JP2000290247A - Method for producing alkene sulfide - Google Patents
Method for producing alkene sulfideInfo
- Publication number
- JP2000290247A JP2000290247A JP11099920A JP9992099A JP2000290247A JP 2000290247 A JP2000290247 A JP 2000290247A JP 11099920 A JP11099920 A JP 11099920A JP 9992099 A JP9992099 A JP 9992099A JP 2000290247 A JP2000290247 A JP 2000290247A
- Authority
- JP
- Japan
- Prior art keywords
- alkene
- sulfide
- amine
- sulfur
- amine salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【課題】 透明性、鉱油への溶解性、溶剤への溶解性が
良好で、硫黄の析出、及び加熱時の硫化水素発生が少な
い硫化アルケンを製造する方法を提供する。
【解決手段】 アミン触媒存在下、アルケン、硫黄、硫
化水素を反応させ、さらに未反応アルケンを減圧蒸留及
び空気の通気により留去して合成した硫化アルケン粗生
成物を空気及び／又は過酸化水素水溶液の様な酸化剤
で、副生する硫黄化合物のアミン塩を硫酸アミン塩及び
／又はチオ硫酸アミン塩に酸化し、アルコールの様な有
機溶媒で抽出除去する。PROBLEM TO BE SOLVED: To provide a method for producing an alkene sulfide having good transparency, good solubility in mineral oil, good solubility in a solvent, little precipitation of sulfur and little generation of hydrogen sulfide during heating. SOLUTION: Alkene, sulfur and hydrogen sulfide are reacted in the presence of an amine catalyst, and unreacted alkenes are distilled off by distillation under reduced pressure and air ventilation to obtain a crude alkene sulfide synthesized by air and / or hydrogen peroxide. The amine salt of a by-product sulfur compound is oxidized to an amine sulfate and / or an amine thiosulfate with an oxidizing agent such as an aqueous solution, and extracted and removed with an organic solvent such as an alcohol.
Description
【０００１】[0001]
【発明の属する技術分野】本発明はより高純度の硫化ア
ルケンの製造方法に関する。より具体的には、アミン触
媒存在下、アルケン、硫黄、硫化水素を反応させて得ら
れるジアルキルポリスルフィド構造を有する硫化アルケ
ンの透明性、鉱油及び溶剤への溶解性、硫黄析出、及び
加熱時の硫化水素発生の改良法に関するものである。The present invention relates to a method for producing a higher purity alkene sulfide. More specifically, in the presence of an amine catalyst, the alkene, sulfur, and hydrogen sulfide are reacted to obtain a dialkylpolysulfide structure, which has a transparency, a solubility in a mineral oil and a solvent, sulfur precipitation, and sulfurization during heating. The present invention relates to a method for improving hydrogen generation.
【０００２】[0002]
【従来の技術】ジアルキルポリスルフィドに代表される
硫化アルケンは、例えば金属同士の摩擦、摩耗減少及び
焼き付きを防止する硫黄系極圧添加剤として、切削油、
塑性加工油、ギヤー油、摺動面油、グリースなどに幅広
く利用されている。2. Description of the Related Art Alkene sulfides represented by dialkyl polysulfides are, for example, cutting oils, sulfur-based extreme pressure additives which prevent friction between metals, reduction of wear and seizure.
It is widely used for plastic working oil, gear oil, sliding surface oil, grease, etc.
【０００３】このジアルキルポリスルフィドの製法とし
ては、例えばアルキルメルカプタンと硫黄から合成する
方法、及び、オレフィン（アルケン）、硫黄、硫化水素
を触媒存在下に反応させ、ジアルキルポリスルフィド構
造を有する硫化アルケンとして合成する方法がある。As a method for producing this dialkyl polysulfide, for example, a method of synthesizing from alkyl mercaptan and sulfur, or a method of reacting an olefin (alkene), sulfur and hydrogen sulfide in the presence of a catalyst to synthesize an alkene sulfide having a dialkyl polysulfide structure. There is a way.
【０００４】後者の硫化アルケン合成法は、安価なアル
ケンが出発原料であり、工業的に有利な方法であり、そ
の合成方法は、数多くの文献により、既に公知である。[0004] The latter method of synthesizing a sulfurized alkene is an industrially advantageous method using an inexpensive alkene as a starting material, and the synthesis method is already known from many documents.
【０００５】これら公知の合成法の触媒としては、アミ
ン、アンモニア、アルカリ金属水酸化物（水酸化ナトリ
ウムなど）、アルカリ金属酸化物（酸化カルシウムな
ど）などの塩基性触媒が有効であるが、特にアミンを用
いた場合が最も収率も高く微臭な生成物が得られる。As catalysts for these known synthesis methods, basic catalysts such as amines, ammonia, alkali metal hydroxides (such as sodium hydroxide), and alkali metal oxides (such as calcium oxide) are effective. When the amine is used, the product with the highest yield and a faint odor is obtained.
【０００６】[0006]
【発明が解決しようとする課題】しかし、反応性の高い
アミンを触媒として用いると、反応中に副生した硫黄化
合物とこのアミンとが塩を作り生成物中に残留する。こ
の副生したアミン塩は生成物への溶解性が高く、ろ過を
行ってもいったんは透明になるが、長期間保管すると再
び分離して、濁りや沈澱の原因となり、製品外観の透明
性に悪影響を及ぼす。However, when a highly reactive amine is used as a catalyst, a sulfur compound by-produced during the reaction and this amine form a salt and remain in the product. The amine salt produced as a by-product has high solubility in the product and becomes transparent even after filtration, but after storage for a long period of time, it separates again, causing turbidity and sedimentation. Adversely affect.
【０００７】また、この硫黄化合物のアミン塩を含む硫
化アルケンを、鉱油に溶解した場合は当初は透明でも、
長期間放置すると、やはりこの副生アミン塩が分離して
濁りが発生するなど、硫黄系極圧添加剤等としての実使
用時においても、製品の油溶性を悪化させる。さらにミ
ネラルターペン、ガソリン、イソオクタン、ベンゼン、
トルエン、ナフサなどの炭化水素系溶剤に溶解した場合
も、やはり当初は透明でも長期間放置すると濁り、沈殿
が発生するなど溶剤への溶解性を悪化させるなどの欠点
を有する。また、硫化アルケン、特にアルキル基の炭素
数が９以下のものは加熱時硫化水素が少量発生する欠点
がある。Further, when the sulfided alkene containing an amine salt of a sulfur compound is dissolved in mineral oil, it is initially transparent,
When left for a long period of time, the amine salt by-product is separated and turbidity is generated, and the oil solubility of the product is deteriorated even in actual use as a sulfur-based extreme pressure additive. In addition, mineral terpenes, gasoline, isooctane, benzene,
Even when dissolved in a hydrocarbon-based solvent such as toluene or naphtha, it is also initially transparent but has a disadvantage that it becomes cloudy when left for a long period of time and precipitates, thereby deteriorating the solubility in the solvent. Alkene sulfides, particularly those having an alkyl group of 9 or less carbon atoms, have the disadvantage that a small amount of hydrogen sulfide is generated during heating.
【０００８】本発明が解決しようとする課題は、硫黄化
合物アミン塩を含む硫化アルケン、例えばアミンを触媒
として合成した硫化アルケンに残留するアミン塩を効率
よく除去し、高純度の硫化アルケンを製造する方法、各
種添加剤として用いる場合において、透明性、油溶性、
炭化水素系溶剤への溶解性を向上させる方法、及び加熱
時に発生する硫化水素を減少させる方法を提供すること
にある。An object of the present invention is to efficiently remove an amine salt remaining in an alkene sulfide containing an amine salt of a sulfur compound, for example, an alkene sulfide synthesized by using an amine as a catalyst, to produce a high-purity alkene sulfide. Method, when used as various additives, transparency, oil solubility,
It is an object of the present invention to provide a method for improving solubility in a hydrocarbon solvent and a method for reducing hydrogen sulfide generated during heating.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために硫化アルケン粗生成物中に残留するア
ミン塩の効率良い除去方法を検討した。その結果、硫黄
化合物のアミン塩をそのまま硫化アルケン粗生成物から
除去するのではなく、酸化してチオ硫酸アミン塩または
硫酸アミン塩として有機溶媒で抽出することで上記課題
を解決することを見い出した。Means for Solving the Problems The present inventors have studied an efficient method for removing amine salts remaining in crude alkene sulfide products in order to solve the above problems. As a result, the inventors have found that the above-mentioned problem can be solved by not extracting the amine salt of the sulfur compound as it is from the crude alkene sulfide product but extracting it with an organic solvent as an thiosulfate amine salt or an amine sulfate salt. .
【００１０】なかでも、例えば、反応終了後、未反応ア
ルケンを減圧蒸留で留去した硫化アルケン粗生成物中に
残留する副生した硫黄化合物のアミン塩を、酸素を含む
ガスによって酸化してチオ硫酸塩及び硫酸塩に変換させ
ると、例えばアルコールで高選択的に抽出出来る。さら
にこのアルコール抽出液を分離することにより、アミン
塩を効率良く系外に除去出来ることを見いだした。ま
た、過酸化水素で緩慢に酸化処理をすると加熱時に分解
して硫化水素を発生するような不安定な部分を安定化す
ることができ、発生硫化水素量を減少させることができ
ることを見いだした。Among them, for example, after the reaction is completed, the amine salt of a by-product sulfur compound remaining in the crude alkene sulfide obtained by distilling off unreacted alkene by distillation under reduced pressure is oxidized with a gas containing oxygen to obtain a thione. When converted to sulfate and sulfate, it can be extracted with alcohol, for example, in a highly selective manner. Furthermore, it has been found that the amine salt can be efficiently removed from the system by separating the alcohol extract. In addition, it has been found that, when the oxidation treatment is performed slowly with hydrogen peroxide, unstable portions that decompose during heating to generate hydrogen sulfide can be stabilized, and the amount of generated hydrogen sulfide can be reduced.
【００１１】本発明は、次の発明を提供する。The present invention provides the following invention.
【００１２】（１） 硫化アルケン（Ａ）と、硫黄化合
物のアミン塩（Ｂ）とを含む硫化アルケン粗生成物を、
酸化剤（Ｃ）で酸化し、チオ硫酸アミン塩及び／又は硫
酸アミン塩（Ｄ）とし、当該アミン塩（Ｄ）を有機溶媒
で抽出除去することを特徴とする高純度硫化アルケンの
製造方法。(1) A crude alkene sulfide product containing an alkene sulfide (A) and an amine salt of a sulfur compound (B) is
A method for producing a high-purity alkene sulfide, comprising oxidizing with an oxidizing agent (C) to form an amine thiosulfate and / or an amine sulfate (D), and extracting and removing the amine salt (D) with an organic solvent.
【００１３】（２） 硫化アルケン（Ａ）と、硫黄化合
物のアミン塩（Ｂ）を含む硫化アルケン粗生成物が、ア
ミン触媒の存在下、アルケンと硫黄と硫化水素から硫化
アルケンを合成し、少なくとも未反応アルケンを除去し
た、硫化アルケン（Ａ）と、硫黄化合物のアミン塩
（Ｂ）を含む硫化アルケン粗生成物である上記（１）記
載の硫化アルケンの製造方法。(2) An alkene sulfide (A) and a crude alkene sulfide containing an amine salt of a sulfur compound (B) are used to synthesize an alkene sulfide from an alkene, sulfur and hydrogen sulfide in the presence of an amine catalyst. The method for producing a sulfided alkene according to the above (1), which is a crude sulfided alkene product containing a sulfated alkene (A) and an amine salt of a sulfur compound (B), from which unreacted alkene has been removed.
【００１４】（３） 酸化剤（Ｃ）が空気である上記
（１）または（２）記載の硫化アルケンの製造方法。(3) The method for producing an alkene sulfide according to the above (1) or (2), wherein the oxidizing agent (C) is air.
【００１５】（４） 酸化剤（Ｃ）が過酸化水素である
上記（１）または（２）記載の硫化アルケンの製造方
法。(4) The method for producing an alkene sulfide according to the above (1) or (2), wherein the oxidizing agent (C) is hydrogen peroxide.
【００１６】（５） 酸化剤（Ｃ）として、空気と過酸
化水素とを併用し、これらをこの順に用いて酸化を行う
上記（１）または（２）記載の硫化アルケンの製造方
法。(5) The method for producing an alkene sulfide according to the above (1) or (2), wherein air and hydrogen peroxide are used in combination as the oxidizing agent (C), and these are used in this order for oxidation.
【００１７】（６） 有機溶媒が、アルコールである上
記（１）〜（５）いずれか記載の硫化アルケンの製造方
法。(6) The process for producing a sulfided alkene according to any one of the above (1) to (5), wherein the organic solvent is an alcohol.
【００１８】（７） アルコールがメタノールまたはエ
タノールである上記（６）記載の硫化アルケンの製造方
法。(7) The method for producing a sulfided alkene according to the above (6), wherein the alcohol is methanol or ethanol.
【００１９】（８） 硫黄化合物のアミン塩（Ｂ）が、
アルキルアミン塩、アリールアミン塩又はポリアミン塩
である上記（１）〜（７）いずれか記載の硫化アルケン
の製造方法。(8) The amine salt of a sulfur compound (B) is
The method for producing a sulfurized alkene according to any one of the above (1) to (7), which is an alkylamine salt, an arylamine salt or a polyamine salt.
【００２０】（９） アミン触媒が、アルキルアミン、
アリールアミン又はポリアミンである上記（１）〜
（８）いずれか記載の硫化アルケンの製造方法。(9) The amine catalyst is an alkylamine,
The above (1) to which are arylamines or polyamines
(8) The method for producing an alkene sulfide according to any one of (1) to (4).
【００２１】（１０） アルケンが、炭素原子数４〜１
８のアルケンである上記（１）〜（９）いずれか記載の
硫化アルケンの製造方法。(10) The alkene has 4 to 1 carbon atoms
The method for producing a sulfided alkene according to any one of the above (1) to (9), which is the alkene of No. 8.
【００２２】[0022]
【発明の実施の形態】本発明では、硫化アルケン（Ａ）
と、硫黄化合物のアミン塩（Ｂ）とを含む硫化アルケン
粗生成物を、酸化剤（Ｃ）で酸化し、チオ硫酸アミン塩
及び／又は硫酸アミン塩（Ｄ）とし、当該アミン塩
（Ｄ）を有機溶媒で抽出除去して、より高純度の硫化ア
ルケンを製造する。DETAILED DESCRIPTION OF THE INVENTION In the present invention, an alkene sulfide (A) is used.
And an amine salt of a sulfur compound (B) are oxidized with an oxidizing agent (C) to obtain an amine thiosulfate and / or an amine sulfate (D). Is extracted with an organic solvent to produce a higher purity alkene sulfide.
【００２３】本発明の対象となる、硫化アルケン（Ａ）
と硫黄化合物のアミン塩（Ｂ）を含む硫化アルケン粗生
成物は、公知慣用の合成方法で得ることが出来る。The alkene sulfide (A) which is the object of the present invention
A crude product of a sulfurized alkene containing an amine salt of sulfur and a sulfur compound (B) can be obtained by a known and commonly used synthesis method.
【００２４】より具体的には、例えばアミン触媒の存在
下、アルケンと硫黄と硫化水素とを反応させることによ
り、前記硫化アルケン粗生成物を合成することが出来
る。More specifically, the alkene sulfide crude product can be synthesized by, for example, reacting an alkene with sulfur and hydrogen sulfide in the presence of an amine catalyst.
【００２５】この合成方法としては、例えばＵＳＰ４１
１９５４９、特開昭５３−５２５１０（ＧＢ３９８２２
/７６）、特開昭５５−３８８１９、特開昭５５−３８
８２０、特開昭６２−２４０３８７（ＵＳ８３１９６
７）、特開昭６３−２４５４９３、特開昭６３−５００
９４９（ＵＳ７７７４７５）、特開平２−２８１４５
（ＵＳ１９５２４６）、特公平４−５７１８（ＵＳ３０
４５２６）などの公知の方法が挙げられる。As the synthesis method, for example, USP 41
19549, JP-A-53-52510 (GB39822)
/ 76), JP-A-55-38819, JP-A-55-38
820, JP-A-62-240387 (US83196)
7), JP-A-63-245493, JP-A-63-500
949 (US777475), JP-A-2-28145
(US195246), Tokuhei 4- 5718 (US30)
Publicly known methods such as 4526).
【００２６】ここでの原料アルケンは、生成した硫化ア
ルケンの臭気や硫黄含有量を考慮すると、炭素原子数４
〜１８のアルケンが適当である。一例としては、イソブ
チレン、１−ヘキセン、１ーオクテン、ジイソブチレ
ン、１ーノネン、１ードデセン、１−ヘキサデセンなど
が挙げられる。これらは混合物であっても良い。The raw alkene used here has 4 carbon atoms in consideration of the odor and sulfur content of the produced sulfided alkene.
１８18 alkenes are suitable. Examples include isobutylene, 1-hexene, 1-octene, diisobutylene, 1-nonene, 1-dedecene, 1-hexadecene, and the like. These may be mixtures.
【００２７】硫黄及び硫化水素も公知慣用のものがいず
れも使用できる。必要なら溶融状態の硫黄を用いてもよ
い。Any known and commonly used sulfur and hydrogen sulfide can be used. If necessary, sulfur in a molten state may be used.
【００２８】使用するアミン触媒としては、公知慣用の
ものがいずれも使用できるが、反応性の良い、例えばア
ルキルアミン、アリールアミン、ポリアミンを用いるこ
とが好ましい。一例としては、例えばブチルアミン、ジ
ブチルアミン、トリブチルアミン、ｎ−オクチルアミ
ン、ｔｅｒｔ−オクチルアミン、ジオクチルアミン、ｔ
ｅｒｔ−ドデシルアミン、ｔｅｒｔ−テトラデシルアミ
ン、ｔｅｒｔ−ヘキサデシルアミン、ｔｅｒｔ−オクタ
デシルアミン、ジシクロヘキシルアミン、アリールアミ
ン、ヘキサメチレンテトラミン等が挙げられる。As the amine catalyst to be used, any known and commonly used one can be used, but it is preferable to use an alkylamine, an arylamine, or a polyamine having good reactivity, for example. Examples include, for example, butylamine, dibutylamine, tributylamine, n-octylamine, tert-octylamine, dioctylamine, t
tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, dicyclohexylamine, arylamine, hexamethylenetetramine and the like.
【００２９】アミン触媒の使用量は、反応性を悪化させ
ない範囲でより少量が好ましく、仕込原料合計の０．０
５〜０．５重量％、実用上は０．１〜０．２重量％とな
る量が適当である。The amount of the amine catalyst used is preferably smaller as long as the reactivity is not deteriorated.
An appropriate amount is 5 to 0.5% by weight, and practically 0.1 to 0.2% by weight.
【００３０】この様な各原料を用いた硫化アルケンの合
成方法のうち、好ましい方法は次の通りである。Among the above methods for synthesizing alkene sulfides using the respective raw materials, preferred methods are as follows.
【００３１】最初に、加圧反応容器に炭素数４〜１８の
アルケン、アミン触媒及び硫黄を仕込み、密閉して硫化
水素ガスを、温度１００〜１５０℃で吹き込む。アルケ
ンの種類によってはさらに温度を１４０〜１７０℃に上
げて反応を完結させる。First, an alkene having 4 to 18 carbon atoms, an amine catalyst and sulfur are charged into a pressurized reaction vessel, which is closed, and hydrogen sulfide gas is blown at a temperature of 100 to 150 ° C. Depending on the type of alkene, the temperature is further raised to 140-170 ° C. to complete the reaction.
【００３２】次に温度７０〜１００℃、圧力１０〜３０
ｍｍＨｇで減圧蒸留を行い、少なくとも未反応アルケン
を留去して硫化アルケン粗生成物を得る。Next, a temperature of 70 to 100 ° C. and a pressure of 10 to 30
Vacuum distillation is performed at mmHg to remove at least unreacted alkene to obtain a crude alkene sulfide product.
【００３３】本発明では、硫化アルケン（Ａ）と、硫黄
化合物のアミン塩（Ｂ）を含む硫化アルケン粗生成物を
酸化剤（Ｃ）で酸化する。In the present invention, a crude alkene sulfide containing an alkene sulfide (A) and an amine salt of a sulfur compound (B) is oxidized with an oxidizing agent (C).
【００３４】硫化アルケン粗生成物としては、硫化アル
ケン（Ａ）と、硫黄化合物のアミン塩（Ｂ）を含む硫化
アルケン粗生成物が、アミン触媒の存在下、アルケンと
硫黄と硫化水素から硫化アルケンを合成したものであれ
ばよいが、少なくとも未反応アルケンを除去した、硫化
アルケン（Ａ）と、硫黄化合物のアミン塩（Ｂ）を含む
硫化アルケン粗生成物であることが好ましい。As crude alkene sulfide products, alkene sulfide (A) and a crude alkene sulfide product containing an amine salt of a sulfur compound (B) are obtained by converting alkene sulfide, sulfur and hydrogen sulfide from alkene sulfide in the presence of an amine catalyst. However, it is preferable to use a crude alkene sulfide alkene (A) from which at least unreacted alkene has been removed and an amine sulfide (B) of a sulfur compound.
【００３５】こうして好適なアミン触媒を用いた場合の
硫化アルケン粗生成物に含まれる硫黄化合物のアミン塩
（Ｂ）は、例えばアルキルアミン塩、アリールアミン塩
またはポリアミン塩となる。The amine salt (B) of the sulfur compound contained in the crude alkene sulfide product when a suitable amine catalyst is used is, for example, an alkylamine salt, an arylamine salt or a polyamine salt.
【００３６】蒸留や不活性ガスを通気することにより、
未反応アルケンや未反応硫化水素を除去することが出来
る。By distillation or aeration of an inert gas,
Unreacted alkenes and unreacted hydrogen sulfide can be removed.
【００３７】ここで酸化剤（Ｃ）としては、例えば酸
素、空気、オゾン、過酸化水素、過炭酸、過酢酸、過塩
素酸等が挙げられる。これらは、それぞれ単独で用いて
もよいし併用することも出来る。中でも、空気と過酸化
水素が好ましい。Here, examples of the oxidizing agent (C) include oxygen, air, ozone, hydrogen peroxide, percarbonate, peracetic acid, perchloric acid and the like. These may be used alone or in combination. Among them, air and hydrogen peroxide are preferred.
【００３８】本発明においては、穏和な条件で比較的短
時間に容易に多量のアミン塩（Ｂ）を酸化でき、経済性
にも優れる点では空気が好ましく、比較的長時間を要し
ても確実な酸化を行いたい場合や臭気の少ない硫化アル
ケンを得ようとする場合には、過酸化水素を用いるのが
好ましい。In the present invention, a large amount of the amine salt (B) can be easily oxidized in a relatively short period of time under mild conditions, and air is preferred in terms of economical efficiency. When it is desired to perform reliable oxidation or to obtain an alkene sulfide having a low odor, it is preferable to use hydrogen peroxide.
【００３９】本発明では、空気で主たる酸化を行ってか
ら、過酸化水素により補足的な酸化を行う様にするのが
好ましい。緩慢な酸化作用と取り扱いの容易さから過酸
化水素が実用的である。この方法では、主たる酸化によ
り、硫黄化合物のアミン塩（Ｂ）は、チオ硫酸のアミン
塩及び／又は硫酸のアミン塩（Ｄ）が主成分となる様に
酸化させ、残留する少量の硫黄化合物のアミン塩（Ｂ）
を過酸化水素で酸化する。こうして、硫黄化合物のアミ
ン塩（Ｂ）を含まないが、硫酸のアミン塩及び／又はチ
オ硫酸のアミン塩（Ｄ）を含む硫化アルケン粗生成物を
得る。In the present invention, it is preferable that after the main oxidation is performed with air, the supplementary oxidation is performed with hydrogen peroxide. Hydrogen peroxide is practical because of its slow oxidation and easy handling. In this method, the amine salt (B) of the sulfur compound is oxidized by the main oxidation so that the amine salt of thiosulfuric acid and / or the amine salt of sulfuric acid (D) becomes the main component, and a small amount of the remaining sulfur compound is removed. Amine salt (B)
Is oxidized with hydrogen peroxide. Thus, a crude alkene sulfide product is obtained which does not contain the amine salt (B) of the sulfur compound but contains the amine salt of sulfuric acid and / or the amine salt (D) of thiosulfuric acid.
【００４０】酸素を含むガスとしては、例えば酸素ガ
ス、空気（窒素と酸素との混合ガス）、酸素とヘリウム
等の不活性ガスとの混合ガス等が挙げられる。空気が、
より穏和に酸化が出来る点、経済性の点で好ましい。Examples of the gas containing oxygen include oxygen gas, air (mixed gas of nitrogen and oxygen), and mixed gas of oxygen and an inert gas such as helium. The air
This is preferable in that oxidation can be carried out more moderately and in terms of economy.
【００４１】酸素を含むガスを通気して硫化アルケン粗
生成物に含まれる硫黄化合物のアミン塩（Ｂ）を酸化を
するに当たっては、温度は酸化反応速度、反応生成物の
分解などを考慮する。酸素を含むガスの通気量は少なす
ぎると酸化効率が悪く、多すぎると粗生成物の飛散が起
こるため、調整することが好ましい。In oxidizing the amine salt (B) of the sulfur compound contained in the crude alkene sulfide product by passing a gas containing oxygen, the temperature takes into consideration the oxidation reaction rate, decomposition of the reaction product, and the like. If the gas flow rate of the oxygen-containing gas is too small, the oxidation efficiency is poor, and if the gas flow rate is too large, the crude product is scattered.
【００４２】好ましくは、この硫化アルケン粗生成物
に、温度７０〜１００℃で、単位時間当たり、使用反応
容器の容量の５〜１０倍の通気量で空気を吹き込み、残
留する未反応の硫化水素や未反応のアルケンを除去する
とともに、副生した硫黄化合物のアミン塩（Ｂ）を酸化
して、硫酸のアミン塩及び／又はチオ硫酸のアミン塩
（Ｄ）に変換させる。Preferably, air is blown into the crude alkene sulfide product at a temperature of 70 to 100 ° C. with a ventilation rate of 5 to 10 times the volume of the reaction vessel used per unit time, and the remaining unreacted hydrogen sulfide is removed. And the unreacted alkene are removed, and the amine salt (B) of a by-product sulfur compound is oxidized to be converted into an amine salt of sulfuric acid and / or an amine salt of thiosulfuric acid (D).
【００４３】上記した通り、蒸留や不活性ガスを通気す
ることにより、未反応アルケンや未反応硫化水素を除去
することが出来るが、この際に空気を用いてやることで
酸化した上で同様な効果を得ることも出来る。As described above, unreacted alkenes and unreacted hydrogen sulfide can be removed by distillation or by passing an inert gas, but at this time, oxidation is performed by using air, and the same reaction is performed. You can also get the effect.
【００４４】次いで、空気の通気を終えた、アミン塩
（Ｄ）を含む硫化アルケン粗生成物に酸化剤として過酸
化水素を加えて、空気で酸化しただけではアミン塩
（Ｄ）としきれなかったアミン塩（Ｂ）をアミン塩
（Ｄ）とし、アミン塩を全てアミン塩（Ｄ）となして、
硫化アルケン中に含まれる不安定成分を安定化する。Next, hydrogen peroxide was added as an oxidizing agent to the crude alkene sulfide alkane containing the amine salt (D) which had been completely ventilated with air and oxidized with air, but the amine salt (D) was not completely obtained. The amine salt (B) is changed to the amine salt (D), and all the amine salts are changed to the amine salt (D).
Stabilizes unstable components contained in sulfided alkenes.
【００４５】過酸化水素による酸化は、例えば酸化剤と
して過酸化水素水溶液及び必要に応じて有機溶媒を加え
て室温〜４０℃で攪拌することにより行うことが出来
る。この有機溶媒は、硫化アルケンと相溶しないものを
用いる様にする。好ましくは、過酸化水素水溶液と水溶
性有機溶媒とを併用する。この酸化は、実質的にアミン
塩（Ｂ）が検出されなくなるまで行えば良い。The oxidation with hydrogen peroxide can be carried out, for example, by adding an aqueous solution of hydrogen peroxide as an oxidizing agent and, if necessary, an organic solvent and stirring the mixture at room temperature to 40 ° C. The organic solvent is incompatible with the alkene sulfide. Preferably, an aqueous hydrogen peroxide solution and a water-soluble organic solvent are used in combination. This oxidation may be performed until the amine salt (B) is not substantially detected.
【００４６】過酸化水素の使用量は、アミン塩（Ｄ）を
含む硫化アルケン粗生成物に対して過酸化水素として
０．１〜１．０重量％が適当である。The amount of hydrogen peroxide to be used is suitably 0.1 to 1.0% by weight as hydrogen peroxide based on the crude product of the sulfided alkene containing the amine salt (D).
【００４７】本発明において水溶性有機溶媒としては、
例えばアルコール、ケトン等が挙げられるが、中でもア
ルコールが好ましい。好適なアルコールとしては、メタ
ノールまたはエタノールが挙げられる。In the present invention, the water-soluble organic solvent includes
For example, alcohol, ketone and the like can be mentioned, and among them, alcohol is preferable. Suitable alcohols include methanol or ethanol.
【００４８】予め過酸化水素水溶液にアルコールを含ま
せておくことにより、当該アミン塩（Ｄ）をアルコール
で容易に抽出することができる。アミン塩（Ｄ）は専ら
アルコール側に抽出される。By preliminarily including alcohol in the aqueous hydrogen peroxide solution, the amine salt (D) can be easily extracted with alcohol. The amine salt (D) is exclusively extracted on the alcohol side.
【００４９】アミン塩（Ｄ）を含む硫化アルケン粗生成
物に対して、アルコールは５〜１０重量％が適当であ
る。The alcohol is suitably used in an amount of 5 to 10% by weight based on the crude product of the sulfurized alkene containing the amine salt (D).
【００５０】より確実に、アミン塩（Ｄ）を粗生成物か
ら分離するに当たっては、前記操作の後にアルコールを
分離後、硫化アルケン粗生成物に再度アルコールを加え
て攪拌して、残った当該アミン塩（Ｄ）を抽出すれば良
い。アルコールを分離後、実質的にはアミン塩（Ｄ）を
全く含まない硫化アルケン粗生成物から減圧蒸留によっ
て残留アルコールを留去すれば、高純度の硫化アルケン
を得ることができる。In order to more surely separate the amine salt (D) from the crude product, the alcohol was separated after the above-mentioned operation, and then the alcohol was added to the crude alkene sulfide product again, followed by stirring to obtain the remaining amine salt. What is necessary is just to extract the salt (D). After the alcohol is separated, a high-purity alkene sulfide can be obtained by removing the residual alcohol by distillation under reduced pressure from the crude alkene sulfide substantially containing no amine salt (D).
【００５１】尚、抽出用アルコールの使用量は、実質的
にはアミン塩（Ｄ）を全く含まない硫化アルケン粗生成
物の５〜１５重量％が適当である。The amount of alcohol used for extraction is suitably from 5 to 15% by weight of the crude alkene sulfide product substantially containing no amine salt (D).
【００５２】こうして得られた高純度の硫化アルケン
は、公知慣用の用途いずれにも使用出来る。より具体的
には、硫黄系極圧添加剤として、例えば切削油、塑性加
工油、ギヤー油、摺動面油、グリース、スピンドル油、
鉱油などに必要量添加することにより、目的とする効果
を発揮することが出来る。The high-purity alkene sulfide thus obtained can be used for any known and commonly used applications. More specifically, as a sulfur-based extreme pressure additive, for example, cutting oil, plastic working oil, gear oil, sliding surface oil, grease, spindle oil,
The desired effect can be exhibited by adding a necessary amount to mineral oil or the like.
【００５３】[0053]
【実施例】以下に実施例を用いて本発明をさらに詳細に
説明するが、本発明はこれらの実施例に限定されるもの
ではない。以下、％は重量％を表す。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Hereinafter,% represents% by weight.
【００５４】調製された硫化アルケンの透明性の評価
は、室温で３０日放置後の外観を、透明持続（○）、か
すみ又は曇り発生（△）、モヤモヤ又は浮遊物発生
（×）、沈殿多量発生（××）の４ランクで評価した。The transparency of the prepared alkene sulfide was evaluated by examining the appearance after standing at room temperature for 30 days: persistence of transparency (透明), generation of haze or cloudiness (△), generation of moyamoya or suspended matter (×), large amount of sediment Evaluation was made in four ranks of occurrence (xx).
【００５５】油溶性の評価は、調製された硫化アルケン
を２０％溶解したスピンドル溶液を室温で３０日放置
し、外観を透明性と同一の４ランクで評価した。炭化水
素系溶剤への溶解性評価は、調製された硫化アルケンを
５０％溶解したイソオクタン溶液を室温で３０日放置
し、発生した不溶解分を秤量し、イソオクタン不溶解分
％で評価した。For evaluation of oil solubility, a spindle solution prepared by dissolving 20% of the prepared alkene sulfide was allowed to stand at room temperature for 30 days, and the appearance was evaluated by four ranks which were the same as the transparency. For the evaluation of solubility in hydrocarbon solvents, the prepared isooctane solution in which 50% of the alkene sulfide was dissolved was allowed to stand at room temperature for 30 days, and the generated insoluble matter was weighed and evaluated as isooctane insoluble matter%.
【００５６】硫酸のアミン塩及びチオ硫酸のアミン塩
は、イオンクロマトグラフィーで、硫酸根（ＳＯ4 2-）
及びチオ硫酸根（Ｓ2Ｏ3 2-）を測定し、ミリ％（１０-3
％）で評価した。The amine salt of sulfuric acid and the amine salt of thiosulfuric acid were subjected to ion chromatography to obtain a sulfate group (SO 4 2- ).
And measuring the thiosulfate root (S 2 O 3 2-), milli% (10 -3
%).
【００５７】イオンクロマトグラフィーの条件は、横河
製カラムＳＡＭ３-１２５を用い、４．４Ｍｏｌ炭酸ナ
トリウムと１．２ＭｏL重炭酸ナトリウム水溶液の溶離
液を、流量２ｍＬ／分で用い、導電率検出器で検出し
た。硫黄析出の評価は、製品を室温で３０日放置し、析
出状態を、硫黄沈殿なし（○）、かすかに硫黄沈殿
（△）、硫黄沈殿（×）、硫黄多量に沈殿（××）の４
ランクで評価した。The ion chromatography conditions were as follows: a column SAM3-125 manufactured by Yokogawa was used, and an eluent of 4.4 Mol sodium carbonate and 1.2 MoL sodium bicarbonate aqueous solution was used at a flow rate of 2 mL / min. Detected. The evaluation of sulfur deposition was performed by leaving the product at room temperature for 30 days and determining the precipitation state as 4 (no sulfur precipitation (○), slight sulfur precipitation (△), sulfur precipitation (×), and large amount of sulfur precipitation (xx)).
It was evaluated by rank.
【００５８】加熱時の硫化水素発生量は、１００ｍＬ試
験管に試料２０ｇをとり密閉して６０℃で１時間加熱
後、上部の硫化水素濃度を硫化水素ガス検知管で測定し
た。The amount of hydrogen sulfide generated during heating was determined by taking 20 g of a sample in a 100 mL test tube, sealing and heating at 60 ° C. for 1 hour, and then measuring the concentration of hydrogen sulfide at the upper portion using a hydrogen sulfide gas detector tube.
【００５９】＜実施例１＞硫化水素吹き込み管、硫化水
素吸収装置及び減圧蒸留装置をを接続した１Ｌオートク
レーブにアルケンとしてジイソブチレン４５０ｇ、硫黄
２２０ｇ、アミン触媒としてジシクロヘキシルアミン
１．５ｇを仕込んだ。装置を密閉し１２０℃で硫化水素
ガス７５ｇを圧力６Ｋｇ／ｃｍ2で吹き込んだ。７０℃
まで冷却後、硫化水素吸収装置に接続した弁を開けて圧
力を常圧に戻した。Example 1 450 g of diisobutylene, 220 g of sulfur, and 1.5 g of dicyclohexylamine were charged as an alkene into a 1 L autoclave to which a hydrogen sulfide blowing tube, a hydrogen sulfide absorbing device, and a vacuum distillation device were connected. The apparatus was closed and 75 g of hydrogen sulfide gas was blown at 120 ° C. at a pressure of 6 kg / cm 2 . 70 ° C
After cooling, the valve connected to the hydrogen sulfide absorber was opened to return the pressure to normal pressure.
【００６０】再び装置を密閉後減圧蒸留装置の接続弁を
開けて７０℃で圧力１０ｍｍＨｇまで徐々に減圧して未
反応のジイソブチレンを留去した。圧力を常圧に戻し、
硫化水素吸収装置に接続した弁を開けて、吹き込み管か
ら空気を吹き込み、残留硫化水素、残留ジイソブチレン
を留去するとともに副生した硫黄化合物アミン塩をチオ
硫酸アミン塩及び硫酸アミン塩に変換させた。After sealing the apparatus again, the connection valve of the vacuum distillation apparatus was opened, and the pressure was gradually reduced to 10 mmHg at 70 ° C. to distill off unreacted diisobutylene. Return the pressure to normal pressure,
The valve connected to the hydrogen sulfide absorption device is opened, air is blown from the blowing pipe to distill off residual hydrogen sulfide and residual diisobutylene, and to convert the by-produced sulfur compound amine salt into amine thiosulfate and amine sulfate. Was.
【００６１】このようにして硫黄含有量３９．９％を有
する濁りのある黄色液体の硫化ジイソブチレン粗生成物
６９４ｇ（収率９３％）を得た。In this way, 694 g (yield: 93%) of a crude product of diisobutylene sulfide as a cloudy yellow liquid having a sulfur content of 39.9% was obtained.
【００６２】この硫化ジイソブチレン粗生成物に３５％
過酸化水素水１．９８ｇ、メタノール６９．４gを加
え、温度２０℃で１時間攪拌し、３０分静置後メタノー
ル層を分離する。さらにメタノール６９．４ｇを加え、
１時間攪拌し、３０分静置後メタノール層を分離する。
製品層を温度７０℃、圧力１０mmHgで減圧蒸留によりメ
タノールを留去し、透明黄色液体の硫化ジイソブチレン
を得た。The crude product of diisobutylene sulfide was added with 35%
1.98 g of aqueous hydrogen peroxide and 69.4 g of methanol were added, and the mixture was stirred at a temperature of 20 ° C. for 1 hour. Further, 69.4 g of methanol was added,
The mixture is stirred for 1 hour, and allowed to stand for 30 minutes, after which the methanol layer is separated.
Methanol was distilled off from the product layer by vacuum distillation at a temperature of 70 ° C. and a pressure of 10 mmHg to obtain a transparent yellow liquid diisobutylene sulfide.
【００６３】＜実施例２＞実施例１において、過酸化水
素使用量を０．３％に変えた以外は実施例１と同様に処
理した。<Example 2> The procedure of Example 1 was repeated, except that the amount of hydrogen peroxide used was changed to 0.3%.
【００６４】＜実施例３＞実施例１において、過酸化水
素使用量を０．５％に変えた以外は実施例１と同様に処
理した。<Example 3> The procedure of Example 1 was repeated, except that the amount of hydrogen peroxide used was changed to 0.5%.
【００６５】＜実施例４＞実施例１での対象となる硫化
ジイソブチレン粗生成物で、過酸化水素を使用せず通気
のみで酸化し、次いでメタノール抽出のみを行った。Example 4 The crude product of diisobutylene sulfide, which was the target of Example 1, was oxidized only by aeration without using hydrogen peroxide, and then only methanol extraction was performed.
【００６６】＜比較例１＞硫化ジイソブチレン粗生成物
で通気のみを行い、メタノール抽出を行わなかった。Comparative Example 1 A crude product of diisobutylene sulfide was subjected to only aeration and no methanol extraction.
【００６７】各実施例及び比較例の処理条件及び透明
性、油溶性、イソオクタン不溶解分、硫酸根及びチオ硫
酸根、硫黄沈殿、加熱時硫化水素濃度、及び製品（調製
された硫化アルケン）硫黄含有量を以下の表ー１にまと
めて示した。Processing conditions and transparency, oil solubility, isooctane-insoluble matter, sulfate and thiosulfate, sulfur precipitation, hydrogen sulfide concentration during heating, and product (prepared alkene sulfide) sulfur in each Example and Comparative Example The contents are shown in Table 1 below.
【００６８】[0068]
【表１】表−１ [Table 1]
【００６９】注１）製品室温３０日後の外観 ４ランク
評価 ［○：透明 △：かすみ、曇り ×：モヤモヤ、浮遊物
発生 ××：沈殿多量］ 注２）２０％スピンドル油溶液 室温３０日後の外観 上記透明性と同一の４ランク評価 注３）５０％イソオクタン溶液 室温３０日後の不溶解
分％ 注４）イオンクロマト法 注５）製品室温３０日後の硫黄析出状態 ４ランク評価 ［○：硫黄沈殿なし △：かすかに硫黄沈殿 ×：硫黄
沈殿 ××：沈殿多量］ 注６）６０℃、１時間加熱後のガス検知管による硫化水
素濃度（ｐｐｍ）Note 1) Appearance after 30 days at room temperature of product 4 rank evaluation [○: Transparent △: Haze, cloudy ×: Moyamoya, suspended matter generation XX: Large amount of sedimentation] Note 2) 20% spindle oil solution 30 days after room temperature at room temperature 4 rank evaluation same as the above transparency Note 3) 50% isooctane solution Insoluble content% after 30 days at room temperature Note 4) Ion chromatography method Note 5) Sulfur precipitation state after 30 days at room temperature of product 4 rank evaluation [○: No sulfur precipitation △: Slightly sulfur precipitation ×: Sulfur precipitation XX: Large amount of precipitation] Note 6) Hydrogen sulfide concentration (ppm) by gas detector tube after heating at 60 ° C for 1 hour
【００７０】硫黄化合物のアルキルアミン塩を含む硫化
イソブチレン粗生成物は、何ら処理を加えないで濾過す
るだけでは透明性、油溶性が悪く、硫黄も少量沈殿し、
硫酸根及びチオ硫酸根も高い数値のままだが、メタノー
ル抽出を行うと硫酸根及びチオ硫酸根が減少し、透明
性、油溶性が明らかに向上し、イソクタン不溶解分が減
少した。また、溶解硫黄が除去減少し、硫黄析出も改良
された。さらに過酸化水素処理を行うと加熱時硫化水素
の発生が抑制された。A crude product of sulfurized isobutylene containing an alkylamine salt of a sulfur compound is poor in transparency and oil solubility only by filtration without any treatment, and a small amount of sulfur precipitates.
Although the values of sulfate and thiosulfate remained high, sulfate extraction and thiosulfate were reduced by methanol extraction, transparency and oil solubility were clearly improved, and isoctane-insoluble matter was reduced. In addition, the amount of dissolved sulfur was reduced and sulfur deposition was improved. Further, when hydrogen peroxide treatment was performed, generation of hydrogen sulfide during heating was suppressed.
【００７１】[0071]
【発明の効果】本発明の硫黄化合物のアミン塩除去方法
によれば、硫化アルケンの製品の沈澱、濁りがなくなり
透明性が持続し、溶存する硫黄が減少する結果、長期保
存中の硫黄の析出が防止できる。さらに、鉱油への溶解
性、炭化水素系溶剤への溶解性が向上する。さらに加熱
時の硫化水素発生が減少する。According to the method for removing an amine salt of a sulfur compound according to the present invention, precipitation and turbidity of a product of an alkene sulfide are eliminated, transparency is maintained, and dissolved sulfur is reduced. Can be prevented. Further, the solubility in mineral oil and the solubility in hydrocarbon solvents are improved. Further, generation of hydrogen sulfide during heating is reduced.
Claims (6)
ン塩（Ｂ）とを含む硫化アルケン粗生成物を、酸化剤
（Ｃ）で酸化し、チオ硫酸アミン塩及び／又は硫酸アミ
ン塩（Ｄ）とし、当該アミン塩（Ｄ）を有機溶媒で抽出
除去することを特徴とする高純度硫化アルケンの製造方
法。1. A crude product of an alkene sulfide containing an alkene sulfide (A) and an amine salt of a sulfur compound (B) is oxidized with an oxidizing agent (C) to obtain an amine thiosulfate and / or an amine sulfate (D). ), Wherein the amine salt (D) is extracted and removed with an organic solvent.
ミン塩（Ｂ）を含む硫化アルケン粗生成物が、アミン触
媒の存在下、アルケンと硫黄と硫化水素から硫化アルケ
ンを合成し、少なくとも未反応アルケンを除去した、硫
化アルケン（Ａ）と、硫黄化合物のアミン塩（Ｂ）を含
む硫化アルケン粗生成物である請求項１記載の硫化アル
ケンの製造方法。2. An alkene sulfide (A) and a crude alkene sulfide containing an amine salt of a sulfur compound (B) are used to synthesize an alkene sulfide from an alkene, sulfur and hydrogen sulfide in the presence of an amine catalyst. The method for producing an sulfide of an alkene according to claim 1, which is a crude sulfide of an alkene sulfide containing an alkene sulfide (A) from which a reaction alkene has been removed and an amine salt of a sulfur compound (B).
の硫化アルケンの製造方法。3. The method according to claim 1, wherein the oxidizing agent (C) is air.
１記載の硫化アルケンの製造方法。4. The method according to claim 1, wherein the oxidizing agent (C) is hydrogen peroxide.
とを併用し、これらをこの順に用いて酸化を行う請求項
１記載の硫化アルケンの製造方法。5. The method for producing an alkene sulfide according to claim 1, wherein air and hydrogen peroxide are used in combination as the oxidizing agent (C), and the oxidation is performed using these in this order.
記載の請求項１記載の硫化アルケンの製造方法。6. The method according to claim 1, wherein the organic solvent is an alcohol.
The method for producing an alkene sulfide according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09992099A JP4075202B2 (en) | 1999-04-07 | 1999-04-07 | Method for producing sulfided alkenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09992099A JP4075202B2 (en) | 1999-04-07 | 1999-04-07 | Method for producing sulfided alkenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000290247A true JP2000290247A (en) | 2000-10-17 |
| JP4075202B2 JP4075202B2 (en) | 2008-04-16 |
Family
ID=14260219
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09992099A Expired - Lifetime JP4075202B2 (en) | 1999-04-07 | 1999-04-07 | Method for producing sulfided alkenes |
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| Country | Link |
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| JP (1) | JP4075202B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263244A (en) * | 2008-04-22 | 2009-11-12 | Dic Corp | Process for producing dialkyl trisulfide |
| CN116120279A (en) * | 2023-02-01 | 2023-05-16 | 广州米奇化工有限公司 | Process for the preparation of sulfurized olefins |
-
1999
- 1999-04-07 JP JP09992099A patent/JP4075202B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263244A (en) * | 2008-04-22 | 2009-11-12 | Dic Corp | Process for producing dialkyl trisulfide |
| CN116120279A (en) * | 2023-02-01 | 2023-05-16 | 广州米奇化工有限公司 | Process for the preparation of sulfurized olefins |
| CN116120279B (en) * | 2023-02-01 | 2024-12-27 | 广州米奇化工有限公司 | Process for preparing sulfurized olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4075202B2 (en) | 2008-04-16 |
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