該餾分的自由基產生劑。 凰通簡單說明 圖1表示本發明的其中一實施型態圖。 圖2表示含有拔除側線餾分步驟之本發明的其中一實 施型態圖。 圖3表示含有二階段的驗性蒸I留步驟之本發明的其中 一實施型態圖。 經濟部智慧財產局員工消費合作社印製 對於這些圖，符號1爲反應釜、符號2爲蒸譜塔、符 號3爲離心分離機、符號4爲第一蒸餾塔、符號5爲第二 蒸餾塔、符號6爲鹼基處理槽、符號7及8爲鹼性蒸鶴塔 〇 實施發明的最佳型熊 以下舉出實施例更詳細說明本發明。 實施例1一1 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -14- 1250975 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（β 高壓反應釜中加入甲醇（15〇〇g)、過丁gD( 3 2 . 2 5 g的二一 t 一丁基過氧化物）及碳酸鈣（ 6 · 5 g )。反應釜中以氮氣取代後，昇溫至1 2 5 t：， 將四赢乙燃控制於壓力〇 · 8 5 Μ P a下邊加入邊使宜進 行2 · 6小時反應。冷卻反應粗製物後，測定重量爲 2 2 7 0 g ’以氣體色譜儀進行分析結果，得知未分解而 殘留的1 5 . 5 g過丁基D。 所得之反應粗製物，依據圖3所示的流程圖以下述方 法進行處理。 首先，將反應粗製物由反應釜1導入離心分離機3， 經離心分離將受酸劑的反應物及未反應的受酸劑除去後， 導入第一蒸餾塔。 其次，將蒸餾塔的壓力控制在0 · 1 M p a下加熱蒸 餾釜。由第一蒸餾塔4的塔頂以8 0至9 0 °C餾出甲醇。 所得之餾分爲1 2 6 . 5 g。分析此餾分得知含有 1 3 . 0 g的過丁基D，與甲醇共同殘存於反應粗製物的 過丁基D，幾乎無分解地餾出。而殘底成分中完全無含有 過丁基D。 其次，將殘底成分由第一蒸餾塔4的塔底中取出，經 蒸餾導入純化步驟。導入殘底成分至第二蒸餾塔5 ，由塔 頂餾出 H C F 2 C F 2 C Η 2 〇 Η ( 6 4 8 . 3 g )，由塔 頂取出Η ( C F 2 C F 2 ) 1 C Η 2〇Η ( 1表不2以上的 整數）。取出所得之H C F 2 C F 2 C Η 2 Ο Η的一部份（ 1 5 0 g )，導入鹼基處理槽6中，該餾分中添加甲醇鈉 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） (請先閱讀背面之注意事項再填寫本頁)-12- 1250975 A7 V. Description of Invention (" ~ -- Indicates. (Please read the note on the back and fill out this page.) The general formula (1) of the fluorine-containing alcohol obtained in the present invention is under 2 ◦ 5 ” The U" luminosity of methanol is 0 _ 1... or less, preferably -0. Below i abs is better - 〇. 2abs or less. The luminosity in methanol is 1 m 1 of the general formula (fluorene) In the fluorocarbons obtained by the production method of the present invention, the term "actually contains no impurities" means that (1) fluorine-containing alcohols are used as the measurement sample. The evaporation residual component is 5 〇mass ppm or less, preferably 2 5 mass ppm or less, more preferably 1 〇mass ppm or less, and/or (i丄) 1] v absorbance in methanol (250 nm) is ◦ Iabs Below, preferably - 〇 _ 1 abs below 'better is one 〇. 2abs or less. The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints a recording layer on the printed substrate that can be recorded and/or read by laser. The prepared information recording medium can be obtained by a general method, that is, containing the general formula (1) of the present invention The solvent is preferably produced by dissolving a dye in a fluorine-based solvent containing the fluorine-containing alcohol, applying the obtained solution to a substrate, and then forming a dye-containing recording layer by a medium. Cyanine dye, phthalocyanine dye, pyrylium salt dye, thiopyranium salt dye, triacontane dye, anthraquinone dye, porphin pigment, anthranil dye, triphenylmethane a dye, a benzophenone dye, an amine key dye, a deinmonium dye, a metal stear salt dye, etc. Examples of the substrate include polycarbonate, polymethyl methacrylate, epoxy resin, and amorphous structure. Polyolefin, polyester, polyvinyl chloride and other plastics, glass, ceramics, etc. Moreover, with the improvement of flatness, the improvement of adhesion, and the paper scale of the recording layer, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable. -13- 1250975 Α7 Β7 5. Inventive Note (11) For the purpose of deterioration prevention, etc., it is also possible to provide a primer layer between the recording layer and the substrate or to provide a protective layer on the upper surface of the recording layer. Note on the back In addition, the present invention can be easily manufactured by providing an information recording medium (CD-R, DVD-R, etc.) formed on a recording layer on which a laser can record and/or read information on a substrate. The photoreceptor of the negative film is preferably made of 'HCF 2 C. F 2 C Η 2〇Η, Η (CF 2 CF 2 ) 2 C Η 2 〇Ή and HCF (CF 3 ) 2 CF which are actually free of impurities. 2 C Η 2〇Η, and the recovered methanol-containing fraction and the radical generator contained in the fraction can be effectively utilized. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an embodiment of the present invention. Fig. 2 is a view showing one of the embodiments of the present invention including the step of removing the side cut. Fig. 3 is a view showing an embodiment of the present invention containing a two-stage electrochemical distillation step. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives, for these figures, the symbol 1 is the reaction kettle, the symbol 2 is the vaporization column, the symbol 3 is the centrifugal separator, the symbol 4 is the first distillation column, the symbol 5 is the second distillation column, Reference numeral 6 is a base treatment tank, and reference numerals 7 and 8 are basic steaming towers. BEST EMBODIMENT OF THE INVENTION The present invention will be described in more detail with reference to the following examples. Example 1 -1 This paper scale applies to China National Standard (CNS) Α4 specification (210Χ297 mm) -14-1250975 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Invention Description (Addition of methanol to β high pressure reactor (15〇〇g), butyl gD (32.25 g of di-t-butyl peroxide) and calcium carbonate (6 · 5 g). After replacing with nitrogen in the reactor, the temperature is raised to 1 2 5 t:, control the four-win acetylation to the pressure 〇· 8 5 Μ P a is added to the side to make the reaction for 2 · 6 hours. After cooling the crude reaction, the weight is determined to be 2 2 7 0 g 'gas chromatograph The analysis results were carried out, and 15.5 g of perbutyl D remaining without decomposition was observed. The obtained reaction crude product was treated in the following manner according to the flow chart shown in Fig. 3. First, the reaction crude material was passed from the reaction kettle. 1 is introduced into the centrifugal separator 3, and the reactant of the acid acceptor and the unreacted acid accepting agent are removed by centrifugation, and then introduced into the first distillation column. Next, the pressure of the distillation column is controlled to be heated at 0·1 MPa. The kettle is distilled from the top of the first distillation column 4 at 80 to 90 ° C. The obtained fraction was 1 2 6 . 5 g. The fraction was analyzed to contain 13.00 g of perbutyl D, and the residual butyl D remaining in the reaction crude product together with methanol was distilled off almost without decomposition. The residue component is completely free of butyl D. Next, the residue component is taken out from the bottom of the first distillation column 4, and introduced into a purification step by distillation. The residue component is introduced into the second distillation column 5, and the column is HCF 2 CF 2 C Η 2 〇Η (6 4 8 . 3 g ) was distilled off, and Η (CF 2 CF 2 ) 1 C Η 2 Η was taken from the top of the column (1 is an integer of 2 or more). A part of HCF 2 CF 2 C Η 2 Ο ( (150 g) is introduced into the base treatment tank 6, and sodium methoxide is added to the fraction. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 X297 mm) (Please read the notes on the back and fill out this page)
-15- 1250975 A7 _____ ___B7 五、發明説明（ (6 g，約0 . 0 3旲耳；作爲2 8 %甲醇溶液）。其次 (請先閱讀背面之注意事項再填寫本頁) ’麵鹼基處理的H C F 2 C F 2 C Η 2〇Η導入鹼性蒸餾塔 了’經蒸餾將甲醇及水由塔頂餾出，將含有 H C F 2 C F 2 C Η 2〇Η的殘底成分送至鹼性蒸餾塔8中 。最後於鹼性蒸態塔8中進行蒸態，於中段部的|留分回收 H C F 2 C F 2 C Η 2〇Η。所得之 H C F 2 C f 2 C Η 2〇Η的蒸餾殘留部分爲1 〇 mass ppm ’ 吸光度（2〇5nm)爲一〇.2abs以下。 實施例1 一 2 由實施例1 一 1回收的含有過丁基D (13 . 0g) 之1 2 6 1 . 5 g的甲醇，再回收至反應釜中再利用。即 ，回收的甲醇中加入2 5 4 g的新品甲醇，再加入過丁基 D ( 1 5 _ 7 5 g )及碳酸鈣（6 · 5 g )，與實施例1 - 1相同進行反應。反應時間爲2 . 7小時。反應終了後 冷卻反應粗製物，測定重量爲2 2 6 5 g，以氣體色譜儀 分析得知殘留1 5 . 1 g的未分解過丁基D。 經濟部智慧財產局員工消費合作社印製 例 施 實 述 上。 與里 理 物處 製行 粗進 應圖 反程 之流 得示 所所 3 圖 如 據 依 同 相 除 4 ， 塔 3 飽 機蒸 離一 分第 心入 離導 入後 導劑 釜酸 應受 反的 由應 物反 製 未 粗及 應物 反應 將反 先的 首劑 ， 酸 即受 去 P度 Μ 溫 1 出 . 離 ο 以 於中 制頂 控塔 力的 壓 4 的塔 塔餾 餾蒸 蒸 一 制第 控於 邊 。 ， 釜 次餾 其蒸 熱 Jn a 至 ο 8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 1250975 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（Μ 9 0 °c.將甲醇餾出。所得餾分爲1 2 6 2 _ 3 g。分析此 離分得知，含有1 2 . 6 g的過丁基D，殘留於反應粗製 物的過丁基D幾乎未反應下與甲醇同時餾出。殘底成分中 完全無含有過丁基D。 其次，將殘底成分由第一蒸餾塔4的塔底取出，經由 蒸餾導入純化步驟。殘底成分導入第二蒸餾塔5，塔頂餾 出 HCF2CF2CH2〇H(644.1g)，含有 H( CF2CF2) iCH2〇H (1表示2以上的整數）的殘底 成分由塔底取出。取出所得之H C FSC F2CH2〇H的 一部份（1 5 0 g )，導入鹼基處理槽6，該餾分中添加 2 8 %甲醇鈉（6 g，約0 . 0 3莫耳）。其次，經鹼基 處理的H C F 2 C F 2 C Η 2〇Η導入鹼性蒸|留塔7，經蒸 餾將甲醇與水由塔頂餾出，含有H C F 2 C F 2 C Η 2〇Η 的殘底成分送至鹼性蒸離塔8中。最後藉由驗性蒸|留塔8 下蒸餾，以中段部分的餾分回收H C F 2 C F 2 C Η 2〇Η 。所得的H C F 2 C F 2 C Η 2〇Η之蒸發殘留部分爲1 〇 mass ppm，υν 吸光度（20 5 nm)爲一〇.2abs 以下。 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)-15- 1250975 A7 _____ ___B7 V. Description of the invention ((6 g, about 0. 0 3 旲; as a 28% methanol solution). Secondly (please read the note on the back and fill out this page) The treated HCF 2 CF 2 C Η 2〇Η is introduced into a basic distillation column. 'Distilled methanol and water are distilled overhead, and the bottom component containing HCF 2 CF 2 C Η 2〇Η is sent to alkaline distillation. In column 8, the vapor phase is finally carried out in the alkaline vapor column 8, and HCF 2 CF 2 C Η 2〇Η is recovered in the middle portion. The obtained distillation residue of HCF 2 C f 2 C Η 2〇Η The fraction is 1 〇mass ppm ' absorbance (2 〇 5 nm) is one 〇.2abs or less. Example 1 1-2 1 2 6 1 . 5 containing n-butyl D (1. 0g) recovered from Example 1 - 1. The methanol of g is recycled to the reactor for reuse. That is, 2,54 g of new methanol is added to the recovered methanol, and then butyl D (1 5 _ 7 5 g ) and calcium carbonate (6 · 5 g) are added. The reaction was carried out in the same manner as in Example 1-1. The reaction time was 2.7 hours. After the completion of the reaction, the reaction crude product was cooled to a weight of 2 2 5 5 g, and analyzed by gas chromatography. Residual 15.1 g of undecomposed butyl D. The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, the printing example, and the implementation of the roughing of the Ricoh Department. According to the same phase division 4, the tower 3 full-machine steaming away from the first centrifugation into the guide after the introduction of the acid in the kettle should be reversed by the object is not coarse and the reaction of the reaction will reverse the first agent, the acid is subject to P degree Μ temperature 1 out. ο 以 以 以 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中 中National Standard (CNS) A4 Specification (210X297 mm) -16-1250975 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Invention Description (Μ 9 0 °c. Distillation of methanol. Distillation fraction 1 2 6 2 _ 3 g. Analysis of this dissociation revealed that 12.6 g of perbutyl D was present, and the residual butyl D remaining in the crude reaction was distilled off simultaneously with methanol under almost unreacted reaction. Containing butyl D. Second, the bottom component is from the bottom of the first distillation column 4. The extraction step is carried out by distillation, and the residue is introduced into the second distillation column 5, and HCF2CF2CH2〇H (644.1 g) is distilled off from the bottom, and H(CF2CF2) iCH2〇H (1 represents an integer of 2 or more) is contained. Take out from the bottom of the tower. A portion (150 g) of the obtained H C FSC F2CH2 〇H was taken out and introduced into the base treatment tank 6, and 28% sodium methoxide (6 g, about 0.03 mol) was added to the fraction. Next, the base-treated HCF 2 CF 2 C Η 2〇Η is introduced into the alkaline distillation|retaining tower 7, and the methanol and water are distilled off from the top by distillation, and the residue containing HCF 2 CF 2 C Η 2〇Η is contained. The ingredients are sent to the alkaline distillation column 8. Finally, H C F 2 C F 2 C Η 2〇Η was recovered as a fraction of the middle portion by anhydrogenation distillation. The resulting evaporation residue of H C F 2 C F 2 C Η 2〇Η is 1 〇 mass ppm, and the υν absorbance (20 5 nm) is one 〇.2abs or less. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)
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