A7 B7 五、發明説明（1 ) 本發明關於一種由元素態黃磷和鹵烷製備烷基亞膦酸 和二烷基膦酸的鹼金屬鹽及/或鹼土金屬鹽之方法。 有機磷化合物在工業上變得愈增重要。它們主要用於 製備除草劑或當作除草劑本身、當作萃取介質及當作火焰 阻滯劑。所用的起始物質主要爲P Η 3及鹵化磷，其必須依 次地由黃磷製備得。 目前，僅知道少數的一些方法可以由簡單的物質製備 具有超過一個磷-碳鍵的有機磷化合。 在超鹼性介質二甲亞硯/氫氧化鉀（DMS 0/ Κ 0 Η )中紅磷與當作烷化劑的乙炔或烯烴反應 (Trofimov 等人，磷、硫及矽 5 5，271 · 1991) 會優先地給予三有機膦和三有機膦氧化物。 用丙腈來烷基化紅磷，在上述條件下用超音波處理反 應混合物，會主要產生二級氧化膦。若採用1，1一二苯 基一乙烯，則其會產生三級氧化膦（3 0%)、二級氧化 膦（1 0 % )及膦酸（3 5 % ) 〔 D. Semenzin等人，四面 體通訊 3 5，3297，1994〕。 經濟部中央樣準局貝工消費合作社印製 已經嘗試（Trofimov 等人，Main Group Chem. News 4，18，1996,磷、硫及矽，10 9/110, 6 0 1，1 9 9 6 )使紅色變體的元素態磷與鹵烷於氫氧 化鉀、水、二噁烷和相轉移觸媒的存在下反應。經發現三 級氧化膦爲主要的產物（高及於7 5%的苄基溴，約6 〇 —65%的丁基溴）。分別製得19%的二級氧化膦及6 %的膦酸酯當作副產品，但是前者僅在鋅粉當作還原劑的 -4 - (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） 經濟部中央棣準局員工消費合作杜印製 A7 B7 五、發明説明（2 ) 存在下形成。 然而，上述方法具有缺點爲必須首先製備紅磷或有機 磷中間體。這些方法在工業上係高度複雜的，因此亦不經 濟的；所製造的產品常常必須經過更進一步的純化，其係 花費勞力的。以高產率特定製備某些化合物常常是特別困 難的。 因此更有利地係考量一種合成方法，其直接由元素態 黃磷開始且其更使用工業上容易取得的物質，將會以簡單 的方式合成所欲的烷基亞膦酸和二烷基膦酸的鹼金屬鹽或 鹸土金屬鹽。 本發明一目的因此在於提供一種製備烷基亞膦酸和二 烷基膦酸的鹼金屬鹽及/或鹼土金屬鹽之方法，其避免上 述缺點且藉此方法可沒有問題及依適當的質量比製備所欲 的終端產品。 藉開頭所述形態的方法可達成此目的，其包括於含水 的鹼金屬氫氧化物或鹸土金屬氫氧化物或它們的混合物之 存在下進行反應。 反應較佳於含水的驗金屬氫氧化物或驗土金屬氫氧化 物或它們的混合物和有機溶劑之兩相系統中進行。 作爲鹵烷，較佳使用氯甲烷或溴甲烷。 作爲有機溶劑，較佳使用未分枝的或分枝的烷類、烷 基取代的芳族熔劑、水不可互混性或僅部分水可互混性的 醇類或酯類，它們係單獨或互相合倂。 作爲有機溶劑，特佳使用甲苯，單獨或與醇類合倂。 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)A7 B7 5. Description of the invention (1) The present invention relates to a method for preparing alkali metal salts and / or alkaline earth metal salts of alkyl phosphinic acid and dialkyl phosphonic acid from elemental yellow phosphorus and haloalkanes. Organophosphorus compounds are becoming increasingly important in industry. They are mainly used in the preparation of herbicides or as herbicides themselves, as extraction media and as flame retarders. The starting materials used are mainly P Η 3 and phosphorus halides, which must be sequentially prepared from yellow phosphorus. At present, only a few methods are known which can be prepared from simple substances by organophosphorus compounds having more than one phosphorus-carbon bond. Red phosphorus reacts with acetylene or olefin as an alkylating agent in dimethylarsine / potassium hydroxide (DMS 0 / K 0 Η) in an overbased medium (Trofimov et al., Phosphorus, sulfur, and silicon 5 5,271 · 1991) Triorganophosphine and triorganophosphine oxide are given priority. Propionitrile is used to alkylate red phosphorus, and the reaction mixture is treated with ultrasound under the above conditions, which will mainly produce secondary phosphine oxide. If 1,1 diphenyl monoethylene is used, it will produce tertiary phosphine oxide (30%), secondary phosphine oxide (10%) and phosphonic acid (35%) [D. Semenzin et al., Tetrahedron Bulletin 3 5, 3297, 1994]. The printing of the Bayer Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs has been attempted (Trofimov et al., Main Group Chem. News 4, 18, 1996, Phosphorus, Sulfur and Silicon, 10 9/110, 6 0 1, 1 9 9 6) The elemental phosphorus of the red variant is reacted with a haloalkane in the presence of potassium hydroxide, water, dioxane and a phase transfer catalyst. Tertiary phosphine oxide was found to be the main product (up to 7 5% benzyl bromide, about 60 to 65% butyl bromide). 19% of secondary phosphine oxide and 6% of phosphonate were prepared as by-products, but the former was only -4 in zinc powder as a reducing agent-(Please read the precautions on the back before filling this page) The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs has been printed by Du A7 B7. 5. Description of the invention (2). However, the above method has a disadvantage in that red phosphorus or an organic phosphorus intermediate must be prepared first. These methods are highly complex in industry and therefore not economical; the products produced often have to undergo further purification, which is labor intensive. The specific preparation of certain compounds in high yields is often particularly difficult. Therefore, it is more advantageous to consider a synthetic method that starts directly from elemental yellow phosphorus and uses more industrially available substances, and will synthesize the desired alkyl phosphinic acid and dialkyl phosphonic acid in a simple manner. Alkali metal salt or earth metal salt. It is therefore an object of the present invention to provide a method for preparing alkali metal salts and / or alkaline earth metal salts of alkyl phosphinic acid and dialkyl phosphonic acid, which avoids the above-mentioned disadvantages and that the method can be free of problems and according to an appropriate mass ratio Preparation of desired end products. This can be achieved by the method described in the opening paragraph, which comprises carrying out the reaction in the presence of an aqueous alkali metal hydroxide or earth metal hydroxide or a mixture thereof. The reaction is preferably performed in a two-phase system containing an aqueous metal hydroxide or an earth metal hydroxide or a mixture thereof and an organic solvent. As the haloalkane, methyl chloride or methyl bromide is preferably used. As the organic solvent, unbranched or branched alkanes, alkyl-substituted aromatic fluxes, water-immiscible or only partially water-miscible alcohols or esters are preferably used. Combine with each other. As the organic solvent, toluene is particularly preferably used, alone or in combination with alcohols. This paper size applies to Chinese national standards (CNS> A4 size (210X297 mm) (Please read the precautions on the back before filling this page)
A7 _____B7 五、發明説明（3 ) 反應較佳於相轉移觸媒之存在中進行。 相轉移觸媒較佳爲鹵化四院基鐵、鹵化三苯基院基銹 或鹵化四有機銨。 反應溫度較佳爲一 2 0至+6 0°C。 溫度特佳爲0至3 Ot。 反應較佳在0至1 0巴的壓力進行。 本發明方法的較佳進行方式爲使得黃磷懸浮在溶劑或 溶劑混合物中，然後與鹵烷及式MOH或M，（〇h)2K 合物或它們的混合物反應，其中Μ係鹼金屬而μ’係驗土 金屬。 黃磷與鹵烷較佳爲互相以1:1至1:3的莫耳比反 應，黃磷對式ΜΟΗ或Μ’ （〇Η)2化合物的莫耳比爲 1 : 1 至 1 : 5。 較佳爲分離反應後所獲得的兩相系統及更進一步加工 成水相。 本發明亦關於使用依本發明所製備的烷基亞膦酸和二 烷基膦酸的鹼金屬鹽及/或鹼土金屬鹽於製備火焰阻滯 劑、萃取介質及植物保護劑。 令人驚異地，已經發現依本發明方法可使元素態黃磷 與鹵烷於兩相系統（有機溶劑/含水的鹼金屬氫氧化物） 中、及於（相轉移）觸媒的不存在或存在中、於極溫和條 件下以形成·一種產品混合物’其包括當作主要產品之對應 的烷基亞膦酸RP ( : 〇) ΗΟΗ之鹽。除了同等價値的 二院基膦酸R2P ( : ◦) 0Η之鹽外’所發現的技術上更 ^紙張尺度適/ΪΓ中國囤家摞+ ( rNS ) Λ4規格（210X 297公釐) 7〇~. 1 j ,_ i - 1 1^1 1 In In - 1 1^1 1^1 ^^1 • ^rr vv 、v't ("先聞讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（4 ) 有用之含磷產品係次磷酸和亞鱗酸之鹽。 (請先閱讀背面之注意事項再填寫本頁) 亦可聯合地形成少量的氧化三烷基膦R 3 P ( : 0 )、 氧化二烷基膦及未經鑑定的磷化合物，以平常方式由產品 混合物中移出它們。此外，形成當作副產品的氫，可毫無 問題地由反應混合物中分離出它。 令人驚異地，本發明方法既不會以明顯量形成膦（ PH3)也不會以明顯量形成烷基膦（RPH2、 R 2 P Η )。藉選擇適當的反應條件，如將少量的醇類加到 有機相中，可使所有未經鑑定的含磷副產品之形成達到最 小的程度，即至所用的黃磷之令人驚異地少數幾莫耳％的 程度，而有利於三種主要的產品，即是烷基亞磷酸鹽、次 磷酸鹽、亞磷酸鹽。 本發明方法之執行方式，例如爲：將溶劑和相轉移觸 媒一起導入，且若適當的話，加熱至黃磷的熔點以上，然 後添加（黃）磷，劇烈攪拌冷卻混合物至溫度（例如）爲 —1 0至+ 3 0 °C，然後添加鹵烷。 藉添加鹼金屬氫氧化物溶液來開始反應。在完成反應 後，可稀釋反應系統，例如用水，然後移除易揮發的成分 (H2、PH3、RPH2、R2PH 及過量的鹵烷）。 依此方式製得含水相/有機相之兩相系統，它們的相 係分開的。藉分析來判這些相的成分。' 藉先前技藝已知的方法來處理水相以產生純酸如烷基 亞膦酸，例如藉離子交換或蒸餾。 在上述反應中，亦可有利地使用鹼金屬氫氧化物與鹼 本紙張尺廋適用中國國家標嗶（（’NS ) Λ4規格（210X297公釐） _ 7 _ few#屮决掠彳局負-7-消费"竹私^-*'!^ A7 _______ 五、發明説明（5 ) 土金屬氫氧化物之混合物，以便分離出反應中所形成的亞 磷酸鹽，例如C a ( Η P 0 3 )。 亦可以依不同順序來添加反應成分，例如依上述界定 的莫耳比將這些連續地導入一反應器（加壓管、加壓反應 器或串級）內及在0 . 5至2小時的滯留時間後再將它們 排放出反應器。相分離後所獲得的有機相仍包括大部分任 何所用的相轉移觸媒，其有利地被循環。 實例1 將2升甲苯及2 5克（0 . 0 5莫耳）溴化三丁基十 六基鱗導入5升的不銹鋼加壓反應器內及加熱至約6 0 °C。將6 2克（2莫耳）熔化的黃磷導入反應器內，然後 劇烈攪拌冷卻至0 °C。然後凝聚出1 5 1克（3莫耳）氯 甲烷。 在0°C時，於一小時的期間泵送6 0 0克5 6%強度 的KOH溶液（6莫耳KOH)。藉冷卻反應器的套層移 除反應熱，在添加期間保持反應器內部溫度於0至+ 2 °C。在0 °C —小時後反應時間之後，將混合物溫熱至室 溫，及用1升的水來稀釋整批。 經由一燃燒系統來擴張反應器，所產生的氫、過量的 氯甲烷及微量的氣態膦（PH3、Me P&2)被燃燒。所 獲得的殘餘物係二均勻的液相，其不再含有任何黃色磷。 分開地將相排出及用3 1 P - N M R光譜作分析。 本紙張尺度適用中國國家標嘩（（、NS)A4規格（2丨〇〆297公釐） -8- (請先閱讀背面之注意事項再填寫本頁)A7 _____B7 V. Description of the invention (3) The reaction is preferably performed in the presence of a phase transfer catalyst. The phase transfer catalyst is preferably a tetrahalogenated iron, a triphenylhalogenated rust, or a tetraorganic ammonium halide. The reaction temperature is preferably -20 to + 60 ° C. The temperature is particularly preferably 0 to 3 Ot. The reaction is preferably carried out at a pressure of 0 to 10 bar. The method of the present invention is preferably carried out in such a manner that yellow phosphorus is suspended in a solvent or a solvent mixture, and then reacted with a haloalkane and a compound of formula MOH or M, (0h) 2K compound or a mixture thereof, wherein M is an alkali metal and μ 'Detecting soil metal. The yellow phosphorus and haloalkanes preferably react with each other at a molar ratio of 1: 1 to 1: 3, and the molar ratio of yellow phosphorus to the compound of formula MOO or M '(〇Η) 2 is 1: 1 to 1: 5. The two-phase system obtained after the separation reaction is preferably processed into an aqueous phase. The present invention also relates to the use of alkali metal salts and / or alkaline earth metal salts of alkyl phosphinic acid and dialkyl phosphonic acid prepared according to the present invention in the preparation of flame retarders, extraction media and plant protection agents. Surprisingly, it has been found that the method according to the invention enables elemental yellow phosphorus and halones to be used in a two-phase system (organic solvent / aqueous alkali metal hydroxide) and in the absence of (phase transfer) catalyst or In existence, under very mild conditions to form a product mixture 'which includes the corresponding alkyl phosphinic acid RP (: 〇) ΗΟΗ salt as the main product. In addition to the equivalent price of dibasic phosphonic acid R2P (: ◦) 0% of the salt, the technology found is more suitable ^ paper size / ΪΓΪ China storehouse 囤 + (rNS) Λ4 size (210X 297 mm) 7〇 ~ . 1 j, _ i-1 1 ^ 1 1 In In-1 1 ^ 1 1 ^ 1 ^^ 1 • ^ rr vv, v't (" Read the precautions on the back before filling this page) A7 B7 5. Description of the invention (4) Useful phosphorus-containing products are salts of hypophosphorous acid and linolenic acid. (Please read the precautions on the back before filling this page) A small amount of trialkylphosphine oxide R 3 P (: 0), dialkylphosphine oxide, and unidentified phosphorus compounds can also be formed in a common way. Remove them from the product mixture. In addition, hydrogen is formed as a by-product and can be separated from the reaction mixture without any problem. Surprisingly, the process according to the invention neither forms phosphine (PH3) nor alkylphosphine (RPH2, R2PΗ) in a significant amount. By selecting appropriate reaction conditions, such as adding a small amount of alcohol to the organic phase, the formation of all unidentified phosphorus-containing by-products can be minimized, that is, to the surprisingly small amount of yellow phosphorus used Ears to the extent that it benefits three main products, namely alkyl phosphites, hypophosphites, and phosphites. The method of the present invention is performed, for example, by introducing a solvent and a phase transfer catalyst together, and if appropriate, heating to a temperature above the melting point of yellow phosphorus, then adding (yellow) phosphorus, and vigorously cooling the mixture to a temperature (for example) of —1 0 to + 3 0 ° C, then add haloalkane. The reaction was started by adding an alkali metal hydroxide solution. After the reaction is complete, the reaction system can be diluted, for example with water, and then volatile components (H2, PH3, RPH2, R2PH and excess haloalkane) are removed. In this way, a two-phase system of aqueous phase / organic phase was prepared, and their phases were separated. The components of these phases are judged by analysis. 'The aqueous phase is treated by methods known in the art to produce pure acids such as alkyl phosphinic acids, for example by ion exchange or distillation. In the above reaction, alkali metal hydroxides and alkaline paper sizes can also be advantageously used. Applicable to the Chinese national standard (('NS) Λ4 specification (210X297 mm) _ 7 _ few # 7-Consumer " Bamboo ^-* '! ^ A7 _______ V. Description of the Invention (5) A mixture of earth metal hydroxides in order to separate the phosphites formed in the reaction, such as C a (Η P 0 3 ). The reaction components can also be added in different orders, for example, these are continuously introduced into a reactor (pressurized tube, pressurized reactor or cascade) according to the Morse ratio defined above and within 0.5 to 2 hours They are discharged out of the reactor after a dwell time. The organic phase obtained after phase separation still includes most of any of the phase transfer catalysts used, which is advantageously recycled. Example 1 2 liters of toluene and 25 grams (0 0.5 mol) tributylhexadecyl bromide was introduced into a 5 liter stainless steel pressurized reactor and heated to about 60 ° C. 62 g (2 mol) of molten yellow phosphorus was introduced into the reactor Then, cool vigorously to 0 ° C. Then 151 g (3 mol) of methyl chloride are condensed. At 0 ° C In one hour, 600 grams of a 5 6% strength KOH solution (6 mole KOH) was pumped. The reaction heat was removed by cooling the jacket of the reactor, and the internal temperature of the reactor was maintained at 0 to + during the addition 2 ° C. After a reaction time of 0 ° C—hours, the mixture was warmed to room temperature and the entire batch was diluted with 1 liter of water. The reactor was expanded through a combustion system. Chloromethane and trace amounts of gaseous phosphine (PH3, Me P & 2) were burned. The obtained residue was a two homogeneous liquid phase, which no longer contained any yellow phosphorus. The phases were discharged separately and subjected to 3 1 P-NMR The spectrum is used for analysis. The paper size is applicable to Chinese national standard ((, NS) A4 specifications (2 丨 〇〆297mm) -8- (Please read the precautions on the back before filling this page)
Ψ 3S&761 at B7五、發明説明（6 ) 水相 * (莫耳％磷） 氧化三甲基磷 2 . ,3 二甲基膦酸鉀鹽 0 · ,5 甲基亞膦鉀鹽 6 4 . 2 亞磷酸鉀鹽 1 5 . 8 次磷酸鉀鹽 1 4 · 2 未經鑑定的化合物 3.1 實例2 遵循實例1之程序，但是反應溫度爲2 5 t： 分析： 氧化三甲基磷 二甲基膦酸鉀鹽 甲基亞膦鉀鹽 亞磷酸鉀鹽 次磷酸鉀鹽 未經鑑定的化合物 實例3 水相 (莫耳％磷） 2.5 18-0 5 4.4 13.3 6.0 5 .7 IJ--：-----o^II (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哗（（’NS ) Λ4規格（210X 297公釐） .Q . 388*161 A7 ----____ 五、發明説明（7 ) 將500毫升二乙二醇二乙醚、13克（〇 . 026 莫耳）溴化三丁基十六基鱗及9 3克（1莫耳）正丁基氯 導入2升的攪拌過燒瓶內。於此溶液內，在室溫中，加入 1 50克NaOH (3 . 75莫耳）/1 50水的溶液。 於0°C —小時的期間將15 . 5克（〇 . 5莫耳）熔 化的黃磷逐滴添加至劇烈攪拌過的二相混合物中。在另3 小時的反應時間後，分離出二澄淸相，及31 P _NMR光 譜來鑑定所獲得的反應產物。 水相 (莫耳％磷） 丁基亞膦鈉鹽 41 次磷酸鈉鹽 3 亞磷酸鈉鹽 56 未經鑑定的化合物 <0.5 實例4 將26.1 〔遺漏〕（0.05莫耳）溴化三丁基十 六基鱗/1 0 0 0毫升甲苯的溶液導入5升不銹鋼壓力反 應器內及預熱至6 0°C。添加6 2克（2莫耳）黃磷後， 強烈攪拌將混合物冷卻至一 1 0 °C，然後k聚出2 0 2克 (4莫耳）氯甲烷。之後，於2小時的期間中添加400 克5 0%強度以重量計的氫氧化鈉水溶液，溫度維持在-1 0 °C。於一小時的期間中添加4 0 0克水，之後將混合 I- ——-I. I Ml In I I I -- - I lr…' ,.^1- I I- - - I ......... ,tT (讀先閱讀背面之注意事項再填寫本I ) 本紙張尺度適川中國阀家標嘈（（、NS ) Λ4規格（210X 297公釐） _ 1〇 .Ψ 3S & 761 at B7 V. Description of the invention (6) Aqueous phase * (Molar% phosphorus) Trimethyl phosphorus oxide 2, 3, Potassium salt of dimethylphosphonic acid 0, 5, Potassium salt of methyl phosphine 6 4 2 Potassium Phosphite 1 5. 8 Potassium Phosphate 1 4 · 2 Unidentified compounds 3.1 Example 2 The procedure of Example 1 was followed, but the reaction temperature was 2 5 t: Analysis: Trimethylphosphonium dimethyl oxide Potassium Phosphonate Methyl Phosphine Potassium Salt Potassium Phosphite Potassium Phosphite Potassium Phosphite Salt Unidentified Compound Example 3 Water Phase (Moore% Phosphorus) 2.5 18-0 5 4.4 13.3 6.0 5.7 IJ-:- --- o ^ II (Please read the notes on the back before filling in this page) This paper size is applicable to the Chinese national standard (('NS) Λ4 size (210X 297 mm). Q. 388 * 161 A7 --- -____ V. Description of the invention (7) 500 ml of diethylene glycol diethyl ether, 13 g (0.026 mol) of tributylhexadecyl bromide and 9 3 g (1 mol) of n-butyl chloride Introduce 2 liters of stirred through the flask. In this solution, at room temperature, add a solution of 150 g of NaOH (3.75 mol) / 1 50 water. During 1 hour at 0 ° C will be 15. 5 Grams (0.5 moles) The yellow phosphorus was added dropwise to the vigorously stirred two-phase mixture. After a reaction time of another 3 hours, the two-phase hydrazone phase was separated, and the 31 P NMR spectrum was used to identify the obtained reaction product. % Phosphorus) Butylphosphine sodium salt 41 Sodium hypophosphite 3 Sodium phosphite 56 Unidentified compound < 0.5 Example 4 26.1 [Missing] (0.05 mol) tributylhexadecyl bromide / A 1000 ml solution of toluene was introduced into a 5 liter stainless steel pressure reactor and preheated to 60 ° C. After adding 62 g (2 moles) of yellow phosphorus, the mixture was cooled with vigorous stirring to a temperature of 10 ° C. Then, 202 g (4 moles) of methyl chloride were polymerized. Thereafter, 400 g of a 50% strength by weight aqueous sodium hydroxide solution was added over a period of 2 hours, and the temperature was maintained at -10 ° C. Add 400 grams of water during the one hour period, after which I- ——- I. I Ml In III --- I lr… ',. ^ 1- I I---I ...... ..., tT (Read the precautions on the back before filling in this I) The paper size is suitable for Sichuan valve valve standard ((, NS) Λ4 specification (210X 297 mm) _ 1〇.
五、發明説明（8 ) 物另攪拌一小時，加熱至室溫’然後藉一燃燒單元來使反 應器降壓。此產生二均勻的液相，它們係分雛的且被分 析。 （ 水相（重量：920克）含有鈉鹽形式的65 . 6莫 耳％甲基亞膦酸、14.9莫耳亞磷酸及13.7莫耳％ 次磷酸和2.8莫耳％二甲基膦酸。 實例5 將2 9克溴化四辛基鱗/1 〇 〇 〇毫升甲苯的溶液導 入5升不銹鋼壓力反應器內及預熱至6 〇t。在添加6 2 克（2莫耳）黃磷後，強烈攪拌將混合物冷卻至一 1 〇 °C ’然後凝聚出202克（4莫耳）氯甲烷。之後，將混 合物加熱至2 0 °C，及於2小時的期間中添加4 0 0克 5 0 %強度以重量計的氫氧化鈉水溶液，溫度維持在2 〇 °C。於一小時的期間中添加4 〇 〇克水，之後將混合物另 攪拌一小時，加熱至室溫’然後藉一燃燒單元來使反應器 降壓。此產生二均勻的液相’它們係分離的且被分析。 水相（重量：940克）含有鈉鹽形式的51 . 2莫 耳％甲基亞膦酸、24 . 7莫耳％亞磷酸及18 . 5莫耳 %次磷酸和2·6莫耳％二甲基膦酸。 依已知的方式可由實例1至5中所製~備的鹽製備得 酸，例如藉離子交換。 本紙張尺廋適川中國國家標,（rNS ) Λ4規格（210X297公楚） (誚先閱讀背面之注意事項再填寫本頁}5. Description of the invention (8) The substance is stirred for another hour, heated to room temperature ', and then a combustion unit is used to depressurize the reactor. This results in two homogeneous liquid phases, which are young and analyzed. (Aqueous phase (weight: 920 g) contains 65.6 mol% methyl phosphinic acid, 14.9 mol% phosphorous acid and 13.7 mol% hypophosphorous acid and 2.8 mol% dimethylphosphonic acid in the form of a sodium salt. Examples 5 Introduce a solution of 29 g of tetraoctyl bromide / 1000 ml of toluene into a 5 liter stainless steel pressure reactor and preheat to 60 t. After adding 62 g (2 moles) of yellow phosphorus, The mixture was cooled to -10 ° C with vigorous stirring, and then 202 g (4 moles) of methyl chloride were condensed. After that, the mixture was heated to 20 ° C, and 400 g 50 was added over a period of 2 hours. % Strength sodium hydroxide aqueous solution by weight, the temperature was maintained at 20 ° C. During the one hour period, 400 g of water was added, after which the mixture was stirred for another hour, warmed to room temperature and then borrowed from a combustion unit To depressurize the reactor. This produces two homogeneous liquid phases, which are separated and analyzed. The aqueous phase (weight: 940 g) contains 51.2 mole% methyl phosphinic acid, 24% in the form of the sodium salt. 7 mol% phosphorous acid and 18.5 mol% hypophosphorous acid and 2.6 mol% dimethylphosphonic acid. The salts prepared in Examples 1 to 5 are prepared from acid, such as by ion exchange. This page}
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