200920696 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種以不同陰離子交換四級烷基銨鹽的 陰離子的方法，更特別係關於經由以不溶性金屬溴化物之 形式移除溴化物離子，來以不同陰離子交換四級四烷基銨 溴化物的溴離子之方法。 【先前技術】 四級銨鹽（Quat)不精確地定義是一化合物之族群，其 將一個氮原子連接至四個有機原子團。由於四級銨化合物 中氮原子上之淨正電荷，時常發現四級銨鹽與一或多個陰 離子相締合。締合之陰離子稱爲平衡離子，而四級銨化合 物和陰離子的組合稱爲四級銨鹽。 四級銨鹽是多種組別的化合物，它不但在木料防腐/殺 生物劑工業方面獲得利用，而且利用於此等工業例如護髮 產物、清潔產物、織物軟化劑、藥物、界面活性劑、除臭 劑、漱口劑、防腐劑、乳化劑、化妝品及採礦業。其中， 四級銨鹽化合物的使用通常記述於美國專利 Nos.3,301，815、3，366,672、4,365,030 和 4,444,790 中。 製造四級銨鹽化合物之方法爲該技藝中普遍熟知。基 本化學教科書教導：氨或胺與烷基鹵化物的反應之最後產 物是四級銨鹽。例如，參閱 Noller，C.R·，Textbook of Organic Chemistry 1 2nd Ed，p . 1 8 8 e t s e q .，W.B.Saunders Co，Philadelphia( 1961)，及 March，J_，Advanced Organic200920696 IX. DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a process for the exchange of anions of quaternary alkyl ammonium salts with different anions, more particularly with respect to removal of bromide ions by insoluble metal bromide , a method of exchanging bromide ions of a quaternary tetraalkylammonium bromide with different anions. [Prior Art] A quaternary ammonium salt (Quat) is not precisely defined as a group of compounds which connects a nitrogen atom to four organic atomic groups. Due to the net positive charge on the nitrogen atom in the quaternary ammonium compound, it is often found that the quaternary ammonium salt is associated with one or more anions. The associated anion is called a counterion, and the combination of a quaternary ammonium compound and an anion is called a quaternary ammonium salt. Quaternary ammonium salts are compounds of various groups that are utilized not only in the wood preservative/biocide industry, but also in such industries as hair care products, cleaning products, fabric softeners, drugs, surfactants, Odors, mouthwashes, preservatives, emulsifiers, cosmetics and mining. The use of the quaternary ammonium salt compound is generally described in U.S. Patent Nos. 3,301,815, 3,366,672, 4,365,030 and 4,444,790. Methods of making quaternary ammonium salt compounds are well known in the art. Basic chemistry textbooks teach that the final product of the reaction of ammonia or an amine with an alkyl halide is a quaternary ammonium salt. See, for example, Noller, C.R., Textbook of Organic Chemistry 1 2nd Ed, p. 1 8 8 e t s e q ., W.B. Saunders Co, Philadelphia (1961), and March, J_, Advanced Organic
Chemistry > 3rd Ed.’ pp.364、365，John Wiley & Sons，New 200920696Chemistry > 3rd Ed.’ pp.364, 365, John Wiley & Sons, New 200920696
York ( 1985 )。甚多之其他公開案舉例而言美國專利案 Nos.5,3 0 8,3 6 3 ' 5,4 3 8,0 3 4 ' 5,5 23,48 7 ' 5,8 5 5,8 1 7 、 6,784,317、 6,090,855、 6,485,790及美國專利申請案公告 2 0 0 3 /002 3 1 0 8中報告製造具有特別類型的取代基及特別平 衡離子之四級銨鹽的特定方法。 即便由已知用於製造四級銨鹽之方法之觀點來看，還 是有改良用於製造四級銨鹽方法之需要，尤其是商業上可 應用之方法。 本發明經由提供間接合成方法來滿足上述需要，可使 用該間接合成方法來製備各種的四（匕至C2。）烷基或芳基 取代之烷基四級銨碳酸鹽及碳酸氫鹽化合物，例如，二 C )二甲基烷基四級銨碳酸鹽和碳酸氫鹽化合物。本 發明的方法包括（a )組合至少四（C 1至C 2 〇 )烷基或芳基 取代之院基四級溴化銨、金屬氫氧化物及具有每1 〇 〇 〇克溶 劑’少於約1克金屬溴化物的溶解度之溶劑，該金屬氫氧 化物係相對於四級溴化銨在化學計量上過量以產生至少四 c c,至C 2。）烷基或芳基取代之烷基四級銨 氫氧化物；及（b )組合至少該四（C,至C2。）烷基或 方基取代之烷基四級銨氫氧化物和二氧化碳以產生至少該 四（匕至c2〇)烷基或芳基取代之烷基四級銨碳酸鹽。 【發明內容】 申請人之方法可大致舉例說明如下： 200920696 (I)· x[(R1R2R3R4N)+]Br'+ 過量 M(OH)x + R5OH x[(R1R2R3R4N)+]OH+MBrx+ 殘餘 M(OH)x+R5OH;及 (II}- [(r1r2r3r4n)+]oh-+ 殘餘 M(OH)X + C02 + R5OH —> [(R1R2R3R4N)+]HC03_ + [(R1R2R3R4N)+]2C〇32'+ M2(C03)x+ r5〇h , 其中（I)式中之MBrjl] (II)式中之M2(C〇3) X沉 殿於溶劑R5OH中，並經由例如，過濾移除；各R1、R2、 R3和R4獨立的爲C!至C2。烷基或芳基取代之烷基（例如， R1和R2可爲不同之C8-C12烷基及R3和R4各可爲甲基等 等）烷基，Μ是單、二或三價金屬，或是 鹼金屬；如果Μ是單價，X是1;如果Μ是二價，X是2; 如果Μ是三價，X是3。因此，鹼金屬像Na或Κ，X是1。 可將（^至C2。烷基或芳基取代之烷基、C,至C2。烷基 或芳基取代之烷基、二甲基四級溴化銨與在化學計量上過 量之金屬氫氧化物於適當溶劑中組合，適當溶劑例如具有 每丨0 0 0克溶劑少於約1克金屬溴化物的溶解度之溶劑，而 在i谷劑中產生Cl至C2。院基或芳基取代之院基、Cl至C2。 烷基或芳基取代之烷基、二甲基四級銨氫氧化物中間物溶 液。然後將羥基四級銨鹽中間物和溶液中殘餘金屬氫氧化 物與二氧化碳組合而產生四級銨碳酸鹽/碳酸氫鹽及不溶 性金屬碳酸鹽。適當溶劑包括R5 〇 Η醇類例如，甲醇、乙醇、 異丙醇、丙醇、異丁醇及其他C,至C 6醇。 具有任何所需要陰離子之四烷銨鹽（例如，磷酸鹽、 乙酸鹽、水楊酸鹽、草酸鹽、氯化物等）可經由氫氧化銨 中間體與相對應之酸組合來製備。 200920696 許多（^至C2。烷基或芳基取代之烷基、（^至c2。烷基 或芳基取代之烷基、二甲基四級銨溴化物是製備羥基四級 銨鹽中間體之適當反應物’例如二癸基二甲銨溴化物係適 合的。溴化四級銨鹽反應物的R 1和R2取代基之選擇是羥基 四級銨鹽中間物之決定因素，而因此是碳酸鹽四級銨鹽產 物的決定因素。許多其他四烷基四級溴化銨亦適合使用於 本發明中，如已知本文內容教旨的利益之精於該技藝者可 能熟知。 例示之方法是那些其中R1是甲基、C8烷基、CN異烷基、 G。烷基、Cl2烷基、Cm烷基、C16烷基或苯甲基；R2是已。 烷基、Cl2烷基、C“烷基或C16烷基：及R3和R4之各是甲 基。 金屬氫氧化物反應物可爲單，二或三價金屬氫氧化物 或是鹼金屬氫氧化物例如氫氧化鈉或氫氧化鉀。金屬溴化 物第一步驟反應產物可沉殿且經由過濾或類似方法可輕易 移除，產生羥基四級銨鹽/溶劑反應產物。若需要，羥基四 級銨鹽可經由乾燥或類似方法自其中分離。 第一反應（I)可在溶劑中實施，溶劑包括Chq醇， 例如乙醇或無水乙醇。形成羥基四級銨鹽之反應典型是平 衡反應’但是醇溶劑之使用快速地驅使該反應成爲 羥基四級銨鹽。 金屬氫氧化物反應物的數量可爲相對於四烷基四級溴 化銨反應物之化學計量數量。因此，在理論基礎上，如果 反應是完全且不平衡，於完成中間反應時，將不會有過量 200920696 的金屬氫氧化物反應物。實際上，當使用化學計 金屬氫氧化物反應物時，產量範圍將自約6 5 %至 但是部分將基於各金屬氧化物反應物而變更。 經由利用範圍自約2%至約50%過量之化學 的金屬氫氧化物，可將羥基四級銨鹽的產量較習 一步改良。如果使用過量之金屬氫氧化物，產量 約9 5 %至約9 9 %，如上述，再變更。 未起反應之金屬氫氧化物可溶於羥基四級| 中間物中。 然後可使羥基四級銨鹽和任何未起反應之金 物與至少化學計量等量的二氧化碳起反應而產生 酸鹽，及如果存在任何未起反應之金屬氫氧化物 金屬碳酸鹽。兩種碳酸化作用中轉化金屬氫氧化 屬碳酸鹽’係進行的最快。金屬碳酸鹽可沉澱且 濾或類似方式輕易地分離，留下穩定的四級銨碳丨 氫鹽或四級銨碳酸鹽/溶劑反應產物。 如所舉例說明，該碳酸化步驟亦產生四級銨 作爲副產物。單獨四級銨碳酸鹽或與四級銨碳酸 適合使用於例如木料防腐系統中。此等四級銨碳 級銨碳酸鹽/碳酸氫鹽組成物不需要金屬親合劑 基體之穩定化。木料防腐系統可不含金屬。 本發明中組份的混合，添加，組合及反應可 精於該技藝者所熟知之習用方法予以實現。任何 中反應物或溶劑的添加順序並不影響方法或程序 量數量的 約 95%， sT里過里 用方法進 將增加自 交鹽/溶劑 屬氫氧化 四級銨碳 ，則產生 物成爲金 可經由過 俊鹽/碳酸 碳酸氫鹽 氫鹽組合 酸鹽或四 用於木料 經由通常 個別步驟 。可將反 -9- 200920696 應物及/或溶劑連續或同時加至任何適當反應容器中。例 如，可將金屬氫氧化物溶入醇中並將所產生之混合物加至 溴化物四級銨鹽或可將溴化物四級銨鹽溶入醇中及將金屬 氫氧化物加至所產生之混合物。重要的是，本發明的方法 適合於商業規模製造技術和設備，尙能便利於小規模操作。 典型，將溴化物四級銨鹽成爲羥基四級銨鹽反應（I) 的反應物和溶劑攪拌並加熱自約2 0 °C至約7 〇 °C及維持在該 溫度歷約1小時至約5小時之一段時間。然後冷卻反應混 C 合物，首先至室溫然後至約οπ，將它維持在此溫度歷約1 小時至約2小時。如該技藝中所熟知，將任何沉澱金屬溴 化物例如經由過濾來收集。 根據本發明，例示之步驟包括製造四級銨氫氧化物溶 液，其方式係由使用KOH處理四級銨溴化物溶液並沈澱 KBr，及轉化溶液中之四級銨氫氧化物成爲碳酸氫鹽/碳酸 鹽。自四級銨氫氧化物中間物，可製備數種其他四級銨鹽 類（即，磷酸鹽、羧酸鹽、其他鹵化物等）。可使用1 -或 1 2 - 丁醇作爲用於製造四級溴化銨溶液之溶劑且爲了得到低 溴値，可將水自丁醇之KOH溶液中移出。當將水自KOH 的丁醇溶液中汽提出時，形成KOBu。將乾燥之KOH溶液 與次化學計量數量（1.5莫耳KOH/莫耳溴化物）的四級溴 化銨溶液混合來沈澱KBr。然後將四級銨丁氧化物/氫氧化 物溶液用 C〇2氣體處理而獲得丁醇中之碳酸四級銨鹽 (carboquat)(碳酸鹽/碳酸氫鹽/碳酸丁酯）溶液。使用C〇2 處理，將氫氧化銨溶液中之過量KOH/KOBu沈澱成爲碳酸 -10- 200920696 鹽並由過爐移出。起始不使用水，然後使用水，將來自碳 酸四級銨鹽溶液之丁醇汽提出，使用少量的5 〇 % H 2 〇 2處理 來使黃色溶液脫色。然後可將所產生之透明碳酸四級銨鹽 溶液（碳酸鹽/碳酸氫鹽）使用充分的水和i，2 -丙二醇稀釋 來符合所需要之規格。 因此’本發明的一個態樣，提供用於製備具有低鹵化 物和良好顏色之約50%水相四烷基或芳基取代 之院基取代之四級鏡碳酸鹽溶液之方法。該方法包括：（i ) 自癸基二甲胺和1-溴癸烷於C4醇中四級銨溴溶液，（U ) 自包括多於1莫耳的KOH/莫耳的四級銨鹽之丁醇溶液以適 當羥例如己烷共沸移除水’（i i i )組合來自（i)之四級溴化銨 溶液及來自（ii)之丁醇溶液並經由例如過濾移除沈澱之 KBr, (iv)將C02氣體吹泡通過（iii)中所獲得之溶液，在 自過量KOH中移除沈澱之固體粒子後獲得丁醇中之碳酸四 級銨鹽溶液，及（v )溶劑交換碳酸四級銨鹽溶液自丁醇至 水，接著添加1 - 5 %過氧化氫。爲獲得低鹵化物和良好顏色 所使用之步驟包括：（a )使用C4醇作爲溶劑，（b )自醇 的KOH溶液移除水及（c )使用過氧化氫將碳酸四級銨鹽 溶液脫色。 【實施方式】 下列實例是本發明原理的舉例說明。應了解：本發明 並不受限爲本文中所例示之任何一個特定實施例，無論其 在實例中或在此專利申請案中其餘者。 -11- 200920696 - 實例1 -四級鉉溴化物溶液之製備 將93g(0.5莫耳）的N，N-二甲基癸胺，lllg(0.5莫 耳）的1 -溴癸烷和1 3 5 g的卜丁醇之混合物倒至配置冷凝 器之乾5〇〇ml燒瓶中。使用電罩將混合物加熱至回流。4 小時後停止加熱。分析四級銨溴化物的透明淡黃色溶液。 分析顯示12.7wt%溴、0.19 wt%自由胺和59.4 wt%四級銨 〇 將65g的2 -丁醇中，93.5g(0.5莫耳）的癸基二甲胺 f 溶液置入燒瓶中及加熱至1 〇 5 t並磁性攪拌。於2小時內， 逐滴添加1-溴癸烷（1 1 1 .5g )並將混合物在105 t時加熱 歷另外4小時。分析透明黃色溶液（269g )發現具有70.6wt %四級銨鹽、1 3.2 7 wt %溴和0.8 8 wt %自由胺。 實例2 -丁醇中烷基四級銨溶液的製備 將含有約15 wt%水，50g之1-丁醇和25g己烷之10g (150mmol )的氫氧化鉀粒片加至2 5 0ml燒瓶中。將該燒 瓶配置Dean-Stark阱及回流冷凝器。將混合物回流並將成 ^ 爲共沸液被移出之水收集在阱中。將混合物回流直至阱中 之水相沒有增加。在周圍溫度時將60g (約90 mmol )之四 級銨溴化物溶液逐滴加至此溶液並予以磁性攪拌。然後將 混合物在冰浴中冷卻歷1小時。將所沈澱之固體粒子在吸 力下過濾並用20ml己烷洗滌。再度過濾略呈混濁濾液而獲 得透明溶液。將C 0 2氣體吹泡通過此溶液歷1小時。將所 沈澱之固體粒子經由通過Whatman濾紙過瀘而移除’獲得 100g的1-丁醇中烷基四級銨之透明黃色溶液。分析顯示該 -12- 200920696 烷基四級銨溶液具有33.2%四級銨鹽和3 4 5ppm之溴。 實例3-烷基四級鋳7k溶液之製備 將含2 3 0 p p m溴之1 - 丁醇中碳酸四級銨鹽溶液（3 4 · 8 wt %)的l〇6g樣品置入500ml燒瓶中並在7〇°C於真空下使 用旋轉蒸發器濃縮至約60g。將去離子水（40g)和1，2-丙 二醇（6 g )加至該混合物並使用旋轉蒸發器濃縮至約6 5 2 ° 重複三次用40g水稀釋並濃縮至約65g。將所產生之蒼黃 色溶液與3 g的5 0 wt %過氧化氫溶液混合並用水稀釋至 74g。所獲得之透明無色溶液具有1的Gardner色値並含 2 94ppm溴（1 30ppm係氯）及5 1 .Owt%四級銨鹽。碳酸四 級銨鹽之明細：四級銨鹽=48.5至5 1 .5 wt% ; Gardner色値 是=< 4 ;鹵化物=< 3 0 0 p p m係氯化物。 應了解者，本說明書或關於此之申請專利範圍中無論 何處，經由化學名稱或化學式所述及之反應物和成分，無 論以單數或複數述及，經識別爲彼等係在與經由化學名稱 或化學型式所述及之另外物質（例如另外反應物，溶劑等） 聯合或開始與彼等接觸前就存在。它與所產生之聯合或溶 液或反應介質中產生（如果有）之化學改變，轉變及/或反 應無關，因爲此等改變轉變及/或反應是在依據本文內容所 要求之條件下，將特定反應物及/或成分集合在一起的自然 結果。 因此，將反應物和成分識別爲與實施所需要之化學反 應相關連或於形成被使用於導引所需要反應之聯合時被集 合在一起之成分。因此，即使下文之申請專利範圍可能以 -13- 200920696 現在時態（“comprises”，“is” ）等述及物質組分及/或成 分’該論述係述及物質組分或成分之狀態如同它依照本發 明內容’恰在它與一或多種其他物質組分及/或成分首次接 觸’聯合摻合或混合前之時間就存在。無論什麼轉變，如 果有，當實施一種反應時它就地發生者是申請專利範圍意 欲涵蓋之項目。因此’事實是在接觸，聯合，摻合或混合 等操作過程期間’一種物質’組分或成分通過化學反應或 轉變可能失去原來屬性’因此如果依照此文內容及連同應 用常識和化學家之通常技藝予以實施。關於正確了解和評 價此文內容及其申請專利範圍的真正意義要旨完全是不重 要。如爲精於該技藝人士所熟悉，如本文中所使用者，術 語「組合的」、「正組合」等係意指將「被組合」或「正 組合」之各組分相互置放一入容器中。同樣地，各組分的 “組合”係指將各組分放置在一起在一個容器中。 雖然本發明已經以一或多個較佳實施例予以敘述，但 是應了解只要不脫離本發明的範圍（其在下列申請專利範 圍中特舉出）可作成其他變更。 【圖式簡單說明】 iffi 。 【主要元件符號說明】 無。 -14-York (1985). A number of other publications are exemplified by the US Patent Nos. 5, 3 0 8, 3 6 3 ' 5, 4 3 8, 0 3 4 ' 5, 5 23, 48 7 ' 5, 8 5 5, 8 1 A specific method for making a quaternary ammonium salt having a particular type of substituent and a particular counterion is reported in U.S. Patent Nos. 6,784,317, 6, 090, 855, 6, 485, 790, and U.S. Patent Application Serial No. 2 0 0 3 /002 3 1 0 8 . Even from the viewpoint of a method known for producing a quaternary ammonium salt, there is a need to improve the method for producing a quaternary ammonium salt, especially a commercially applicable method. The present invention satisfies the above needs by providing an indirect synthesis method which can be used to prepare various tetra(anthracene to C2.) alkyl or aryl substituted alkyl quaternary ammonium carbonate and bicarbonate compounds, for example, , di C ) dimethylalkyl quaternary ammonium carbonate and bicarbonate compounds. The method of the present invention comprises (a) combining at least four (C 1 to C 2 fluorene) alkyl or aryl substituted terphenyl ammonium bromide, metal hydroxide and having less than 1 gram of solvent per gram of solvent A solvent of about 1 gram of solubility of the metal bromide which is stoichiometrically excess relative to the fourth grade ammonium bromide to produce at least four cc to C2. An alkyl or aryl substituted alkyl quaternary ammonium hydroxide; and (b) combining at least the tetra (C, to C2.) alkyl or aryl substituted alkyl quaternary ammonium hydroxide and carbon dioxide An alkyl quaternary ammonium carbonate substituted with at least the four (匕 to c2 〇) alkyl or aryl group is produced. SUMMARY OF THE INVENTION Applicants' methods can be roughly exemplified as follows: 200920696 (I)· x[(R1R2R3R4N)+]Br'+ excess M(OH)x + R5OH x[(R1R2R3R4N)+]OH+MBrx+ residual M ( OH)x+R5OH; and (II}-[(r1r2r3r4n)+]oh-+ residual M(OH)X + C02 + R5OH —> [(R1R2R3R4N)+]HC03_ + [(R1R2R3R4N)+]2C〇32 '+ M2(C03)x+ r5〇h , wherein M2(C〇3) X in the formula (I) is in the solvent R5OH, and is removed by, for example, filtration; each R1 , R2, R3 and R4 are independently C! to C2. Alkyl or aryl substituted alkyl (for example, R1 and R2 may be different C8-C12 alkyl groups and R3 and R4 may each be methyl, etc.) Alkyl, hydrazine is a mono-, di- or trivalent metal, or an alkali metal; if Μ is a unit price, X is 1; if Μ is divalent, X is 2; if Μ is trivalent, X is 3. Therefore, alkali The metal is like Na or yttrium, and X is 1. (^ to C2. alkyl or aryl substituted alkyl, C, to C2. alkyl or aryl substituted alkyl, dimethyl tetraammonium bromide In combination with a stoichiometric excess of metal hydroxide in a suitable solvent, for example, having less than about 1 gram of gold per 00 gram of solvent a solvent for the solubility of bromide, and a Cl to C2 in the i-rich. A yard- or aryl-substituted yard, Cl to C2. Alkyl or aryl-substituted alkyl, dimethyl quaternary ammonium hydroxide Intermediate solution. The hydroxy quaternary ammonium salt intermediate and the residual metal hydroxide in the solution are combined with carbon dioxide to produce a quaternary ammonium carbonate/bicarbonate and an insoluble metal carbonate. Suitable solvents include R5 sterols. For example, methanol, ethanol, isopropanol, propanol, isobutanol, and other C, to C6 alcohols. Tetraallammonium salts having any desired anion (eg, phosphate, acetate, salicylate, grass) Acidates, chlorides, etc. can be prepared by combining an ammonium hydroxide intermediate with a corresponding acid. 200920696 Many (^ to C2. alkyl or aryl substituted alkyl, (^ to c2. alkyl or aryl) Substituted alkyl, dimethyl quaternary ammonium bromide is a suitable reactant for the preparation of a hydroxy quaternary ammonium salt intermediate, such as dimercaptodimethylammonium bromide. Suitable for the brominated quaternary ammonium salt reactant. The choice of the 1 and R2 substituents is determined by the intermediate of the hydroxy quaternary ammonium salt. a factor, and thus a determinant of the carbonate quaternary ammonium salt product. Many other tetraalkyl fourth ammonium bromides are also suitable for use in the present invention, as is known to those skilled in the art. The methods exemplified are those wherein R1 is methyl, C8 alkyl, CN isoalkyl, G. alkyl, Cl2 alkyl, Cm alkyl, C16 alkyl or benzyl; R2 is already. An alkyl group, a C2 alkyl group, a C"alkyl group or a C16 alkyl group: and each of R3 and R4 is a methyl group. The metal hydroxide reactant may be a mono-, di- or trivalent metal hydroxide or an alkali metal hydroxide. For example, sodium hydroxide or potassium hydroxide. The first step reaction product of the metal bromide can be easily removed by filtration or the like to produce a hydroxy quaternary ammonium salt/solvent reaction product. If desired, hydroxy quaternary ammonium The salt may be isolated therefrom by drying or the like. The first reaction (I) may be carried out in a solvent including a Chq alcohol such as ethanol or absolute ethanol. The reaction for forming a hydroxy quaternary ammonium salt is typically an equilibrium reaction 'but an alcohol solvent The use rapidly drives the reaction to a quaternary ammonium quaternary ammonium salt. The amount of metal hydroxide reactant can be stoichiometric relative to the tetraalkyl fourth ammonium bromide reactant. Therefore, on a theoretical basis, if the reaction It is completely and unbalanced, and when the intermediate reaction is completed, there will be no excess of the metal hydroxide reactant of 200920696. In fact, when using the chemist metal hydroxide reactant, the yield is It will vary from about 65% to but some will be based on each metal oxide reactant. By using a metal hydroxide ranging from about 2% to about 50% excess, the yield of hydroxy quaternary ammonium salt can be compared. A further improvement. If an excess of metal hydroxide is used, the yield is about 95% to about 99%, as described above, and the unreacted metal hydroxide is soluble in the hydroxy quaternary | intermediate. The hydroxy quaternary ammonium salt and any unreacted gold species can be reacted with at least a stoichiometric amount of carbon dioxide to produce an acid salt, and if any unreacted metal hydroxide metal carbonate is present. The medium conversion metal hydroxide carbonate ' is the fastest. The metal carbonate can be precipitated and easily separated by filtration or the like, leaving a stable quaternary ammonium carbonium hydrogen salt or a quaternary ammonium carbonate/solvent reaction product. As illustrated, the carbonation step also produces quaternary ammonium as a by-product. Separate quaternary ammonium carbonate or quaternary ammonium carbonate is suitable for use in, for example, wood preservative systems. These quaternary ammonium carbon grades. The carbonate/bicarbonate composition does not require stabilization of the matrix of the metal affinity agent. The wood preservative system may be free of metal. The mixing, addition, combination and reaction of the components of the present invention may be carried out by conventional methods well known to those skilled in the art. The order of addition of any reactants or solvents does not affect the amount of the method or the amount of the program is about 95%, and the method of adding sT to increase the self-crossing salt/solvent is quaternary ammonium hydroxide, the product becomes The gold may be passed through the usual individual steps via a salt of a salt/bicarbonate hydrogenate or a mixture of four for wood. The anti-9-200920696 reagent and/or solvent may be added to any suitable reaction vessel continuously or simultaneously. For example, a metal hydroxide can be dissolved in an alcohol and the resulting mixture can be added to the bromide quaternary ammonium salt or the bromide quaternary ammonium salt can be dissolved in the alcohol and the metal hydroxide added to the resulting mixture. Importantly, the method of the present invention is suitable for commercial scale manufacturing techniques and equipment, and is convenient for small scale operations. Typically, the bromide quaternary ammonium salt is converted to a hydroxy quaternary ammonium salt reaction (I) and the solvent is stirred and heated from about 20 ° C to about 7 ° C and maintained at that temperature for about 1 hour to about 5 hours period. The reaction mixture is then cooled, first to room temperature and then to about οπ, which is maintained at this temperature for about 1 hour to about 2 hours. Any precipitated metal bromide is collected, for example, via filtration, as is well known in the art. According to the invention, the exemplified step comprises the manufacture of a quaternary ammonium hydroxide solution by treating the quaternary ammonium bromide solution with KOH and precipitating KBr, and converting the quaternary ammonium hydroxide in the solution to bicarbonate/ Carbonate. Several other quaternary ammonium salts (i.e., phosphates, carboxylates, other halides, etc.) can be prepared from the quaternary ammonium hydroxide intermediate. 1 - or 1 2 -butanol can be used as a solvent for producing a four-stage ammonium bromide solution and in order to obtain a low bromine hydrazine, water can be removed from the KOH solution of butanol. When water is stripped from the butanol solution of KOH, KOBu is formed. The dried KOH solution was mixed with a substoichiometric amount (1.5 mol KOH/mole bromide) of a four-stage ammonium bromide solution to precipitate KBr. The quaternary ammonium butoxide/hydroxide solution is then treated with a C 〇 2 gas to obtain a solution of a carboquat (carbonate/bicarbonate/butyl carbonate) in butanol. Excess KOH/KOBu in the ammonium hydroxide solution was precipitated into a carbonate--10-200920696 salt using a C〇2 treatment and removed from the furnace. Initially no water was used, then the butanol from the quaternary ammonium carbonate solution was stripped using water and treated with a small amount of 5 〇 % H 2 〇 2 to decolorize the yellow solution. The resulting clear quaternary ammonium carbonate solution (carbonate/bicarbonate) can then be diluted with sufficient water and i,2-propylene glycol to meet the desired specifications. Thus, in one aspect of the invention, a method for preparing a quaternary mirror carbonate solution substituted with a low alkyl halide and a good color of about 50% aqueous tetraalkyl or aryl substituted. The method comprises: (i) a solution of a quaternary ammonium bromide from a decyl dimethylamine and a 1-bromodecane in a C4 alcohol, (U) comprising from a quaternary ammonium salt of more than 1 mole of KOH/mole. The butanol solution is azeotropically removed with a suitable hydroxy group such as hexane' (iii) combined with the quaternary ammonium bromide solution of (i) and the butanol solution from (ii) and the precipitated KBr is removed, for example by filtration, ( Iv) blowing CO 2 gas through the solution obtained in (iii), removing the precipitated solid particles from excess KOH to obtain a quaternary ammonium carbonate solution in butanol, and (v) solvent exchanged carbonic acid grade 4 The ammonium salt solution is from butanol to water, followed by the addition of 1-5 % hydrogen peroxide. The steps used to obtain the low halide and good color include: (a) using a C4 alcohol as a solvent, (b) removing water from the alcoholic KOH solution, and (c) decolorizing the carbonic acid quaternary ammonium salt solution using hydrogen peroxide. . [Embodiment] The following examples are illustrative of the principles of the invention. It should be understood that the invention is not limited to any specific embodiment exemplified herein, whether in the examples or in the remainder of the patent application. -11- 200920696 - Example 1 - Preparation of a quaternary phosphonium bromide solution 93 g (0.5 mol) of N,N-dimethyl decylamine, lllg (0.5 mol) of 1-bromodecane and 1 3 5 A mixture of g of butanol was poured into a dry 5 〇〇 ml flask equipped with a condenser. The mixture was heated to reflux using an electric hood. Stop heating after 4 hours. A clear pale yellow solution of the quaternary ammonium bromide was analyzed. Analysis shows 12.7 wt% bromine, 0.19 wt% free amine and 59.4 wt% quaternary ammonium hydrazine. In 65 g of 2-butanol, 93.5 g (0.5 mol) of decyl dimethylamine f solution was placed in a flask and heated. To 1 〇 5 t with magnetic stirring. 1-bromodecane (1 1 1 .5 g) was added dropwise over 2 hours and the mixture was heated at 105 t for an additional 4 hours. Analysis of the clear yellow solution (269 g) found to have 70.6 wt% quaternary ammonium salt, 13.2 wt% bromine, and 0.88 wt% free amine. Example 2 - Preparation of an alkyl quaternary ammonium solution in butanol A 10 g (150 mmol) piece of potassium hydroxide containing about 15 wt% water, 50 g of 1-butanol and 25 g of hexane was added to a 250 ml flask. The flask was equipped with a Dean-Stark trap and a reflux condenser. The mixture was refluxed and the water removed as azeotrope was collected in a trap. The mixture was refluxed until the aqueous phase in the trap did not increase. 60 g (about 90 mmol) of the quaternary ammonium bromide solution was added dropwise to the solution at ambient temperature and magnetically stirred. The mixture was then cooled in an ice bath for 1 hour. The precipitated solid particles were filtered under suction and washed with 20 ml of hexane. The slightly cloudy filtrate was again filtered to obtain a clear solution. C0 2 gas was bubbled through the solution for 1 hour. The precipitated solid particles were removed by passing through a Whatman filter paper to obtain 100 g of a clear yellow solution of alkyl quaternary ammonium in 1-butanol. Analysis showed that the -12-200920696 alkyl quaternary ammonium solution had 33.2% quaternary ammonium salt and 345 ppm bromine. Example 3 - Preparation of alkyl quaternary ruthenium 7k solution A sample of 〇6g of a solution of quaternary ammonium carbonate in 1 - butanol containing 2,300 ppm of bromine (3 4 · 8 wt %) was placed in a 500 ml flask and Concentrate to about 60 g at 7 ° C under vacuum using a rotary evaporator. Deionized water (40 g) and 1,2-propanediol (6 g) were added to the mixture and concentrated to about 6 5 2 ° using a rotary evaporator, diluted three times with 40 g of water and concentrated to about 65 g. The resulting pale yellow solution was mixed with 3 g of a 50 wt% hydrogen peroxide solution and diluted to 74 g with water. The clear, colorless solution obtained had a Gardner color of 1 and contained 2 94 ppm bromine (1 30 ppm chlorine) and 5 1 .Owt% quaternary ammonium salt. Details of the quaternary ammonium carbonate: quaternary ammonium salt = 48.5 to 5 1.5 wt%; Gardner color 値 = <4; halide = < 3 0 0 p p m is a chloride. It should be understood that wherever the specification or the patent application is concerned, the reactants and components described in the chemical name or formula, whether referred to in the singular or plural, are identified as their Additional substances (e.g., additional reactants, solvents, etc.) as described in the name or chemical formula are present or may be present prior to contact with them. It is not related to the chemical interactions, transformations and/or reactions that are produced, if any, in the resulting solution or reaction medium, as such changes and/or reactions are specified under the conditions required herein. The natural result of bringing together reactants and/or ingredients. Thus, the reactants and components are identified as components that are associated with the chemical reaction required for implementation or that are brought together when forming a combination that is used to guide the desired reaction. Therefore, even if the scope of the following patent application may refer to the material composition and/or composition of the present tense ("comprises", "is"), etc., the status of the substance component or component is as It is present in accordance with the teachings of the present invention 'just prior to its incorporation or mixing with one or more other substance components and/or ingredients'. Regardless of the transition, if any, when it is implemented, it occurs locally and is the project that the patent application is intended to cover. Therefore 'the fact is that during a process of contact, union, blending or mixing, the 'a substance' component or component may lose its original properties through a chemical reaction or transformation', so if it is in accordance with this text and together with the application common sense and the chemist's usual Skills are implemented. The true meaning of correctly understanding and evaluating the content of this article and the scope of its patent application is completely unimportant. As is familiar to those skilled in the art, as used herein, the terms "combined", "positive combination", etc. mean that the components of "combined" or "positive combination" are placed one upon another. In the container. Similarly, "combination" of each component means placing the components together in a single container. Although the present invention has been described in terms of one or more preferred embodiments, it is understood that other modifications may be made without departing from the scope of the invention. [Simple description of the figure] iffi. [Main component symbol description] None. -14-