d5 896 A A7 B7 五、發明說明（1 ) 本發明係提供一種鑭系金屬羧酸鹽的製造方法，以及 以該製法製得之產物的用途，特別是指一種利用多量的水 參與反應，以增加鑭系金屬羧酸鹽的收率，縮短製程時間 ，並且製得之鑭系金屬羧酸鹽可被應用作為二稀系單體之 聚合觸媒。 按’ 一般二烯系單體聚合反應中較常用的稀土族鋼系 (Lanthanides)金屬羧酸鹽大致有以下兩類： —、钕（Neodymium，以下簡稱Nd)化合物：其較常使用者 有環烷酸鉉[Neodymium trinaphthates，以下簡稱 Nd(Naph)3]、新癸酸鈥（Neodymium versatates，以 下簡稱NdV3)。 二、鈥元素及其他稀土金屬元素混合的化合物。 上述兩種鈥化合物的製備方法已被詳盡記載於先前的 專利案以及書籍中’例如：美國第4, 520, 1 77號發明專 利案中曾ΐ己載’使氣化敍（Neodymium chloride，化學式 為NdC!3)溶液與新癸酸納溶液（Sodium versatate)反應， 並以甲笨為溶劑萃取後，再以蒸發器乾燥，並經過過濾器 過濾’即可製得NdV3之钕化合物；另一種已知的稀土金 屬羧酸鹽的製造方法’係由中國科學院之長春應用化學研 究所所開發，其並記載於1 9 8 0年「中國科學出版社」 所出版之稀土催化合成橡膠文集令的第三八一頁至第三八 七頁中’其係為一種直接萃取法，主要係在三氧化二鉉 (Neodymium oxide ’化學式為Nd203)中加入濃鹽酸，以產 生氯化敍（NdCl；j)之後’再與氫氧化銨（Ammoniura 第3頁 本紙張尺度適用中國國豕標準（CNS)A4規格（210x297公楚） --------------裝— (請先wtt背面之注意事項再填寫本頁) -訂· 經濟部智慧財產局員工消費合作社印製 4 5 89 b 4 A? _____B7 五、發明說明（2 ) hydroxide)、環烷酸（naphthenic acid)混合，即可生成d5 896 A A7 B7 V. Description of the invention (1) The present invention provides a method for producing a lanthanide metal carboxylate and the use of the product prepared by the method, especially a method that uses a large amount of water to participate in the reaction to Increasing the yield of lanthanide metal carboxylate, shortening the process time, and the lanthanide metal carboxylate obtained can be used as a polymerization catalyst for dilute monomers. According to the general rare earth steel (Lanthanides) metal carboxylates commonly used in the polymerization of general diene monomers, there are roughly the following two types:-Neodymium (hereinafter referred to as Nd) compounds: more common users have a ring Neodymium trinaphthates (hereinafter referred to as Nd (Naph) 3), neodecanoic acid '(Neodymium versatates (hereinafter referred to as NdV3)). Second, “elements and other rare earth metal elements mixed compounds. The preparation methods of the above two compounds have been described in detail in previous patents and books. For example, US Patent No. 4,520, 177 has been included in the patent case of “Enodymium chloride (chemical formula NdC! 3) solution is reacted with sodium neodecate solution (Sodium versatate) and extracted with methylbenzyl as a solvent, then dried in an evaporator and filtered through a filter to obtain a neodymium compound of NdV3; another The known method for the production of rare earth metal carboxylates was developed by the Changchun Institute of Applied Chemistry of the Chinese Academy of Sciences, and it is recorded in the Rare Earth Catalytic Synthetic Rubber Essay Order published by the Chinese Science Press in 1980. On pages 38 to 387, 'It is a direct extraction method, which mainly involves adding concentrated hydrochloric acid to Neodymium oxide' (Nd203) to produce chloride (NdCl; j ) 'And then ammonium hydroxide (Ammoniura page 3 This paper size applies the Chinese National Standard (CNS) A4 specification (210x297)) -------------- installation— (please first (Notes on the back of wtt, please fill out this page)- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 5 89 b 4 A? _____B7 V. Description of the invention (2) hydroxide) and naphthenic acid can be mixed to produce
Nd(Naph)3之溶液，之_後以氧水中和使溶液之ρ η呈中性 ，再經 >儿降將水相及油相分離，最後再蒸齒即可製得 Nd(Naph)3溶液；由長春化學研究所製得之Nd(Naph)3，其 游離酸（即未與Nd化合之RC00H)對於鑭系金屬的莫耳比 在0· 45/1〜〇. 8/1之間，其殘留的水份在78〜425 ρριη之 間’而由此法所製得之Nd(Naph) 3再配合以烷基氣化鋁 及有機紹化合物製成丁二稀聚合用之觸媒系統，其游離酸 在0.71/1〜0.8/1之間，而水份含量在138〜287ppm之 間，此觸媒系統之聚合轉化率良好。 前述兩種鑭系金屬羧酸鹽合成方法共同的缺點是需要 經過萃取、過濾等步驟’因此其合成步驟繁雜需要的生產 設備也多，此外，由於鈉金屬會殘留於產品中，因此產品 必需再經過純化步驟，造成收率下降。 另外’美國第5, 220, 045號發明專利案則揭露，在硝 酸化欽[Nd(N03)3] '新癸酸及氨中加入例如環己炫的溶荆 ’在室溫下攪拌反應’即可製得NdV3的水溶液，之後利 用水萃取，再經由蒸餾將水除去，即可製得NdV3的化合 物；此種製法由於合成的過程中必需利用水來萃取，因此 製程繁雜’另外[Nd(N03)3]化合物較不易取得，將不利於 生產。·_ 今本案發明人經銳意研究發現，直接將鑭系金屬化合 物與有機羧酸溶劑及多量的水，使其反應形成油水混合之 鑭系金屬羧酸鹽混合液後，再經沉降步驟使油相及水相分 第4頁 本紙張尺度適用令國國家標準（CNS)A4規格（2〗0 X 297公釐） ----------------- {請先閱讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作杜印製 /1 p； 4 A7 ___ B7 .經濟部智慧財產局員工消費合作社印製 五、發明說明（3 ) 離’之後楮由蒸德除去油相溶液中的水，即可以簡單的製 程在缩短製程時間的情況下’製得高收率的鑭系金屬m酸 鹽，遂有本發明之產生。 因此，本發明之主要目的係在提供一種製程簡單、產 物收率高，且沉降速度快’而可大幅縮短製程時間之鋼系 金屬羧酸鹽的製造方法，以及利用前述方法製得之金屬敌 酸鹽’做為一種活性良好之二烯系單體聚合反應之觸媒。 爰是，本發明之鑭系金屬羧酸鹽的製造方法，係用來 製造具有Ln(RCOO)3結構式之產物，上述結構式中之l代 表稀土族之鋼系金屬，原子序介於57〜71，其係選自： 鈽、鐯、鈥、釓、鑭及釤，而R代表具有1〜1 9個碳原 子之碳氫化合物，其主要成份包含： (A) 鋼系（Ln)金屬之氧化物； (B) 具有2〜20個碳原子之有機羧酸； (C) 水；及 (D) 惰性溶劑，其係為脂肪族、環狀脂肪族、或者具有6 到2 0個碳原子之芳香族烴； 其中，水與鑭系金屬之莫耳比在5 : 1以上，上述鑭 系金屬之氧化物（A)、有機羧酸（B)、水（C )及惰性溶液（D) 在G〜3 0 0 °C溫度下反應後，經由水相及油相之分離步驟 後，再將油相蒸餾至含水量20 0 0 ppm以下而得。 本發明以上述鑭系金屬羧酸鹽的製造方法所製得之產 物’其係用於二烯系單體的聚合反應中作為觸媒，藉以提 高二烯系單體聚合時之轉化率。 第5頁 (請先閱讀背面之注意事項再填寫本頁) 表紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公楚） A7 ---—---B7__ —------ 五、發明說明（4 ) f請先閱請背面之注*?事項再填寫本頁) 本發明鑭系金屬之氧化物（A)中的鑭系金屬係為稀土 族（rare earth)的元素’其原子序介於5 7〜7 1之間， 此範圍之元素包含有筛（cerium)、鐯（praseodymium)、敍 (neodymium)、亂（gadolinium)、鋼（lanthanum)及衫 (samarium )，其中，以钕為較佳，另外亦可為上述各元 素混合。本發明鑭系金屬之氧化物（A)的具體代表例有： 三氧化二鈥（Nd 2 03) '十六氧化十一镨（ρΓί1〇ι6)、三氧化 二鈽（Ce203 )、三氧化二鑭（La203 )及三氧化二釓（Gd203 )等 ’以化合物取得之容易度，以及作為觸媒系統時之催化活 性作考量，尤以採用三氧化二钕為較佳。 本發明具有2〜2 0碳原子的有機羧酸（B)乃使用脂 肪族（a 1 i phat i c)叛酸類或環脂肪族（cy c 1 oa 1 i phat i c)敌 酸類或芳香族有機羧酸，其具有下列結構式： R - C Ο Ο Η 其中，R代表碳原子數1〜1 9的烷基、環烷基、芳 香族羥基、芳烷基等。 經濟部智慧財產局員工消費合作社印製 本發明之有機叛酸的具體例子有：乙酸（aceticacid) 、丙酸（propionic acid)、正 丁基酸（n-butyric acid)、 異 丁基酸（isobutyl acid)、戊酸（valeric acid)、三甲 基乙酸（pivalic acid)、己院甲酸（hexane carboxylic acid) 、 2 —己院曱酸（2-hexane carboxylic acid)、環 己烧甲酸（cyclohexane carboxylic acid)、3 —環己基 丙酸（3-cyclohexyl propionic acid) 、 2 —乙基己院甲 酸（2-ethylhexane carboxylic acid) 、 2 —甲基一2 ~ 第6頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 * 297公« ) α6 89δ^ at Β7 五、發明說明（5 〉 乙基戊酸（2-methyl-2-ethyl pentanoic acid)、2 ，2 —二乙基戊酸（2, 2-diethyl pent anoic acid)、2，2 — 二甲基己酸（2,2-dimethyl hexanoic acid)、2 —甲基一 2 —乙基己酸（2-methyl-2-ethyl hexanoic acid)、2， 2—二乙基己酸（2,2-(1161±7111。又311〇1。&(：1(1)、2 —乙 基一2 — 丙基己酸（2-ethy 1-2-propyl hexanoic acid)、 2 — 乙基一2 — 丁 基己酸（2-ethyl 2-butyl hexanoic acid)、2，2 —二乙基庚酸（2,2-diethyl heptanoicacid) 、2，2—二乙基辛酸（2,2-£1161;1171〇(^311〇1〇3。1(1)、 2 —甲基一2 — 丁 基辛酸（2-methyl-2-butyl octanoic acid)、1—庚酸（1-heptanoic acid)、1—辛院甲酸（1-octane carboxlic acid) 、 1 —壬烧甲酸（1-nonane 經濟部智慧財產局員工消費合作社印製 -------------裝-------:訂. (請先閱讀背面之注意事項再填寫本頁) carboxlic acid)、新癸酸（versatic acid，正式稱為 neodecanoic acid，化學式為 C9H19-C00H)、十二烧酸 (lauric acid)、十四院酸（myristic acid)、十六烧酸 (palmitic acid)、十八炫酸（stearic acid)、十八碳-9-烯酸（oleic acid)、苯甲酸（benzoic acid)、環烧酸 (naphthenic acid)、苯基醋酸（phenyl acetic acid)、 三笨基醋酸（triphenyl acetic acid )及三環己基醋酸 (tricyclohexyl acetic acid)，其較佳的例子為：環烷 酸 '新癸酸等。上述有機羧酸可被單獨使用或混合使用。 本發明所使用具有2至2 0個碳原子的有機羧酸（b) 與鑭系金屬（Ln)之莫耳比（即RCOOH/Ln)在2/1〜100/1 間，較佳為2/1〜20/1之間，更佳則為3/1〜10/1。 第7頁 本紙張尺度適用中國國-家標準（CNS)A4規格（210 X 297公釐） A7 458964 B7_____ 五、發明說明（6 ) {請先閱讀背面之注意事項再填寫本頁) 本發明所使用的水（C)，其添加量與鑭系金屬（Ln)的 莫耳比dO/Ln)在5/1以上，亦即，本發明必需使用足 夠的水才能達到預期的目的；當兩者之莫耳比在5/1以 下時’後述製造方法的油相與水相分離時間冗長，產品之 收率大幅降低’且分離後的水相及油相中反應不完全，會 有許多的未反應物夾雜其中，並使得水相與油相呈現混濁 狀’而不利於整個製程之生產。此外，本發明亦可依需要 在水（C)中加入例如：氣化氩等酸性化合物來幫助反應的 進行® 適合於本發明之惰性溶劑（D)有：脂肪族、環狀脂肪 族、或者具有6到2 0個碳原子之芳香族烴，其中芳香族 煙又以含有6到1 〇個碳原子為較佳，其具體之例子有： 丁烷、戊烷、己烷、庚烷、辛烷、環戊烷、環癸烷、甲苯 ’以及剛述成份的對比同質異性體（C〇rreSP〇nding i S〇mer) ’較佳之具體例子為：正一己烷和環己烷。上述惰性溶劑 (D)可被單獨使用或者混合使用，並藉由適當的先前測試 來決定最佳的混合比例。 經濟部智慧財產局員工消费合作社印製 本發明之製造方法乃將鑭系金屬氧化物（A)、具有2 〜2 0個碳原子之有機羧酸（B)、水（c)及惰性溶劑（D)依 適當的比例泵送至反應槽内，其中，水與鑭系金屬氧化物 (A)間的莫耳比必需以在5/丨以上，其反應溫度則控制在 ◦〜3 0 〇 °C ’較佳為2 5〜1 6 0 °C，攪拌反應時間在 0 · 1〜8小時，即可生成金屬羧酸鹽[Ln(RC〇〇)3]溶液 ’將其靜置待水相及油相分離，其分離時間在數分鐘至2 第8頁 本紙張尺度適用中國國家標準（CNS)A_4規格（210 X 297公釐） 4 5 8 9 6 4 A7 B7 五、發明說明（7 ) 小時之間即可完成，此時油相在水相之上，且其分界點清 晰可見，沒有混濁的現象，將下層水相排出’且將含有金 屬羧酸鹽之油相蒸餾到含水量在2000 ppra以下（基於1〇〇 重量％之金屬羧酸鹽溶液），即可製得含有Ln(RCOO)3結 構式之鑭系金屬羧酸鹽溶液。 基於提供做為二烯系單體聚合反應之觸媒用途，本發 明所製得含有Ln(RCOO)3結構式之讕系金屬羧酸鹽溶液， 其含水量不可超過2000 ppm，較佳為1500 ppm以下，更 佳在100 Oppm以下；當前述溶液之含水量高於20 0 0 ppm時 ’其使用於二烯系單體聚合時會造成活性降低，並且使得 二烯系單體之轉化率下降。 本發明所製得之鑭系金屬羧酸鹽可作為二烯系單體聚 合時之觸媒，前述二烯系單體可為丁二稀（butadiene)、 異戊間二烯（isoprene)、2 —笨基 丁二烯（2-phenyi b u t a d i e n e)、 2 ， 3 — 二甲基 丁二烤（2，3 - d i m e t h y 1 butadiene)、1 ，3 -己二烯（1, 3-hexadiene)，以及 1 ’ 3 —辛二稀（l，3-octadiene)等。 經濟部智慧財產局員工消费合作社印製 --------------裝--- (請先閱請背面之注惠事項再填寫本頁) 本發明之鑭系金屬羧酸鹽（1 )必需和烷基氣化鋁化合 物（2)(alkyl alum i num chloride compound)，以及有機 在呂 4b 合物（3 ) (organo aluminum compound)共用，作為二 烯系單體聚合之觸媒系統溶液。 上述烷基氣化鋁化合物（2)可在觸媒系統中使用，其 具有R2AlCl2、R23Al2Cl3以及R22A1C1等結構式，其中 為含有8到1 2個碟原子之煙’其典型的例子有直鏈及侧 第9頁 本紙張尺度適用中國國家標準（CNS)A4蜆格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 458964 A7 ____B7____ 五、發明說明（8 ) 鏈型式的脂肪族官能基，例如：辛基、二-乙己基（2-ethyi hexyl)、壬基、癸基、十一烷基、十二烷基以及類似物。 而具體的烷基氯化鋁化合物（2)沒有待別的限制，其較適 合的例子有：二辛基氯化鋁（dioctyl aluminum chloride) 、辛基倍半氣化鋁（octyl aluminum sesquichloride)、 辛基二氣化 IS (octyl aluminum dichloride )、二發基氣 化鋁（didecyl aluminum chloride ) '癸基倍半氣化鋁 (decyl aluminum sesquichloride)、癸基二氯化鋁（decyl aluminum dichloride)、二癸基氣化鋁（didodecyl alurainum chloride)、十二烷基倍半氯化鋁（dodecyl aluminum sesquichloride)、十二烷基二氯化鋁（dodecyl aluminum dichloride )及其類似物。除此之外，本發明 亦可使用：二曱基氣化銘（dimethyl aluminum chloride) 、二乙基氱化紹（diethyl aluminum chloride )、二乙基 漠化 ί呂（diethyl aluminum bromide)、二乙基姨化鋁 (diethyl aluminum iodide)、二乙基氟化鋁（diethyl aluminum fluoride)、二正丙基氣化銘（di-n-pr〇pyl aluminum chloride)、二正丁基氣化鋁（di-n-butylaluminum chloride)、二異丁 基氣化銘（di-isobutylaluminum chloride，簡稱 DIBAC)、甲基氣化鋁 (methylaluminum chloride)、氣化乙基ί呂（ethylaluminum chloride)、異丁基氣化紹（isobutylalum in um chloride) 、曱基倍半氣化銘（sesQuimethylaluminum chloride)、 乙基倍半氣化 is (sesquiethylalurainura chloride )、異 第10頁 本紙張尺度適用_國國家標準（CNS)A4規格（210 X 297公« ) --- - -- - ----· I I---- l· 訂•丨 — I!--- (請先閱讀背面之注意事項再填寫本頁) 8964 A7 B7 五、發明說明（9 ) (請先閱讀背面之;1意事項再填寫本頁) 丁 基倍半氣化紹（sesquiisobutylaluminum chloride)、 三氯化鋁（aluminuni trichloride)、三溴化鋁（aluminum tribromide、三蛾化鋁（alum 丨 num triiodide)、三氟化鋁 (aluminum tri fluoride)及其類似物，前述化合物可單獨 使用或者併用。以觸媒系統為優先考慮，該烷基氣化鋁化 合物（2)最佳為二異丁基氣化鋁（DIBAC)，在使用烷基氣 化鋁化合物（2 )當觸媒系統時，通常可加入溶劑，而配製 成含有院基氣化is化合物（2 )溶液。 本發明之有機鋁化合物（3)為具有R32A1H的結搆式 ，其中R為含有2到6個碳原子的烷基官能基，具體的有 機鋁化合物（3)沒有特別的限制，其可使用例如：二乙基 氫化鋁（diethyl aluminum hydride)、二丙基氫化銘 (dipropyl aluminum hydride)、二異丙基氫 匕 |g 經濟部智慧財產局員工消費合作社印製 (diisopropyl aluminum hydride)、二丁基氫化鋁（dibutyl aluminum hydride)、二異丁基氫化鋁（diisobutyl aluminum hydride，以下簡稱DIBAH)、二戊基氫化鋁 (dipentyl aluminum hydride)、二己基氫化鋁（dihexyl a 1 urai num hydr i de)及其類似物。以本觸媒系統為優先考 慮的因素，該有機鋁化合物（3)的具體代表例中，以二乙 基氫化鋁、二異丙基氩化鋁、二異丁基氫化鋁為較佳，尤 以二異丁基氫化鋁（DIBAH)為更佳；在使用有機鋁化合物 (3)當觸媒系統時，通常可加入溶劑，而配製成含有溶劑 之有機鋁化合物（3 )溶液。 為了達到高轉化率之二烯系聚合反應，上述觸媒的比 第11頁 本紙張尺度適用尹國囷家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 458964 五、發明說明（K)) 率必需加以限制，即鑭系金屬羧酸鹽（;丨）對烷基氣化鋁化 合物（2)及有機鋁化合物（3)二者之和的莫耳比[0)/(2) + (3)]為1 : 1 . 5〜1 : 1〇〇間，最好為1 : 1 .5〜 1 : 6 0的範圍，而鑭系金屬羧酸鹽（丨）與烷基氣化鋁化 合物（2)的莫耳比[(1)/(2)]控制在1 : . 5〜1 : 1〇 ’最好為1 : 1〜1 : 5 ，而鑭系金屬羧酸鹽（1)和有機 銘化合物（3)間的莫耳比[(1)/(3)]為1 : 1〜1 : 5 0 ’最好為1:2〜1:20;此外，本發明二烯系單體聚 合時’可依需要再加入適當的溶劑做為聚合的介質，適合 用來作為聚合媒介之惰性碳氫化合物包括有；脂肪族、環 脂族、芳香族以及單烯屬烴或其混合物；前述碳氫化合物 特別是選自於：含有4〜8個碳原子之脂肪族碳氫化合物 、含有5〜1 〇個碳原子之環狀脂肪族碳氫化合物、含有 6〜9個破原子之芳香族碳氫化合物、含有4〜8個碳原 子之單烯屬烴以及其混合物。上述碳氩化合物之實例包括 (但不限於）：丁烷、戊烷、己烷、庚烷、環戊烷、環己 烷、笨、甲笨、二甲苯、1一丁烯及1_戊烯。本發明之 方法中較佳係在一不含芳香烴之聚合媒介中進行，亦即， 本方法係在選自於下列之烴類中進行：c4〜％脂肪烴、c5 〜Cia。環脂烴及Cs〜Cg芳香烴、C4〜C8單烯屬烴及其混 合物’因為該觸媒系統在此一聚合媒介中展現了較佳之活 性。 用來作為聚合媒介之惰性烴’較佳係選自於己炫及環 己烧。 第12頁 本纸張尺度適用1f»國國家標準（CNS)A4规格（210 X 297公釐） — — — — — — — —--— I- ---- I I -----I · (請先閱讀背面之注意事項再填W?本頁) 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（11 ) 上述作為聚合二烯系單體的觸媒系統配置者包含：鑭 系金屬羧酸鹽π、# + ’各液、院基氣化銘化合物（2)溶液，以 及有，紹化合物（3)溶液與適當的溶劑混合搜拌均勻，而 觸媒系統配置的溫度受到溶劑的熔點及沸點限制，其範圍 需要控制在—2 0〜1 2 〇t為佳。而前述各觸媒在添加 夺可各另】加入，較佳則是先加入有機鋁化合物（3)及鑭系 金屬羧酸鹽（丨）’之後再加入烷基氣化鋁化合物（2)，若有 需要亦可在聚合反應之前，先將有機ί呂化合物（3)及鑭系 金屬羧酸鹽（1)混合在一起使用。 本發明在配置觸媒系統溶液時，可加入適量的共軛二 烯’以增加觸媒的活性，並且縮短觸媒在起始聚合階段的 誘導時間，而共輛二烯加入觸媒系統的時間可在各觸媒成 份加入之任何時間，使用量則以鑭系金屬羧酸鹽（丨）為基 準，即鑭系金屬羧酸鹽㈠）/共軛二烯之莫耳比=1 : 〇 〜1 · 1000 ’又以1 : 0 · 5〜丄：500為較佳， 最佳為1 · 2〜1 · 1〇〇，上述共耗二稀可為異戍間二 烯、丁二烯及1，3-戊二烯等。 二稀系單體聚合時，二#系單體可在觸媒力0人之称或 加入之後泵入反應槽内，或在一個觸媒及另一個觸媒添加 的時間内加入，其可一次加入反應，亦可分次加入。：發 明所使用之反應槽以附有攪拌設備者為佳，其可使用一個 或多個串聯之反應槽，當聚合完成達到某—轉化率時，需 加入觸媒去活化劑（deactivate agent)，例如水、乙醇等 。當殘留的觸媒以水或乙醇去除之後，使聚合完成的聚合 第13頁 - ----I I I I--- I I - I I 11 1 I I- ·1-11111!1 (請先閱讀背面之注意事項再填寫本頁> 458964 A7 -—------------ 五、發明說明（l2 ) 物再經過蒸發器及乾择击聰 C滞步騍，即可得到聚丁二烯橡膠，以 本發明所製得之鋼系金屬護酸鹽⑴進行丁二稀單體聚合 (請先閱讀背面之注意事項再填寫本頁) 時可付至1! μ 1，4-順式結構的丁二烯橡膠，前述i，4一順 式結構含量一般在95%以上。 為了更具想說明本發明，麦再以實施例及比較例加以 "兒明其中’實施例1〜了用以製造本發明之網系金屬叛 ㈣，而實施例8〜9則為利用上揭實施例製得之產品， 再進一步聚合二稀系單體之製造方法。 <實施例1 > 將〇.500kg(純度為99%，相當於146莫耳）之三氧化 一敍與2.100 kg(由Shell chemie公司出品，酸價為 3 2 4 ’相當於12.16莫耳）之新癸酸（以下以versatic acid表示）混合均勻’再加入3. 7〇〇 kg(相當於42. η莫 耳）之正-己烷（n-hexane)、2.100 kg(相當於116.7莫 經濟部智慧財產局員工消費合作社印製 耳）之水泵送入20公升的反應槽内，在反應溫度95 °C下 反應2. 5小時之後靜置3 Q分鐘’待其油相及水相分離完 成，此時油相及水相皆為澄清透明，反應器底部也沒有三 氧化二敛的沉殿物，然後將下層的水相排出，剩餘的上層 為含有Nd(Versatate)3及正-已烷的油相，最後再以蒸館 器將油相液體蒸餾，即可得到本發明之Nd(Versatate)3 溶液，其含水量為120 ppra’而Nd(Versatate)3的收率為 99.5¾ 。 <實施例2 > 第14頁 本紙張尺度適用中國國家標準（CNS)A4規格（2〗〇 x 297公4 ) A7 B7______ 五、發明說明（l3 ) 成份及反應條件大致相同於實施例1 ’不同之處在於 (請先閱讀背面之注意事項再填寫本頁> 將水由〈實施例1 >的2. 100 kg減少到1. 050 kg(相當 於58. 3莫耳），之後同樣將三氧化二鉉、versatic acid 及n-hexane泵送入20公升的反應槽内’在反應溫度95 °C下反應2. 5小時之後靜置6 0分鐘。同樣待油相及水相 分離完成，此時，油相及水相亦澄清透明’反應槽底部也 沒有三氧化二鈥的沉澱物，然後將下層的水相排出，剩餘 的上層亦含有Nd(Versatic)3的油相，之後以蒸餾器蒸餾 即可得到Nd(Versatate)3溶液，產物之含水量為220ppro ，而 Nd(Versatate)3 的收率為 95%。 <實施例3 > 成份及反應條件大致相同於 < 實施例1 > ’不同之處 在於將水（C)的使用量由原來的2. 100 kg增加到3. 47 kg ，如此水（C)的莫耳數增加為193，由於水的增加，使得 H20/Ln之莫耳比增加到66 : 1 ，經過相同的反應、靜 置條件，可製得含水量為280 ppm之Nd(Versatate)3溶 液’而 Nd(Versatate)3 的收率為 99.5%。 <實施例4 > 經濟部智慧財產局員Η消費合作社印製 如附表1所示，本實施例之反應成份、使用量及反應 條件大致相同於 < 實施例1 >，即將三氧化二鉉、vers at i c acid、n-hexane及水泵送入20公升的反應槽内，不同之 處在於：versatic acid之量改為1.44 kg(相當於8,76 莫耳）1在反應溫度95°C下反應2. 5小時之後靜置30分 鐘，待油相及水相分離完成，同樣將下層的水相排出’並 第15頁 本紙張尺度適用中國國家標準（CNS)A4規格<210 X 297公釐> 經濟部智慧財產局員工消費合作社印製 45 896 4 A? __ B7 五、發明說明（14 ) 將上層含有Nd(Versatate)3的油相蒸餾，即可得到 Nd(Versatate)3溶液產物，產物中的含水量為150 ppm， 而 Nd(Versatate)3 的收率為 98%。 〈實施例5 > 如附表1所示者，本實施例之反應成份、使用量及反 應條件大致相同於〈實施例1 >，差別在於將versatic acid之使用量由2. 100 kg增加到3. 000 kg，而使得 versatic acid/三氧化二钕間之莫耳比改變為6 / 1 ， 製得之Nd(Versatate)3溶液中其含水量為450 ppm，而 Nd(Versatate)3 的收率為 99.5%。 <實施例6 > 反應成份及使用量相同於<實施例1>，但在反應中 再加入1 0 ml的氣化氫溶液（35_ 5%)，之後在反應溫度80 °C下反應4. 0小時後靜置60分鐘，同樣可達到油相及水 相澄清透明之液體，反應槽底部也沒有三氧化二鉉的沉澱 物，之後同樣將下層水相排出，並將上層含有Nd(Ver-satate)3之油相蒸餾，即可得到含水量 500 ppm之The solution of Nd (Naph) 3, and then neutralize the ρ η of the solution with oxygen water, and then separate the water phase and the oil phase by > drop, and finally steam the teeth to obtain Nd (Naph) 3SOLUTION; Nd (Naph) 3 prepared by Changchun Institute of Chemistry, its free acid (ie, RC00H not combined with Nd) has a molar ratio of lanthanoid metal of 0.45 / 1 to 0.8 / 1 of In the meantime, the residual moisture is between 78 ~ 425 ρριη ', and the Nd (Naph) 3 prepared by this method is then combined with an aluminum alkylate and an organic compound to make a catalyst for the polymerization of succinic acid. In the system, the free acid is between 0.71 / 1 ~ 0.8 / 1 and the water content is between 138 ~ 287ppm. The polymerization conversion rate of this catalyst system is good. The common disadvantage of the two lanthanide metal carboxylate synthesis methods is that they need to be subjected to extraction, filtration, and other steps. Therefore, the synthesis steps are complicated and many production equipment are required. In addition, because sodium metal will remain in the product, the product must be re- After the purification step, the yield is reduced. In addition, U.S. Patent No. 5,220,045 discloses that nitric acid [Nd (N03) 3] 'neodecanoic acid and ammonia is added with a solution of cyclohexanine to stir reaction at room temperature' An NdV3 aqueous solution can be prepared, and then NdV3 compounds can be prepared by using water extraction and then removing water through distillation. This method requires complex extraction because of the need to use water during the synthesis process. In addition [Nd ( N03) 3] Compounds are not easy to obtain, which will be detrimental to production. · _ The inventor of this case has made intensive research and found that the lanthanide metal compound is directly reacted with the organic carboxylic acid solvent and a large amount of water to form an oil-water mixed lanthanide metal carboxylate mixed solution, and then the oil is passed through the sedimentation step Phase and Water Phase Division Page 4 This paper applies the national standard (CNS) A4 specification (2〗 0 X 297 mm) ----------------- {Please Read the notes on the back and fill in this page) Order · Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economics / 1 p; 4 A7 ___ B7. Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 'Afterwards, the water in the oil phase solution is removed by steaming, that is, a simple process can be performed under the condition of shortening the process time.' A lanthanide metal mate having a high yield is produced, which is produced by the present invention. Therefore, the main object of the present invention is to provide a method for manufacturing a steel-based metal carboxylate which has a simple process, a high product yield, and a high sedimentation rate, and can greatly shorten the process time, and a metal enemy prepared by the aforementioned method. Acid salt 'is used as a catalyst for polymerization of diene monomers with good activity. Europium is, the method for producing a lanthanide metal carboxylate according to the present invention is used to produce a product having the structural formula Ln (RCOO) 3, wherein l in the above structural formula represents a steel metal of the rare earth group, and the atomic number is between 57 ~ 71, which is selected from the group consisting of: 鐯, 钸, 鐯, 釓, lanthanum, and ytterbium, and R represents a hydrocarbon having 1 to 19 carbon atoms, and its main components include: (A) steel (Ln) metal Oxides; (B) organic carboxylic acids having 2 to 20 carbon atoms; (C) water; and (D) inert solvents, which are aliphatic, cyclic aliphatic, or have 6 to 20 carbons Atomic aromatic hydrocarbon; wherein the molar ratio of water to lanthanoid metal is 5: 1 or more, the above-mentioned lanthanoid metal oxide (A), organic carboxylic acid (B), water (C) and inert solution (D ) After the reaction at a temperature of G ~ 300 ° C, after the water phase and the oil phase separation step, the oil phase is distilled to a water content of less than 2000 ppm. In the present invention, the product obtained by the above-mentioned method for producing a lanthanide-based metal carboxylate is used as a catalyst in the polymerization reaction of diene-based monomers, thereby improving the conversion rate during the polymerization of diene-based monomers. Page 5 (Please read the notes on the back before filling this page) The paper size of the table is applicable to China National Standard (CNS) A4 (210 x 297 cm) A7 -------- B7__ ------- -5. Description of the invention (4) f Please read the note on the back *? Matters before filling out this page) The lanthanide metal oxide in the lanthanide metal oxide (A) of the present invention is an element of the rare earth group (rare earth) 'Its atomic order is between 5 7 and 71, and the elements in this range include cerium, praseodymium, neodymium, gadolinium, lanthanum, and samarium. Among them, neodymium is preferred, and the above elements may be mixed. Specific representative examples of the lanthanide-based metal oxide (A) of the present invention include: Dioxide (Nd 2 03) '11 hexadecyl oxide (ρΓί1〇ι6), dithium oxide (Ce203), dioxide Lanthanum (La203) and gadolinium trioxide (Gd203), etc., are taken into consideration in terms of the ease of obtaining the compound and the catalytic activity when used as a catalyst system, and neodymium trioxide is particularly preferred. The organic carboxylic acid (B) having 2 to 20 carbon atoms in the present invention is an aliphatic (a 1 i phat ic) renegade acid or a cycloaliphatic (cy c 1 oa 1 i phat ic) anti-acid or aromatic organic carboxylic acid. An acid having the following structural formula: R-C Ο Ο Η where R represents an alkyl group, a cycloalkyl group, an aromatic hydroxy group, an aralkyl group, and the like having 1 to 19 carbon atoms. Specific examples of the organic tantalum acid printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are: aceticacid, propionic acid, n-butyric acid, isobutyl acid acid), valeric acid, pivalic acid, hexane carboxylic acid, 2-hexane carboxylic acid, cyclohexane carboxylic acid ), 3-cyclohexyl propionic acid, 3-ethylhexyl propionic acid, 2-ethylhexane carboxylic acid, 2-methyl-1 2 ~ page 6 This paper applies Chinese national standards (CNS) ) A4 specification (210 * 297 public «) α6 89δ ^ at Β7 V. Description of the invention (5> 2-methyl-2-ethyl pentanoic acid, 2, 2-diethylvaleric acid (2, 2-diethyl pent anoic acid), 2,2-dimethyl hexanoic acid, 2-methyl-2-ethyl hexanoic acid, 2,2-diethylhexanoic acid (2,2- (1161 ± 7111. And 31101. & (: 1 (1), 2-B 2-ethy 1-2-propyl hexanoic acid, 2-ethyl 2-butyl hexanoic acid, 2, 2-diethyl Heptanoic acid (2,2-diethyl heptanoicacid), 2,2-diethyloctanoic acid (2,2- £ 1161; 1171〇 (^ 311〇1〇3. 1 (1), 2-methyl-1 2-butane 2-methyl-2-butyl octanoic acid, 1-heptanoic acid, 1-octane carboxlic acid, 1-nonane formic acid Printed by the Consumer Cooperative of the Property Bureau ------------- Installation -------: Order. (Please read the precautions on the back before filling this page) carboxlic acid), Xingui Acid (versatic acid, formally called neodecanoic acid, chemical formula: C9H19-C00H), dodecanoic acid (lauric acid), myristic acid, palmitic acid, octadecanoic acid ( stearic acid, oleic acid, benzoic acid, naphthenic acid, phenyl acetic acid, triphenyl acetic acid And tricyclohexyl acetate ohexyl acetic acid), a preferred example of which is: naphthenic acid 'neodecanoic acid and the like. The above organic carboxylic acids may be used alone or in combination. The molar ratio (ie, RCOOH / Ln) of the organic carboxylic acid (b) having 2 to 20 carbon atoms and the lanthanoid metal (Ln) used in the present invention is between 2/1 to 100/1, preferably 2 / 1 to 20/1, and more preferably 3/1 to 10/1. Page 7 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 458964 B7_____ V. Description of the invention (6) {Please read the precautions on the back before filling this page) The amount of water (C) used is more than 5/1 with the molar ratio dO / Ln of the lanthanide metal (Ln), that is, the present invention must use enough water to achieve the intended purpose; when both When the molar ratio is less than 5/1, the separation time of the oil phase and the water phase in the production method described later is lengthy, and the yield of the product is greatly reduced, and the reaction in the water phase and the oil phase after separation is incomplete, and there are many unsettled The reactants are mixed in and make the water phase and the oil phase appear cloudy, which is not conducive to the production of the entire process. In addition, the invention can also add acidic compounds such as gasified argon to water (C) to help the reaction as needed. The inert solvents (D) suitable for the invention are: aliphatic, cyclic aliphatic, or Aromatic hydrocarbons having 6 to 20 carbon atoms, of which aromatic cigarettes preferably contain 6 to 10 carbon atoms. Specific examples are: butane, pentane, hexane, heptane, octane Alkane, cyclopentane, cyclodecane, toluene 'and the comparative heterogeneous body (CorreSPonding iSomer) of the components just mentioned are preferably specific examples: n-hexane and cyclohexane. The above inert solvents (D) can be used alone or in combination, and the appropriate mixing ratio is determined by appropriate previous testing. The manufacturing method of the present invention is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The manufacturing method of the present invention is to lanthanide metal oxide (A), organic carboxylic acid (B) having 2 to 20 carbon atoms, water (c), and an inert solvent ( D) Pumped into the reaction tank according to an appropriate ratio, wherein the molar ratio between water and the lanthanide metal oxide (A) must be 5 / 丨 or more, and the reaction temperature is controlled to ◦ ~ 3 0 ° C 'is preferably 2 5 to 16 0 ° C, and the reaction time of stirring is from 0 · 1 to 8 hours, and a metal carboxylate [Ln (RC〇〇) 3] solution can be formed' and left to stand in the aqueous phase And oil phase separation, the separation time is several minutes to 2. Page 8 This paper size is applicable to China National Standard (CNS) A_4 specifications (210 X 297 mm) 4 5 8 9 6 4 A7 B7 V. Description of the invention (7) It can be completed within hours. At this time, the oil phase is above the water phase, and its demarcation point is clearly visible. There is no turbidity. The lower water phase is discharged ', and the oil phase containing the metal carboxylate is distilled to a water content of Below 2000 ppra (based on 100% by weight of a metal carboxylate solution), a lanthanide metal carboxylate containing the structural formula Ln (RCOO) 3 can be obtained Acid solution. Based on the use as a catalyst for the polymerization reaction of diene monomers, the hydrazone metal carboxylate solution containing the Ln (RCOO) 3 structural formula prepared by the present invention, the water content of which cannot exceed 2000 ppm, preferably 1500 Less than ppm, more preferably less than 100 Oppm; when the water content of the aforementioned solution is higher than 2000 ppm, its use in the polymerization of diene monomers will cause a decrease in activity and reduce the conversion of diene monomers. . The lanthanide metal carboxylate prepared by the present invention can be used as a catalyst for the polymerization of diene monomers. The diene monomers can be butadiene, isoprene, 2 —2-phenyi butadiene, 2, 3-dimethy 1 butadiene, 1, 3-hexadiene, and 1 '3--octadiene, etc. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ---------------------- (Please read the note on the back before filling this page) The lanthanide metal carboxylate of the present invention The acid salt (1) must be used in combination with the alkyl alum i num chloride compound (2) and the organic 4b compound (3) (organo aluminum compound) as a diene monomer. Catalyst system solution. The above-mentioned alkylated aluminum compound (2) can be used in a catalyst system. It has a structural formula such as R2AlCl2, R23Al2Cl3, and R22A1C1, among which is a smoke containing 8 to 12 disc atoms. Typical examples are straight-chain and The page size on this page applies to the Chinese National Standard (CNS) A4 grid (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 458964 A7 ____B7____ 5. Description of the invention (8) Chain-type aliphatic functions Groups, such as: octyl, 2-ethyi hexyl, nonyl, decyl, undecyl, dodecyl, and the like. The specific alkyl aluminum chloride compound (2) is not subject to other restrictions, and suitable examples thereof include: dioctyl aluminum chloride, octyl aluminum sesquichloride, Octyl aluminum dichloride, decyl aluminum chloride, decyl aluminum sesquichloride, decyl aluminum dichloride, two Didodecyl alurainum chloride, dodecyl aluminum sesquichloride, dodecyl aluminum dichloride, and the like. In addition, the present invention can also be used: dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl Diethyl aluminum iodide, diethyl aluminum fluoride, di-n-prOpyl aluminum chloride, di-n-butyl aluminum vapor -n-butylaluminum chloride), di-isobutylaluminum chloride (DIBAC), methylaluminum chloride, ethylaluminium chloride, isobutyl gasification Shao (isobutylalum in um chloride), sesquii methylaluminum chloride (sesQuimethylaluminum chloride), ethyl sesquigasification (sesquiethylalurainura chloride), different page 10 This paper is applicable to the national standard (CNS) A4 specifications ( 210 X 297 male «) ---------- · I I ---- l · Order • 丨 — I! --- (Please read the notes on the back before filling this page) 8964 A7 B7 V. Description of Invention (9) (This page) sesquiisobutylaluminum chloride, aluminuni trichloride, aluminum tribromide, alum num num triiodide, aluminum trifluoride fluoride) and its analogues, the aforementioned compounds can be used alone or in combination. Taking the catalyst system as a priority, the alkyl gasified aluminum compound (2) is most preferably diisobutyl aluminum gasified (DIBAC). When the base gasified aluminum compound (2) is used as a catalyst system, a solvent can usually be added to prepare a solution containing the base gasified is compound (2). The organoaluminum compound (3) of the present invention has a structural formula of R32A1H Wherein R is an alkyl functional group containing 2 to 6 carbon atoms, and the specific organoaluminum compound (3) is not particularly limited. For example, diethyl aluminum hydride, dipropyl hydrogenation can be used. Dipropyl aluminum hydride, diisopropyl hydrogen hydride | g Diisopropyl aluminum hydride, dibutyl aluminum hydride, diiso aluminum hydride Diisobutyl aluminum hydride (hereinafter referred to as DIBAH), dipentyl aluminum hydride, dihexyl a 1 urai num hydr i de, and the like. Taking this catalyst system as a priority factor, in the specific representative examples of the organoaluminum compound (3), diethylaluminum hydride, diisopropylaluminum argon hydride, and diisobutylaluminum hydride are preferred, especially Diisobutyl aluminum hydride (DIBAH) is more preferred; when an organoaluminum compound (3) is used as a catalyst system, a solvent can usually be added to prepare an organoaluminum compound (3) solution containing a solvent. In order to achieve high conversion of diene-based polymerization, the ratio of the above catalysts on page 11 is based on the Yin Guomin Family Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 458964 5. Explanation of the invention (K)) The rate must be limited, that is, the molar ratio of the lanthanide metal carboxylate (; 丨) to the sum of the alkylated aluminum compound (2) and the organoaluminum compound (3) [ 0) / (2) + (3)] is in the range of 1: 1. 5 to 1: 100, preferably in the range of 1: 1.5 to 1: 60, and the lanthanide metal carboxylate (丨) And the molar ratio [(1) / (2)] of the alkylated aluminum compound (2) is controlled to 1: 5 to 1: 10 ′, and it is preferably 1: 1 to 1 to 5, and the lanthanide The molar ratio [(1) / (3)] between the metal carboxylate (1) and the organic compound (3) is 1: 1 to 1: 5 0 'preferably 1: 2 to 1:20; When the diene monomer of the present invention is polymerized, an appropriate solvent may be added as a polymerization medium as needed. Inert hydrocarbons suitable for use as a polymerization medium include: aliphatic, cycloaliphatic, aromatic, and monomers. Olefinic hydrocarbons or mixtures thereof; Especially selected from: aliphatic hydrocarbons containing 4 to 8 carbon atoms, cyclic aliphatic hydrocarbons containing 5 to 10 carbon atoms, aromatic hydrocarbons containing 6 to 9 broken atoms , Monoolefins containing 4 to 8 carbon atoms, and mixtures thereof. Examples of the above argon compounds include, but are not limited to, butane, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, methylbenzene, xylene, 1-butene, and 1-pentene . The method of the present invention is preferably performed in a polymerization medium containing no aromatic hydrocarbons, that is, the method is performed in a hydrocarbon selected from the group consisting of c4 to% aliphatic hydrocarbons and c5 to Cia. Cycloaliphatic hydrocarbons and Cs ~ Cg aromatic hydrocarbons, C4 ~ C8 monoolefinic hydrocarbons and their mixtures' because the catalyst system exhibits better activity in this polymerization medium. The inert hydrocarbon ' used as a polymerization medium is preferably selected from the group consisting of hexane and cyclohexane. Page 12 This paper size is applicable to 1f »National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — I- ---- II ----- I · (Please read the precautions on the back before filling in this page?) A7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. A description of the invention (11) The above catalyst system configuration as a polymerized diene monomer includes: lanthanum Series metal carboxylates π, # + 'Each solution, the solution of the compound (2), and the compound (3) of the solution and the appropriate solvent are mixed and mixed uniformly, and the temperature of the catalyst system configuration is affected by The melting point and boiling point of the solvent are limited, and its range needs to be controlled within -20 to 12 ot. Each of the aforementioned catalysts can be added separately. It is preferable to add the organoaluminum compound (3) and the lanthanide metal carboxylate (丨) 'first, and then add the alkylated aluminum compound (2). If necessary, the organic compound (3) and the lanthanide metal carboxylate (1) may be mixed together before the polymerization reaction. In the configuration of the catalyst system solution of the present invention, an appropriate amount of conjugated diene 'can be added to increase the catalyst's activity and shorten the induction time of the catalyst in the initial polymerization stage, while the total time of the diene to be added to the catalyst system It can be used at any time when each catalyst component is added, and the amount used is based on the lanthanide metal carboxylate (丨), that is, the molar ratio of lanthanide metal carboxylate ㈠) / conjugated diene = 1: 〇 ~ 1 · 1000 'and 1: 0 · 5 to 500: 500 is more preferable, and the most preferable is 1 · 2 to 1 · 100. The above-mentioned total consumed dilutes may be isoprene, butadiene and 1 , 3-pentadiene, etc. When dilute monomers are polymerized, the # 2 monomers can be pumped into the reaction tank after the catalyst power is 0 or added, or it can be added at the same time when one catalyst and another catalyst are added. The reaction can be added in portions. : The reaction tank used in the invention is preferably equipped with stirring equipment. It can use one or more reaction tanks connected in series. When the polymerization reaches a certain conversion rate, a catalyst deactivating agent needs to be added. For example, water and ethanol. After the residual catalyst is removed with water or ethanol, the polymerization is completed. Page 13 ----- III I --- II-II 11 1 I I- · 1-11111! 1 (Please read the Matters needing attention to fill in this page > 458964 A7 ------------- V. Description of the invention (l2) After passing through the evaporator and dry-selecting Cong C stagnation, you can get Butadiene rubber can be polymerized with butadiene monomers by using the steel-based metal protecting salt prepared by the present invention (please read the precautions on the back before filling this page), and you can pay up to 1! Μ 1,4- For cis-structured butadiene rubbers, the content of the aforementioned i, 4-cis-structure is generally above 95%. In order to explain the present invention more, Mai Zai will use the examples and comparative examples to add "Example 1" ~ The manufacturing method of the net-based metal rebel of the present invention is used, and Examples 8 to 9 are the manufacturing methods of using the product prepared in the above-mentioned embodiment to further polymerize the dilute monomer. ≪ Example 1 > 0.50kg (99% purity, equivalent to 146 mol) of trioxide and 2.100 kg (produced by Shell chemie company, the acid value is 3 2 4 'equivalent to 12.16 mol The new capric acid (hereinafter expressed as versatic acid) is mixed well, and then 3.700 kg (equivalent to 42. ηmol) of n-hexane, 2.100 kg (equivalent to 116.7 mol) are added. The Ministry of Intellectual Property Bureau employee consumer cooperative printed ears) pumped into a 20 liter reaction tank and reacted at a reaction temperature of 95 ° C for 2.5 hours and then left to stand for 3 Q minutes after the oil phase and water phase were separated. At this time, the oil phase and the water phase are both clear and transparent, and there is no sanitary matter trapped in the bottom of the reactor, and then the lower water phase is discharged. The remaining upper layer contains Nd (Versatate) 3 and n-hexane. Finally, the oil phase liquid is distilled by a steamer to obtain the Nd (Versatate) 3 solution of the present invention, which has a water content of 120 ppra 'and a yield of Nd (Versatate) 3 of 99.5¾. Example 2 > page 14 This paper size applies the Chinese National Standard (CNS) A4 specification (2〗 〇x 297 公 4) A7 B7______ 5. Description of the invention (l3) The composition and reaction conditions are approximately the same as in Example 1 ' The difference is that (please read the precautions on the back before filling in this page> Example 1. > 2.100 kg was reduced to 1.050 kg (equivalent to 58.3 mol), and then dioxin trioxide, versatic acid and n-hexane were also pumped into a 20 liter reaction tank ' After reacting at a reaction temperature of 95 ° C for 2.5 hours, it was allowed to stand for 60 minutes. Similarly, after the separation of the oil phase and the water phase is completed, at this time, the oil phase and the water phase are also clear and transparent. There is no precipitate of trioxide 'at the bottom of the reaction tank, and then the lower water phase is discharged, and the remaining upper layer also contains Nd ( The oil phase of Versatic) 3 was then distilled with a distiller to obtain a Nd (Versatate) 3 solution. The water content of the product was 220 ppro and the yield of Nd (Versatate) 3 was 95%. < Example 3 > The composition and reaction conditions are substantially the same as < Example 1 > 'The difference is that the amount of water (C) used is increased from 2.100 kg to 3.47 kg, so water (C) The mole number is increased to 193. Due to the increase in water, the molar ratio of H20 / Ln is increased to 66: 1. After the same reaction and standing conditions, Nd with a water content of 280 ppm can be obtained ( Versatate) 3 solution 'and Nd (Versatate) 3 yield was 99.5%. < Example 4 > Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and a Consumer Cooperative, as shown in Table 1, the reaction components, usage amounts and reaction conditions of this example are approximately the same as < Example 1 >铉, vers at ic acid, n-hexane and water pumped into a 20 liter reaction tank, the difference is that the amount of versatic acid is changed to 1.44 kg (equivalent to 8,76 mol) 1 at a reaction temperature of 95 ° The reaction under C was left for 2.5 minutes and then left for 30 minutes. After the separation of the oil phase and the water phase was completed, the lower water phase was also drained out '. Page 15 This paper applies Chinese National Standard (CNS) A4 specifications < 210 X 297 mm > Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 45 896 4 A? __ B7 V. Description of the invention (14) Distilling the oil phase containing Nd (Versatate) 3 in the upper layer to obtain Nd (Versatate) 3 The solution product has a water content of 150 ppm, and the yield of Nd (Versatate) 3 is 98%. <Example 5 > As shown in Table 1, the reaction components, the amount of use and the reaction conditions of this example are approximately the same as those of <Example 1 >, the difference is that the amount of versatic acid used is increased from 2. 100 kg To 3.000 kg, and the molar ratio between versatic acid / neodymium trioxide is changed to 6/1, the water content of the prepared Nd (Versatate) 3 solution is 450 ppm, and the Nd (Versatate) 3 The yield was 99.5%. < Example 6 > The reaction components and usage amounts were the same as < Example 1 >, but 10 ml of a hydrogenated gas solution (35_5%) was added during the reaction, and then the reaction was performed at a reaction temperature of 80 ° C. 4. Let stand for 60 minutes after 0 hours. The oil and water phases are clear and transparent. The bottom of the reaction tank is also free of precipitates of trioxide. After that, the lower water phase is also discharged, and the upper layer contains Nd ( Ver-satate) 3 oil phase distillation can get 500 ppm water content
Nd(Versatate)3 溶液’上述 Nd(Versatate)3 的收率為 99¾ 〇 <實施例7 > 將0. 170 kg(相當於〇 5莫耳）之三氧化二鈦，與 0.760kg(相當於 4.07 莫耳）之環烷酸（Naphthenic acid ’酸價300)混合均勻’再加入3.400 kg(相當於43. 了莫 耳）之正-己烷、1.410 kg(相當於78_3莫耳）之水泵送入 第16頁 本紙張尺度適用+國國家標準（CNS)A4規格（210 * 297公釐） I--------- · I I I 丨 L 訂1·--I--〆的 (請先閱讀背面之注意事項再填寫本頁) A7 4 5 B 9 υ ^ ：· B7_____ 五、發明說明（15 ) (請先閱讀背面之注意事項再填寫本頁) 2〇公升的反應槽内，在反應溫度i5(rc下反應3小時之 後靜置1. 5小時’待其油相及水相分離完成，之後同樣排 出下層的水相’剩餘的上層則含有Nd(Naph)3及正己烧 的油相’之後以蒸餾器蒸餾即可得到Nd(Naph)3溶液，其 含水量為500 ppm，而Nd(Naph)3的收率為90%。 <比較例1 > 同 < 實施例1 >之操作步驟，但將2. 100 kg的水 (116.7莫耳）改為0.017 kg的水（0.9莫耳），亦即，將 HsO/U之莫耳比改為〇· 31/1，其餘操作條件不變，反應 之後’靜置長達1 5小時之後油相與水相雖然會分離，但 油相與水相呈現混濁狀態，在反應槽底部也產生沉 殿物’由沉澱物顯示反應不完全，因此必需將油相取出後 再以高速旋轉離心機處理，使油相中沉澱出Nd203等反應 不完全物質；之後將油相以蒸餾器蒸餾去除水份方可製得Nd (Versatate) 3 solution 'The yield of the above-mentioned Nd (Versatate) 3 was 99 ¾ 〈Example 7〉 0.170 kg (equivalent to 0.05 mole) of titanium dioxide was 0.760 kg (equivalent to Naphthenic acid (acid value 300) at 4.07 mol), mix well and add 3.400 kg (equivalent to 43. mol) of n-hexane, 1.410 kg (equivalent to 78_3 mol) of water pump Send to page 16 This paper is applicable to the paper size + National Standard (CNS) A4 specification (210 * 297 mm) I --------- · III 丨 L Order 1 · --I--〆 of ( Please read the precautions on the back before filling this page) A7 4 5 B 9 υ ^ ： · B7_____ V. Description of the invention (15) (Please read the precautions on the back before filling out this page) Inside the 20 liter reaction tank, At the reaction temperature i5 (3 hours after the reaction at rc, let stand for 1.5 hours. 'After the oil phase and the water phase are separated, the lower water phase is also discharged.' The remaining upper layer contains Nd (Naph) 3 and n-hexane. After the oil phase is distilled by a still, a Nd (Naph) 3 solution can be obtained, the water content of which is 500 ppm, and the yield of Nd (Naph) 3 is 90%. ≪ Comparative Example 1 > Same as < Example 1 > operation steps, but 2.100 kg of water (116.7 moles) was changed to 0.017 kg of water (0.9 moles), that is, the molar ratio of HsO / U to 0.31 / 1. The rest of the operating conditions remain the same. After the reaction, 'the oil phase and the water phase will separate after standing for 15 hours, but the oil phase and the water phase will appear turbid. The reaction showed incomplete reaction, so it was necessary to take out the oil phase and then treat it with a high-speed rotary centrifuge to precipitate the incomplete reaction materials such as Nd203 in the oil phase; then the oil phase was distilled to remove water by distillation.
Nd(Versatate)3溶液，溶液之含水量為280ppm，而 Nd(Versatate)3產物之收率為78%。 <比較例2 > 經濟部智慧財產局員工消費合作社印製 同 < 實施例4 >之操作步驟，但將2. 100 kg的水 (116.7莫耳）改為0.0072 kg的水（0.4莫耳），亦即，將 LO/Ln之莫耳比改為〇,丨4 :1，其餘操作條件不變，反應 元後靜置長達1 2小時後，油相與水相雖會分離，但油相 與水相仍呈現混濁狀態’在反應槽底部亦會有沉澱 物，因此必需將油相取出後並以高速旋轉離心機處理，使 油相中沉澱出Nd2〇3等反應不完全物質，即可製得未經蒸 第17頁 本紙張尺度適用中國S家標準（CNS)A4規格（210 X 297公爱） 8964 A7 ---- B7____ 五、發明說明（l6 ) (諳先閱讀背面之注意事項再填鸾本頁) 餾之NdCVersatate)3溶液，溶液中的含水量為1〇2〇〇 ppm ’而Nd(Versatate)3產物之收率為45% ;另取用此一 Nd(Versatate)3溶液進行如同後述〈實施例8 >之丁二烯 聚合’結果觸媒含水量高無法進行聚合反應a <實施例8 > 取 < 實施例1 >所製得之Nd(Versatate)3溶液 14. 900kg(相當於 〇.256 莫耳之 Nd(Versatate)3 ，與 66.270kg的二異丁基氫化鋁/正己烷（以下簡稱D〖BAH/n_ hexane溶液，相當於dibah 83 6莫耳）及2〇, 54公斤 的一異丁基氣化鋁/正一己烷（DIBAC/n-hexane)溶液（相 當於DIBAC 20.9莫耳），搜拌混合均勻後，即可製得觸媒 系統溶液。 爾後將10. 73kg(相當於198莫耳）的ι，3-丁二烯單體 經濟部智慧財岌局員工消費合作社印製 置於200公升的反應槽中，上述丨，3_ 丁二烯單體係經過 蒸餾純化至含水量在2 ppm以下，而觸媒配製或聚合反應 中所使用的正-己烷皆經過蒸餾純化，使其含水量皆在 2ppm以下，使用之反應槽内則附有攪拌器及冷卻系統， 之後再於反應槽中加入82.23 kg (相當於954莫耳）的正-己院’以及0. 678 kg的觸媒系統溶液進行反應，反應之 溫度乃控制在90t ,且攪拌反應時間為丨〇〇分鐘，當反 應完成後使聚合物溶液經由蒸發器蒸發、乾燥步驟，即可 得到1，4-順式聚丁二烯產物，上述產物中的丨，4_順式結 構在98%’測得的丁二烯之轉化率為95%，木尼黏度（m〇〇ney viscosty)為 40 。 第18頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）The Nd (Versatate) 3 solution has a water content of 280 ppm, and the yield of the Nd (Versatate) 3 product is 78%. < Comparative Example 2 > The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the same procedures as < Example 4 >, but changed 2.100 kg of water (116.7 mol) to 0.0072 kg of water (0.4 Moore), that is, the molar ratio of LO / Ln is changed to 〇, 丨 4: 1, the remaining operating conditions remain unchanged, and the oil phase and the water phase will separate after standing for 12 hours. However, the oil phase and the water phase are still turbid. 'There will also be precipitates at the bottom of the reaction tank. Therefore, it is necessary to remove the oil phase and treat it with a high-speed rotary centrifuge to precipitate Nd203 in the oil phase and the reaction is not complete. Substances can be made without steaming. Page 17 This paper is sized for China Standards (CNS) A4 (210 X 297). 8964 A7 ---- B7____ 5. Description of the invention (l6) (谙 Read first Note on the back of this page, please fill in this page) Distilled NdCVersatate) 3 solution, the water content in the solution is 10200ppm ', and the yield of Nd (Versatate) 3 product is 45%; another Nd (Versatate) 3 solution was subjected to butadiene polymerization as described later in Example 8 > as a result, the catalyst had a high water content and could not proceed with the polymerization reactiona < Example 8 > Take the obtained Nd (Versatate) 3 solution 14.900kg (equivalent to 0.256 mol Nd (Versatate) 3) and 66.270kg of diisobutyl Aluminum hydride / n-hexane (hereinafter abbreviated as D 〖BAH / n_hexane solution, equivalent to dibah 83 6 mol) and 2,54 kg of monoisobutyl aluminum vaporized / n-hexane (DIBAC / n-hexane) Solution (equivalent to DIBAC 20.9 mol), after searching and mixing, the catalyst system solution can be prepared. Then 10.73kg (equivalent to 198 mol) of ι, 3-butadiene monomer Ministry of Economic Affairs wisdom It is printed in a 200-litre reaction tank by the Finance and Economics Bureau's Consumer Cooperative. The above-mentioned 3, butadiene single system is purified by distillation to a moisture content of less than 2 ppm. -Hexane is purified by distillation to make the water content below 2ppm. The reaction tank used is equipped with a stirrer and cooling system, and then 82.23 kg (equivalent to 954 mol) is added to the reaction tank. Jiyuan 'and 0. 678 kg of catalyst system solution were reacted, the reaction temperature was controlled at 90t, and the reaction was stirred The time is 丨 00 minutes. After the reaction is completed, the polymer solution is evaporated and dried through an evaporator to obtain a 1,4-cis-polybutadiene product. The conversion of butadiene measured at 98% 'was 95% and the muni viscosity (money viscosty) was 40. P.18 This paper is sized for China National Standard (CNS) A4 (210 x 297 mm)
經濟部智慧財產局員工消費合作社印*'1衣 五、發明說明（17 ) <實施例9 > 取< 實施例4>製備之Nd(Versatate)3溶液4〇 27 kg[相當於 Nd(Versatate)3 0.7 莫耳]，與 DIBAH 溶液（相 當於70莫耳之DIBAH)55‘27 kg及20.54公斤的DIBAC/ η-hexane溶液（相當於DIBAC 20.9莫耳），授拌混合均 勻後’即可製得觸媒系統溶液。 之後將10_ 73kg(相當於198莫耳）的丨，3-丁二烤單體 置於200 kg的反應槽中，上述ι，3-丁二烯單體、觸媒配 製以及聚合反應中使用的正-已烧’皆經過蒸餾純化，其 含水量皆在2ppm以下，使用之反應槽内同樣附有搜拌器 及冷卻系統。之後再於反應槽中加入82 23 kg(相當於954 莫耳）的正，己烷，以及0· 71 kg的觸媒系統溶液，反應 溫度則控制在95乞，且攪拌反應時間為丨丨〇分鐘，當反 應完成後同樣使聚合物溶液經由蒸發器蒸發、乾燥步驟， 即可得到1，4-順式聚丁二烯產物，上述產物中的丨，4_順 式結構在98%，測得丁二烯之轉化率為94% ，木尼黏度為 42 0 綜上所述’由前述各實施例與比較例之說明可知，本 發明在鋼系金屬乳化物中加入溶劑及大量的水，並使水和 鋼系金層間的莫耳比大於5/1 1將可使反應完全，收率 提高’油相與水相快速的分離，並且省略了離心處理的步 鄉；因此’本發明前述製造方法的創新，瑞實可以更為巧 單快速的製程’來製造出高收率之產物；前述產物運用在 二稀系單體的聚合反應中’亦可提高單體之反應速率，因Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * '1. V. Invention Description (17) < Example 9 > Take < Example 4 > Nd (Versatate) 3 solution prepared 407 kg [equivalent to Nd (Versatate) 3 0.7 mol], and mixed with DIBAH solution (equivalent to 70 mol DIBAH) 55'27 kg and 20.54 kg of DIBAC / η-hexane solution (equivalent to DIBAC 20.9 mol), The catalyst system solution can be obtained. After that, 10_73kg (equivalent to 198 moles) of 丨, 3-butadiene roasted monomer was placed in a 200 kg reaction tank. The above-mentioned ι, 3-butadiene monomer, catalyst preparation, and polymerization reaction were used. "Zheng-burned" is purified by distillation, and its water content is below 2ppm. The reaction tank used is also equipped with a stirrer and cooling system. After that, 82 23 kg (equivalent to 954 mol) of n-, hexane, and 0.71 kg of the catalyst system solution were added to the reaction tank, the reaction temperature was controlled at 95 ° C, and the stirring reaction time was 丨 丨 〇 After the reaction is completed, the polymer solution is also evaporated and dried through an evaporator to obtain a 1,4-cis polybutadiene product. The above-mentioned product has a cis and 4-cis structure at 98%. The conversion of butadiene was 94%, and the viscosity of Muni was 42. In summary, from the description of the foregoing examples and comparative examples, it can be known that the present invention adds a solvent and a large amount of water to the steel-based metal emulsion. Making the molar ratio between water and steel-based gold layers greater than 5/1 1 will make the reaction complete and increase the yield. 'The oil phase and the water phase are quickly separated, and the step of centrifugation is omitted. Therefore,' the foregoing of the present invention The innovation of the manufacturing method allows Rui Shi to use a more simple and rapid process to produce high-yield products; the aforementioned products are used in the polymerization of dilute monomers and can also increase the reaction rate of monomers, because
第19 I 本纸張尺度適用尹國國家標準（CNS)A4規格（210 X 297公釐） -------------- - - - - ---^訂-------I I (請先閱讀背面之沒意事項再填寫本頁) 458964 A7 B7 五、發明說明（is ) 此’本發明確為一創新之製造方法，並可供產業上利用。 淮以上所述僅為本發明數較佳可行實施例，舉凡熟悉 此項技藝人仕，其依本發明精神範疇所做之修飾或變更， 均理應包含在本案申請專利範圍内。 附表一：本發明之實施例〜7以及比軾例 、反應條件及產物内容比较表a 2的成份 -------------裝--------L訂· (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 頁 20 第 本紙張尺度適用中國國家標準（CNS)A4規格（210 * 297公爱）The 19th paper size applies the Yin National Standard (CNS) A4 specification (210 X 297 mm) --------------------- ^ order --- ---- II (Please read the unintentional matter on the back before filling this page) 458964 A7 B7 V. Description of the Invention (is) This invention is indeed an innovative manufacturing method and can be used in industry. The above descriptions are only a few of the preferred embodiments of the present invention. For those skilled in the art, any modifications or changes made according to the spirit of the present invention should be included in the scope of patent application in this case. Attached Table 1: Examples 7 to 7 of the present invention, comparison examples, reaction conditions, and product content comparison Table a 2 components ------------------------- L Order · (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Page 20 This paper size applies to the Chinese National Standard (CNS) A4 (210 * 297).