43^246 五、發明説明（/) (请先閲讀背面之注意事項再填寫本頁) 本發明係有關以氯化磷腈與醇類在三級胺催化劑中 進行酯化反應，同時通入氨氣不斷再生三級胺的烷氧基磷 腈無水化製備法；此改良製備法的重點是在酯化反應過程 .中通入氨氣，將三級胺的鹽酸鹽不斷再生成三級胺使其可 再參與反應的方法《«此法因不斷再生三級胺來使用，故可 大幅減少其使用量至催化劑。 本發明方法無水洗步驟，不僅無廢水問題，可減少許 多回收步驟，且回收含三級胺的溶劑不須純化可直接再用 於下批次反應；產品顏色可改善成無色至淡棕色。氯化銨 副產物可用於製造氯化磷腈或直接販售，故也無廢料問題 U)發明背景 經濟部智慧財產局員工消費合作社印製 本發明係有關以氯化磷腈與醇類在三級胺催化劑中進 行酯化反應，以無水化製程回收三級胺及溶劑的烷氧基磷 腈製備法。磷腈化物（Phosphazenes)是含磷氮雙鍵結構化 物之總稱，其一般式爲：[N=P(R)2 ]n，（I)，nS3，R可 爲各類有機或無機之取代基，結構上可分爲環狀（Π、m) 或直鏈狀（IV);此類化合物因含磷、氮具相乘難燃效果之 元素’因此一直被認爲是良好的難燃劑β尤其含正丙烷氧 基取代結構者，[N=P(〇C3 H7) 2]n，（V)，因對酸鹼的環境 均穩定’故自1970年來一直被硏究使用於製成難燃嫘縈， 且製成商品。此類難燃劑尙可應用於其他塑膠及樹脂，製 成難燃化材料。 本紙乐尺度適用中國國家標準（CNS ) A4規格（210X292公釐） Λ34 A7 B7 五、發明説明（乙）43 ^ 246 V. Description of the invention (/) (Please read the notes on the back before filling out this page) The present invention is related to the esterification reaction of triphosphine catalyst with phosphphosphazene chloride and alcohols, while introducing ammonia An alkoxyphosphazene anhydrous production method for continuously regenerating tertiary amines; the emphasis of this improved preparation method is on the esterification reaction. Ammonia gas is passed into the tertiary amine hydrochloride to continuously generate tertiary amines. The method to make it possible to participate in the reaction again «This method is used because the tertiary amine is continuously regenerated, so the amount of use can be greatly reduced to the catalyst. The method of the invention has no water washing step, not only no waste water problem, but also can reduce many recovery steps, and the recovered tertiary amine-containing solvent can be directly used in the next batch reaction without purification; the product color can be improved to colorless to light brown. The by-product of ammonium chloride can be used in the manufacture of phosphazene chloride or directly sold, so there is no waste problem U) Background of the Invention Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs An alkoxyphosphazene preparation method in which an esterification reaction is performed in a secondary amine catalyst, and the tertiary amine and the solvent are recovered in an anhydrous process. Phosphazenes is a general term for phosphorus-nitrogen-containing double bond structure compounds. Its general formula is: [N = P (R) 2] n, (I), nS3, and R can be various types of organic or inorganic substituents. Structurally, it can be divided into cyclic (Π, m) or linear (IV); such compounds have been considered as good flame retardants because of their phosphorus and nitrogen elements that have a multiplicative flame retardant effect. Especially those with n-propalkoxy substituted structures, [N = P (〇C3 H7) 2] n, (V), are stable to acids and bases, so they have been studied and used for flame retardant since 1970 Alas, and made into goods. These flame retardants can be used in other plastics and resins to make flame retardant materials. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X292 mm) Λ34 A7 B7 V. Description of the invention (B)
R RR R
(請先閱讀背面之注意事項再填寫本頁) ΪΤ-l· r 經濟部智慧財產局員工消費合作社印製 [NPR2] 4 (nr ) [NPR2]n 3 (IV ) OC3H7 - 丨 J 7 Π —N = P-Η n ^ 3 OC3H7 (V ) 製備烷氧基磷腈（[NP(OR) 2]n)傳統上有兩種方式：（1)例 如美國專利 389 1448、3986882、3990900、401 1089、401-7562等使用氯化磷腈（[NPCl2]n)與醇鈉（NaOR)化物在二甲 苯溶劑中加熱回流反應（方程式1)。 (2)如美國專利3974242、4081593使用氯化磷膳和酸猫( ii.1 本紙乐尺度適用中國國家標準（CNS M4現格（210X2孖公釐） 經濟部智慧財產局員工消費合作杜印製 434246 A7 B7 五、發明説明（9) ROH)化物在三級胺（NR3)中反應（方程式2)，三級胺以吡啶 (Pyridine)效果佳。 此二種方法在傳統製程中均以水洗方式分離產品，故產生 .·大量的廢水。尤其以三級胺當溶劑兼制酸劑的製程除回收 三級胺所產生大量的鹼性廢水外，尙有多道純化步驟的問 題，如美國專利：4141937。以吡啶爲例，已知的方法是以 氫氧化鈉與吡啶鹽酸鹽（C5 H5 N.HC1)行中和反應（方程式3) ，靜置分離，脫水乾燥，分離，蒸餾等步驟始能獲得可再用之 吡啶因此在原料成本、設備投資、時間、環保等因素下 ，此類烷氧基磷腈化物一直無法經濟化生產。 針對上述缺點，已獲得中華民國專利090483號，利用氨氣 再生吡啶鹽酸鹽的無水化製程。此製程雖可非常有效的回 收吡啶及未反應的原料，但缺點是吡啶用量大，價格高， 且易造成產品顏色爲棕色至深棕色。 1. 2Na + 2ROH — 2NaOR + H2 个 2nNaOR + [NPCIJn ^ [NP(OR) 2]n + 2nNaCl 2. [NPC12 ]n + 2nR0H ^ [NP(OR) 2 ]n +2nNR3 HC1 3. C5 H5 N.HC1 + NaOH — C5 H5 N+NaCl +H20 4. C5 Hs N.HCI+NH3 C5 H5 N+NH4 Cl (2)發明槪述 本發明有鑑於前述吡啶製程之缺點，結合改變溶劑、 吡啶用量及氨氣再生吡啶鹽酸鹽的原理，提供新方法。本 發明是在酯化反應過程中通入氨氣（將吡啶的鹽酸鹽不斷 的再生成吡啶使其再參與反應的方法，因此可使吡啶原需 的二莫耳量減少成催化劑量。丨比法涨步.驟，不僅無_ 本紙張尺度通用中國國家標準（CMS ) A4規格UiOX 29f公釐） (請先閲讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling out this page) ΪΤ-l · r Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy [NPR2] 4 (nr) [NPR2] n 3 (IV) OC3H7-丨 J 7 Π — N = P-Η n ^ 3 OC3H7 (V) There are traditionally two ways to prepare alkoxyphosphazene ([NP (OR) 2] n): (1) For example, US patents 389 1448, 3988882, 3990900, 401 1089 , 401-7562, etc. use a phosphazene chloride ([NPCl2] n) and a sodium alkoxide (NaOR) compound in a xylene solvent under heating and refluxing (Equation 1). (2) For example, U.S. Pat. 434246 A7 B7 V. Explanation of the invention (9) ROH) compounds are reacted in tertiary amine (NR3) (Equation 2), and the tertiary amine is better with pyridine. These two methods are washed by water in the traditional process. The product is separated, so a large amount of wastewater is produced. Especially the process of using tertiary amine as a solvent and acid generator, in addition to recovering a large amount of alkaline wastewater produced by tertiary amine, there are problems with multiple purification steps, such as the US patent : 4141937. Taking pyridine as an example, the known method is a neutralization reaction (Equation 3) with sodium hydroxide and pyridine hydrochloride (C5 H5 N.HC1), separation by standing, dehydration drying, separation, distillation and other steps. Reusable pyridine was only available, so such alkoxyphosphazides have not been economically produced due to factors such as raw material cost, equipment investment, time, and environmental protection. In response to the above shortcomings, the Republic of China Patent No. 090483 has been used to utilize Ammonia Anhydrous process of raw pyridine hydrochloride. Although this process can very effectively recover pyridine and unreacted raw materials, the disadvantages are the large amount of pyridine, the high price, and the color of the product is easily brown to dark brown. 1.2 Na + 2ROH — 2NaOR + H2 2nNaOR + [NPCIJn ^ [NP (OR) 2] n + 2nNaCl 2. [NPC12] n + 2nR0H ^ [NP (OR) 2] n + 2nNR3 HC1 3. C5 H5 N.HC1 + NaOH — C5 H5 N + NaCl + H20 4. C5 Hs N.HCI + NH3 C5 H5 N + NH4 Cl (2) Description of the invention The present invention has the disadvantages of the aforementioned pyridine process in combination with changing the solvent, the amount of pyridine and the ammonia to regenerate pyridine The principle of hydrochloride provides a new method. The present invention is a method of introducing ammonia gas during the esterification reaction (the method of continuously regenerating pyridine hydrochloride to pyridine to participate in the reaction again, so that The amount of two moles is reduced to the amount of catalyst. 丨 The ratio is increased. The steps are not only _ This paper size is common Chinese National Standard (CMS) A4 specification UiOX 29f mm) (Please read the precautions on the back before filling this page)
434246 A7 經濟部智慧財產局員工消費合作杜印製 B7__五、發明説明（ιΑ ) 廢水問題，且減少許多回收步驟。回收含吡啶的溶劑不須 純化可直接再用於下批次反應。產品顏色可改善成無色至 淡棕色。氯化銨副產物可用於製造氯化磷腈或販售，故也 .·無廢料問題。經此改進使烷氧基磷腈化物更具經濟化生產 價値。 (3)發明的詳細說明 本發明係以氯化磷腈先溶於適量的醇類及溶劑中，然 後加入三級胺類化合物行酯化反應。反應液保持在適當的 溫度下持續通入氨氣，使氨氣與吡啶鹽酸鹽行再生反應， 生成吡啶及氯化銨固體析出（方程式4) »通入所需的氨氣 後，吡啶可完全被再生。此時反應液中含大量的溶劑、烷 氧基磷腈及氯化銨固體，少量的醇化物及三級胺。反應液 經過濾掉氯化銨後，液體部份行減壓蒸餾除去溶劑、三級 胺及醇化物，可得烷氧基磷腈化物。 含少量三級胺、醇化物的回收溶劑可直接使用於下批 次反應。氯化銨以適當方法純化後可資供利用。本發明之 置換反應爲放熱反應，須以適當手段保持反應液溫度在0-70° C。通入氨氣時可在0.5-1.5大氣壓下進行。 實施例一： 取348公克氯化磷睛與1000公克正丙醇置於3公升的反 應器中。將150公克吡啶於半小時內逐滴加入反應器中， 期間維持反應液溫度在20至30° C.加完料後，常壓下以0.5 公升/分之流速將氨氣通入反應器內，反應液溫度維持在 30-35= C.當氨氣通入量達102公克後停止。反應液過濾掉 氯化銨，液體部份經減懕蒸餾植吡啶及ΤΗ丙醇後得淡結任 -本纸張尺度適用中國國家標準（cns ) Α4说格（2丨〇；<2蚱公釐） (請先閲讀背面之注意事項再填寫本頁) 7·: -^ 4 經濟部智慧財產局員工消費合作社印製 3 42 4 G at B7 ____·、_ _ _五、發明説明（i) 液體狀的正丙氧基磷腈450公克，黏度500cps/25° C。 實施例二：（對照用） 取348公克氯化磷腈與1000公克吡啶置於3公升的反應 器中。將400公克正丙醇於半小時內逐滴加入反應器中， 期間維持反應液溫度在20至3 0° C.加完料後，常壓下以0.5 公升/分之流速將氨氣通入反應器內，反應液溫度維持 在30-35 ° C.當氨氣通入量達102公克後停止。反應液過濾 掉氯化銨，液體部份經減壓蒸餾掉吡啶及正丙醇後得深棕 色液體狀的正丙氧基磷腈460公克，黏度l〇〇〇Cps/25° C。 實施例三： 取2320公克氯化磷腈、500公克Dtfc啶與6公升氯苯置於 12公升的反應器中。將2600公克正丙醇於二小時內逐滴加 入反應器中，期間維持反應液溫度在20至30° Ο 加完料 >轰維持反應液溫度30-35° C，常壓下以3公升/分之流速將 氨氣通入反應器內。當氨氣通入量達680公克後停止。反 應液過濾掉氯化銨|液體部份經減壓蒸餾掉氯苯、吡啶及 正丙醇後得淡棕色液體狀的正丙氧基磷腈2820公克•黏度 700cps/25。 C 。 實施例四：（對照用） 取11.6公斤氯化磷腈與32公升吡啶置於50公升的反應 器中。將15公斤正丙醇於4小時內逐滴加入反應器中，期 間維持反應液溫度在20至35° C。加完料後維持反應液溫 度35° C，19小時。然後在常壓下通氨氣入反應器內，反應 液溫度維持在40-55° C。當氨氣通入量逹3.4公斤後停[卜_ 本纸張尺度適用中國國家標準（CNS ) A4規格（210X295^釐） (請先閣讀背面之注意事項再嚴寫本頁) 訂 4 3 4246 A7 B7 五、發明説明（6 ) 。反應液過濾掉氯化銨，液體部份經減壓蒸餾掉吡啶及正 丙醇後得棕色液體狀的正丙氧基磷腈13.5公斤，黏度800 cps/25。 C 。 本發明係有關一種以氨氣不斷再生三級胺催化劑的 製備烷氧基磷腈化物的方法，其特徵在使用三級胺當催 化劑下，使氯化磷腈與醇類化物在溶劑中進行酯化反應 ，於酯化反應過中同時通入氨氣與三級胺鹽酸鹽行置換 再生反應，使反應中三級胺使用量降至催化劑量；其中 所指三級胺可爲吡啶，其使用量爲氯化磷腈當量値的20 -80%，其較佳使用量爲氯化磷腈當量値的30-60% ;其中 醇類可爲正丙醇；其中溶劑可爲醇類或含氯有機溶劑； 本發明方法具有使用少量三級胺，例如吡啶；其中，烷 氧基磷腈化物基本化學式爲[NP(OR) 2 ]n，R爲1至4個碳的 烷基，ng 3的整數，環狀物佔50-95%，直鏈狀物佔5-50% :本發明製程具有回收物步驟簡便，產物呈淡棕色等優 點，爲一項具有產業上利用性之新發明》 經濟部智慧財產局員工消費合作社印製 ...,ί、、 (請先閱讀背面之注意事項再填寫本頁)434246 A7 Consumption Cooperation by Employees of Intellectual Property Bureau, Ministry of Economic Affairs, Du B7__V. Description of Invention (ιΑ) Wastewater problem, and reduce many recycling steps. Recovery of the pyridine-containing solvent can be reused in the next batch without purification. Product color can be improved from colorless to light brown. Ammonium chloride by-products can be used in the manufacture or sale of phosphazene chloride, so there is no waste problem. With this improvement, the alkoxyphosphazide is produced more economically. (3) Detailed description of the invention The present invention is based on dissolving phosphphosphazene chloride in an appropriate amount of alcohols and solvents, and then adding a tertiary amine compound for esterification reaction. The reaction solution is kept at an appropriate temperature, and ammonia gas is continuously introduced to regenerate the ammonia gas and pyridine hydrochloride to generate pyridine and ammonium chloride solids (Equation 4). After passing the required ammonia gas, pyridine can Completely regenerated. At this time, the reaction solution contained a large amount of solvent, solid alkoxyphosphazene and ammonium chloride, a small amount of alcoholate and tertiary amine. After the ammonium chloride was filtered off from the reaction solution, the solvent, the tertiary amine and the alcoholate were distilled off under reduced pressure to obtain an alkoxyphosphazide. The recovered solvent containing a small amount of tertiary amine and alcoholate can be directly used in the next batch of reactions. Ammonium chloride is available for use after purification by appropriate methods. The displacement reaction of the present invention is an exothermic reaction, and the temperature of the reaction solution must be maintained at 0-70 ° C by appropriate means. The introduction of ammonia gas can be carried out at 0.5-1.5 atm. Example 1: 348 grams of phosphorous chloride and 1000 grams of n-propanol were placed in a 3 liter reactor. 150 grams of pyridine was added dropwise to the reactor within half an hour, during which the temperature of the reaction solution was maintained at 20 to 30 ° C. After the addition was completed, ammonia gas was passed into the reactor at a flow rate of 0.5 liters per minute under normal pressure. The temperature of the reaction solution is maintained at 30-35 = C. When the ammonia gas flow reaches 102 grams, it stops. The reaction solution was filtered out of ammonium chloride, and the liquid portion was lightly distilled after reducing the distillation of phytopyridine and T-propanol.-This paper size applies the Chinese national standard (cns). A4 cells (2 丨 〇; < 2 grasshopper (Mm) (Please read the notes on the back before filling this page) 7 ·:-^ 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 42 4 G at B7 ____ ·, _ _ _V. Invention Description (i ) Liquid n-propoxyphosphazene 450 g, viscosity 500cps / 25 ° C. Example 2: (for comparison) 348 grams of phosphazene chloride and 1000 grams of pyridine were placed in a 3 liter reactor. 400 grams of n-propanol was added dropwise to the reactor within half an hour, during which the temperature of the reaction solution was maintained at 20 to 30 ° C. After the addition was completed, ammonia gas was passed in at a flow rate of 0.5 liters per minute under normal pressure. In the reactor, the temperature of the reaction solution was maintained at 30-35 ° C. When the ammonia gas flow reached 102 grams, it stopped. The reaction solution was filtered to remove ammonium chloride, and the liquid portion was distilled away under reduced pressure to remove pyridine and n-propanol to obtain 460 g of n-propoxyphosphazene as a dark brown liquid with a viscosity of 1000 Cps / 25 ° C. Example 3: Take 2,320 grams of phosphazene chloride, 500 grams of Dtfc, and 6 liters of chlorobenzene in a 12-liter reactor. 2600 grams of n-propanol was added dropwise to the reactor within two hours, during which the temperature of the reaction solution was maintained at 20 to 30 ° C. After the addition was completed, the temperature of the reaction solution was maintained at 30-35 ° C, and 3 liters at normal pressure. A flow rate of 1 / min passes ammonia gas into the reactor. Stop when the ammonia gas flow reaches 680 grams. The reaction solution was filtered to remove ammonium chloride. The liquid portion was distilled under reduced pressure to remove chlorobenzene, pyridine and n-propanol to obtain n-propoxyphosphazene 2820 g as a light brown liquid with a viscosity of 700 cps / 25. C. Example 4: (for comparison) 11.6 kg of phosphazene chloride and 32 liters of pyridine were placed in a 50 liter reactor. 15 kg of n-propanol was added dropwise to the reactor over 4 hours, while maintaining the temperature of the reaction solution at 20 to 35 ° C. After the addition was completed, the temperature of the reaction solution was maintained at 35 ° C. for 19 hours. Then, ammonia gas was introduced into the reactor under normal pressure, and the temperature of the reaction solution was maintained at 40-55 ° C. Stop when the ammonia gas flow rate is 3.4 kg. [Bu _ This paper size applies the Chinese National Standard (CNS) A4 specification (210X295 ^ cent) (please read the precautions on the back before writing this page strictly) Order 4 3 4246 A7 B7 5. Description of the invention (6). The reaction solution was filtered out of ammonium chloride, and the liquid portion was distilled under reduced pressure to remove pyridine and n-propanol to obtain 13.5 kg of n-propoxyphosphazene as a brown liquid with a viscosity of 800 cps / 25. C. The invention relates to a method for preparing an alkoxyphosphazide by continuously regenerating a tertiary amine catalyst with ammonia gas, which is characterized in that a tertiary amine is used as a catalyst, and the phosphphosphazene chloride and an alcohol compound are esterified in a solvent. In the reaction, the ammonia gas and the tertiary amine hydrochloride are replaced by the regeneration reaction at the same time as the esterification reaction, so that the amount of tertiary amine used in the reaction is reduced to the amount of the catalyst; the tertiary amine may be pyridine. The amount used is 20-80% of the phosphazene chloride equivalent 値, the preferred amount is 30-60% of the phosphazene chloride equivalent 値; where the alcohols can be n-propanol; where the solvent can be alcohols or containing Chlorine organic solvent; the method of the present invention uses a small amount of tertiary amine, such as pyridine; wherein the basic chemical formula of the alkoxyphosphazide is [NP (OR) 2] n, R is an alkyl group of 1 to 4 carbons, ng 3 It is an integer of 50-95% for cyclics and 5-50% for linears. The process of the present invention has the advantages of simple steps for recycling and a light brown product. It is a new invention with industrial applicability. " Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ..., ί ,, (Please read the note on the back first (Fill in this page again)
本紙乐尺度適用中国國家摞準（CNS ) A4規格（210X29?公釐）This paper scale is applicable to China National Standard (CNS) A4 (210X29? Mm)