JPH06287580A - Preparation of mixture of sulfurized alkaline earth metal salts of salycyclic acid and phenol - Google Patents
Preparation of mixture of sulfurized alkaline earth metal salts of salycyclic acid and phenolInfo
- Publication number
- JPH06287580A JPH06287580A JP9539493A JP9539493A JPH06287580A JP H06287580 A JPH06287580 A JP H06287580A JP 9539493 A JP9539493 A JP 9539493A JP 9539493 A JP9539493 A JP 9539493A JP H06287580 A JPH06287580 A JP H06287580A
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- JP
- Japan
- Prior art keywords
- alkaline earth
- earth metal
- reaction
- added
- mol
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、潤滑油および燃料油に
添加する清浄剤として極めて有用な、サリチル酸類およ
びフェノール類のアルカリ土類金属塩硫化混合物の製法
に関するものであり、さらに詳細には、製品の色相改善
および回収フェノールの白濁を防止し得る改良された上
記製法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for preparing an alkaline earth metal sulfide mixture of salicylic acids and phenols, which is extremely useful as a detergent added to lubricating oils and fuel oils. The present invention relates to the above-mentioned improved production method capable of improving the hue of a product and preventing clouding of recovered phenol.
【０００２】[0002]
【従来の技術】本発明者らは、アルカリ土類金属酸化
物、水酸化物またはそれらの混合物（以下、「アルカリ
土類金属試薬」という。）、アルキルフェノールおよび
二価アルコールを混合反応させ、その後水と二価アルコ
ールを留去し、得られたアルカリ土類金属フェネートに
二酸化炭素処理を施すことによりヒドロキシアルキル安
息香酸塩（サリシレート）を形成し、それに元素硫黄を
反応させることによりヒドロキシアルキル安息香酸およ
びアルキルフェノールのアルカリ土類金属塩硫化混合物
ならびにその製造法を得ることに成功した（特開昭６４
−２９３５４）。この方法は、アルカリ金属を使用する
必要がなく、アルカリ土類金属フェネートから直接アル
カリ土類金属ヒドロキシアルキル安息香酸塩を形成する
ことにより製造工程を著しく単純化した点に特色があ
る。また、特願平４−２７５０２６では、ヒドロキシア
ルキル安息香酸塩を形成後、硫化をする際にアルカリ土
類金属試薬と二価アルコールを再び添加して硫化金属付
加反応を行うことにより生成するヒドロキシアルキル安
息香酸およびアルキルフェノールのアルカリ土類金属塩
硫化混合物の塩基価を向上し、さらに色相を明るくし
た。これら２つの方法は、フェノール類の存在はアルキ
ルサリチル酸の生成を妨害するという従来からの考えを
覆すもので、これにより、アルキルフェノールを溶媒と
して使用することが可能となり特殊な溶媒や添加物を必
要とせず、希釈油として使用する鉱油を除けば全て反応
に直接用いられるもののみを原料として用いている。し
たがって、使用原料の種類を必要最小限にとどめている
点で優れている。2. Description of the Related Art The inventors of the present invention carry out a mixed reaction of an alkaline earth metal oxide, a hydroxide or a mixture thereof (hereinafter referred to as "alkaline earth metal reagent"), an alkylphenol and a dihydric alcohol, and thereafter. Water and dihydric alcohol are distilled off, and the obtained alkaline earth metal phenate is subjected to carbon dioxide treatment to form a hydroxyalkyl benzoate (salicylate), which is reacted with elemental sulfur to produce a hydroxyalkyl benzoic acid. Succeeded in obtaining an alkaline earth metal sulfide mixture of alkylphenol and alkylphenol and a method for producing the same (JP-A-64)
-29354). This method is characterized in that the production process is remarkably simplified by forming an alkaline earth metal hydroxyalkyl benzoate directly from an alkaline earth metal phenate without the need to use an alkali metal. Further, in Japanese Patent Application No. 4-275026, after forming a hydroxyalkyl benzoate, a hydroxyalkyl produced by carrying out a sulfide metal addition reaction by adding an alkaline earth metal reagent and a dihydric alcohol again at the time of sulfurization. The base number of the alkaline earth metal sulfide mixture of benzoic acid and alkylphenol was improved, and the hue was further lightened. These two methods overturn the conventional belief that the presence of phenols interferes with the formation of alkylsalicylic acid, which allows alkylphenols to be used as solvents, requiring no special solvents or additives. However, except for mineral oil used as diluent oil, only those directly used in the reaction are used as raw materials. Therefore, it is excellent in that the number of types of raw materials used is kept to a minimum.
【０００３】また、本発明者らは特願平５−２０５８１
で、硫化反応時にエチレングリコールを添加することに
より、得られる製品の色相が著しく明るくなることを見
いだしている。Further, the present inventors have filed Japanese Patent Application No. 5-20581.
It has been found by adding ethylene glycol during the sulfurization reaction that the hue of the obtained product becomes significantly brighter.
【０００４】[0004]
【発明が解決しようとする課題】しかし、特開昭６４−
２９３５４の方法は、得られる製品の色相が著しく暗い
という欠点が、特願平４−２７５０２６の方法は、得ら
れる製品の色相は明るくなるが、工程数（炭酸化反応工
程）が増えるため、製造時間が長くなり、各種ユーティ
リティーにかかるコストが大きくなるといった欠点が、
また特願平５−２０５８１では、製品の色相は明るくな
るが、硫化反応を常圧または加圧の密閉系で行うと、そ
の後のフェノール類回収の際に回収フェノール類が白濁
してしまうという欠点があった。回収フェノール類は、
循環して再利用することが好ましく、再利用できないと
フェノール類を多量に使用するため原料コストが莫大に
かかってしまう。この回収フェノール類が白濁する理由
は詳かではないが、サリチル酸類およびフェノール類の
アルカリ土類金属塩硫化混合物を製造する際に、硫化を
二価アルコールの存在下に製造段階の後期に行うためで
あり、ポリスルフィド等の副生物が回収フェノール類中
に混入するためと考えられる。白濁したフェノール類
は、フェノール類としての商品価値が低いことは勿論、
フェネートやサリシレートの製造に再使用する原料とし
ても、望ましくない副反応が生じることが予想され、ま
た最終製品の油溶性低下の原因となるため適当でない。However, JP-A-64-64
The method of 29354 has a drawback that the hue of the obtained product is remarkably dark, but the method of Japanese Patent Application No. 4-275026 makes the hue of the obtained product bright, but the number of steps (carbonation reaction step) increases, so The drawback is that it takes longer time and the cost for various utilities increases.
Further, in Japanese Patent Application No. 5-20581, the hue of the product becomes brighter, but when the sulfurization reaction is carried out in a closed system of normal pressure or pressure, the recovered phenols become cloudy during the subsequent recovery of the phenols. was there. The recovered phenols are
It is preferable to circulate and reuse, and if it cannot be reused, a large amount of phenols is used, resulting in enormous raw material cost. The reason why the recovered phenols become cloudy is not clear, but in the production of a mixture of salicylic acids and phenols with alkaline earth metal salts, sulfurization is carried out in the presence of a dihydric alcohol in the latter stage of the production process. It is considered that this is because by-products such as polysulfide are mixed in the recovered phenols. Of course, cloudy phenols have low commercial value as phenols,
It is also unsuitable as a raw material to be reused in the production of phenates and salicylates, since undesirable side reactions are expected to occur and the oil solubility of the final product is reduced.
【０００５】本発明の目的は、工程数、使用原料を必要
最小限にとどめながら、製品が明るい色相を有し、かつ
回収フェノール類が濁らずに再使用可能であり、そして
酸中和能力の高いサリチル酸類およびフェノール類のア
ルカリ土類金属塩硫化混合物を製造する方法を提供する
ことにある。The object of the present invention is that the product has a light hue and the recovered phenols can be reused without turbidity, while the number of steps and the raw materials used are kept to the minimum necessary, and the acid neutralization ability is improved. It is an object of the present invention to provide a method for producing an alkaline earth metal salt sulfurized mixture of high salicylic acids and phenols.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らはこ
れらの課題を解決するために鋭意検討を重ねた結果、硫
化反応を反応温度１６０℃以上、常圧または加圧の開放
系にて二価アルコールを特定量存在させる条件下で行う
ことにより、工程数を増やすことなく製品の色相を明る
くし、かつ回収フェノール類が濁らずに再使用可能とな
ることを見いだし、本発明を完成したものである。Therefore, as a result of intensive studies to solve these problems, the present inventors have found that the sulfurization reaction is carried out at a reaction temperature of 160 ° C. or higher at an atmospheric pressure or an open system. The present invention was completed by discovering that the hue of the product can be brightened and the recovered phenols can be reused without becoming turbid without increasing the number of steps by carrying out under the condition that a specific amount of dihydric alcohol is present. It is a thing.
【０００７】すなわち、本発明の要旨は、フェノール
類、二価アルコール類、アルカリ土類金属試薬よりなる
反応原料混合物またはこれらに水を加えたものを反応さ
せ、次いで水および二価アルコールを留去して得られた
蒸留塔底物に二酸化炭素を反応させ、得られた生成物に
二価アルコール類および元素硫黄を添加して硫化反応を
行うことからなるサリチル酸類およびフェノール類のア
ルカリ土類金属塩硫化混合物の製法において、（ａ）硫
化反応の際、反応温度を１６０℃以上、加圧開放系で反
応を行い、添加する二価アルコール類をアルカリ土類金
属試薬１モル当たり２．０モル以上とするか、あるいは
（ｂ）硫化反応の際、反応温度を１６０℃以上、常圧開
放系で反応を行い、添加する二価アルコール類をアルカ
リ土類金属試薬１モル当たり０．５モル以上とすること
を特徴とするサリチル酸類およびフェノール類のアルカ
リ土類金属塩硫化混合物の製法に存する。That is, the gist of the present invention is to react a reaction raw material mixture consisting of phenols, dihydric alcohols and alkaline earth metal reagents or a mixture thereof with water, and then distill off water and dihydric alcohol. Alkaline earth metal of salicylic acids and phenols, which is obtained by reacting carbon dioxide to the bottom product of the distillation column obtained in this way and adding a dihydric alcohol and elemental sulfur to the obtained product to carry out a sulfurization reaction. In the method for producing a salt-sulfide mixture, (a) in the sulfurization reaction, the reaction temperature is 160 ° C. or higher and the reaction is performed in a pressure open system, and the dihydric alcohol to be added is 2.0 mol per mol of the alkaline earth metal reagent. Or (b) during the sulfurization reaction, the reaction temperature is 160 ° C. or higher and the reaction is carried out in an atmospheric pressure open system, and the added dihydric alcohol is added to the alkaline earth metal reagent 1 mol. Consists in preparation of the alkaline earth metal salt or the alcohol is unsaturated salicylic acids and phenols, characterized in that the per 0.5 mol or more.
【０００８】本発明に使用されるフェノール類は、炭素
数４〜３６個、好ましくは炭素数８〜３２個の炭化水素
側鎖、例えばアルキル基、アルケニル基、アラルキル基
等を有するモノまたはジ置換フェノール類を挙げること
ができる。具体的には、ブチル、アミル、オクチル、ノ
ニル、ドデシル、セチル、エチルヘキシル、トリアコン
チル等の炭化水素基、あるいは流動パラフィン、ワック
ス、オレフィン重合体（ポリエチレン、ポリプロピレ
ン、ポリブテン等）の石油炭化水素から誘導される基を
有するフェノール類が単独、あるいはこれらの混合物に
て使用される。通常約１３０℃、好ましくは約１２０℃
で液状となり得るものが望ましい。これらフェノール類
の具体例としては、ブチルフェノール、オクチルフェノ
ール、ノニルフェノール、ドデシルフェノール、セチル
フェノール、ポリブテンでアルキル化したアルキルフェ
ノール、ジノニルフェノール、ジドデシルフェノールな
どが挙げられる。The phenol used in the present invention is a mono- or di-substituted one having a hydrocarbon side chain having 4 to 36 carbon atoms, preferably 8 to 32 carbon atoms, such as an alkyl group, an alkenyl group or an aralkyl group. Mention may be made of phenols. Specifically, it is derived from hydrocarbon groups such as butyl, amyl, octyl, nonyl, dodecyl, cetyl, ethylhexyl and triacontyl, or petroleum hydrocarbons such as liquid paraffin, wax and olefin polymers (polyethylene, polypropylene, polybutene, etc.). Phenols having a group which is used alone or in a mixture thereof. Usually about 130 ° C, preferably about 120 ° C
It is desirable that it can be liquid. Specific examples of these phenols include butylphenol, octylphenol, nonylphenol, dodecylphenol, cetylphenol, alkylphenols alkylated with polybutene, dinonylphenol and didodecylphenol.
【０００９】アルカリ土類金属試薬としては、通常アル
カリ土類金属の酸化物、あるいは水酸化物ないしはそれ
らの混合物が用いられる。例えばカルシウム、バリウ
ム、ストロンチウム、マグネシウム等の酸化物あるいは
水酸化物ないしはそれらの混合物が用いられる。フェノ
ール類に対するアルカリ土類金属試薬の使用量は、使用
フェノール１当量当たり約０．９９当量以下、好ましく
は０．０１〜０．９８当量である。As the alkaline earth metal reagent, an alkaline earth metal oxide, a hydroxide or a mixture thereof is usually used. For example, oxides or hydroxides of calcium, barium, strontium, magnesium, etc. or mixtures thereof are used. The amount of the alkaline earth metal reagent used with respect to the phenols is about 0.99 equivalents or less, preferably 0.01 to 0.98 equivalents, per equivalent of the phenol used.
【００１０】フェノール類に対するアルカリ土類金属試
薬の量が多過ぎると中間体がゲル化してそれ以上反応が
進まないため、目的とする良好な生成物が得られない。
また、少な過ぎると原料に対する製品の収率が低下する
ばかりか、フェノール類の回収に費やすユーティリティ
や時間が大となり、経済的に不利である。If the amount of the alkaline earth metal reagent with respect to the phenols is too large, the intermediate will gel and the reaction will not proceed any further, and the desired good product cannot be obtained.
On the other hand, if the amount is too small, not only the yield of the product with respect to the raw material is lowered, but also the utility and time spent for recovery of phenols become large, which is economically disadvantageous.
【００１１】次に、二価アルコールとしては、比較的低
沸点かつ低粘度で反応性に富むものが使用される。二価
アルコールは、炭素数が２〜６を有することが好まし
く、特に、エチレングリコール、プロピレングリコール
等が好ましい。二価アルコールはフェノール類とアルカ
リ土類金属試薬との反応による油溶性物質への転化を助
け、一部は生成物中に取り込まれる。Next, as the dihydric alcohol, one having a relatively low boiling point, a low viscosity and a high reactivity is used. The dihydric alcohol preferably has 2 to 6 carbon atoms, and ethylene glycol and propylene glycol are particularly preferable. The dihydric alcohol aids in the conversion of the phenols with alkaline earth metal reagents to oil-soluble materials, some of which is incorporated into the product.
【００１２】本発明法においては、金属付加反応は、反
応促進効果のある水を添加して行っても、添加しないで
行っても良く、水を添加して行う場合、二価アルコール
の使用量はアルカリ土類金属試薬１モル当たり約０．１
５〜３．０モル、特に約０．３〜１．５モルが好まし
い。また水を添加しないで行う場合、二価アルコールの
使用量はアルカリ土類金属試薬１モル当たり、約１．０
〜３．０モル、特に約１．２〜２．０モルが好ましい。In the method of the present invention, the metal addition reaction may be carried out with or without the addition of water having a reaction promoting effect. When water is added, the amount of dihydric alcohol used is Is about 0.1 per mole of alkaline earth metal reagent.
5 to 3.0 moles, especially about 0.3 to 1.5 moles are preferred. When water is not added, the amount of dihydric alcohol used is about 1.0 per mol of the alkaline earth metal reagent.
˜3.0 mol, especially about 1.2-2.0 mol is preferred.
【００１３】二価アルコールの使用量が少なすぎると反
応原料、特にアルカリ土類金属試薬のアルカリ土類金属
フェネートへの転化率が低下する。それにより不溶解分
が増加し、ろ過が困難になるばかりでなく、後のカルボ
キシル化工程で、カルボキシル化率が低下し、ヒドロキ
シベンゾエート生成量が減少する。また、多すぎるとフ
ェノール類への金属付加反応は円滑に進行するが、反応
生成物から過剰の二価アルコールを蒸留留去する時間お
よびユーティリティーが過大にかかってしまう。If the amount of the dihydric alcohol used is too small, the conversion rate of the reaction raw material, particularly the alkaline earth metal reagent, to the alkaline earth metal phenate will be lowered. As a result, not only the amount of insoluble matter increases and filtration becomes difficult, but also the carboxylation rate decreases in the subsequent carboxylation step, and the amount of hydroxybenzoate produced decreases. On the other hand, if the amount is too large, the metal addition reaction to the phenols proceeds smoothly, but the time and utility for distilling off the excess dihydric alcohol from the reaction product and the utility become excessive.
【００１４】また、後記する硫化反応時に使用する二価
アルコールの使用量は、反応を加圧開放系で行う場合、
アルカリ土類金属試薬１モル当たり２．０〜１０モル、
好ましくは２．０〜５．０モル、反応を常圧開放系で行
う場合、アルカリ土類金属試薬１モル当たり０．５〜１
０モル、好ましくは１．０〜５．０モルとする。二価ア
ルコールの使用量が多すぎると、反応生成物から過剰の
二価アルコールを蒸留留去する時間およびユーティリテ
ーが過大にかかってしまう。また、上記した範囲より二
価アルコールの使用量が少ないと、回収フェノールの白
濁を防止するという効果が得られなくなる。ここで開放
系とは、ある一定の圧力を保持するのに反応の進行によ
り変化する反応器内の圧力をガスの出し入れにより調節
する系を言う。The amount of the dihydric alcohol used in the sulfurization reaction described below is such that when the reaction is carried out in a pressure open system.
2.0 to 10 moles per mole of alkaline earth metal reagent,
It is preferably 2.0 to 5.0 mol, and when the reaction is carried out in an atmospheric pressure open system, 0.5 to 1 per mol of the alkaline earth metal reagent.
The amount is 0 mol, preferably 1.0 to 5.0 mol. If the amount of the dihydric alcohol used is too large, it takes too much time and utility to distill off the excess dihydric alcohol from the reaction product. If the amount of dihydric alcohol used is less than the above range, the effect of preventing clouding of the recovered phenol cannot be obtained. Here, the open system refers to a system in which the pressure in the reactor, which changes according to the progress of the reaction in order to maintain a certain constant pressure, is adjusted by taking gas in and out.
【００１５】フェノール類へのアルカリ土類金属試薬の
金属付加反応工程において反応を促進するために反応系
中に水を添加する場合は、蒸留水はもちろん缶水や工業
用水、金属付加反応で生成する水などが使用でき、その
品質に特に制限はなく、冷水、温水、水蒸気等どのよう
な状態の水でも使用できる。金属付加反応促進のために
用いる水の反応器への添加は水単独で行ってもよいし、
一部あるいは全部をフェノール類や二価アルコールなど
ほかの原料との混合物として添加してもよい。反応器へ
の水の添加時期は特に制限はなく、水以外の全反応原料
が混合される前でも後でも良いが、全反応原料混合後約
１時間以内に添加するのが好ましい。When water is added to the reaction system in order to promote the reaction in the metal addition reaction step of the alkaline earth metal reagent to phenols, not only distilled water but also can water, industrial water, and metal addition reaction are generated. Water, etc. can be used, and the quality thereof is not particularly limited, and water in any state such as cold water, hot water and steam can be used. The water used to accelerate the metal addition reaction may be added to the reactor by water alone,
Part or all of them may be added as a mixture with other raw materials such as phenols and dihydric alcohols. The timing of adding water to the reactor is not particularly limited and may be before or after all the reaction raw materials other than water are mixed, but it is preferable to add water within about 1 hour after mixing all the reaction raw materials.
【００１６】反応系中への金属付加反応促進のために用
いる水の添加量は使用するアルカリ土類金属試薬１モル
当たり約０．０１〜１０モル、望ましくは０．１〜２．
０モルである。外部から水を反応系中に添加して金属付
加反応を行うと、水を添加しない以外は同一の条件で反
応を行う場合に比べて反応が円滑に進行する。反応系中
へ添加する水が少なすぎるとその効果は減少してしま
う。また逆に多すぎれば反応後の蒸留工程が簡略化され
るという利点が失われる。The amount of water used for accelerating the metal addition reaction into the reaction system is about 0.01 to 10 mol, preferably 0.1 to 2 mol per mol of the alkaline earth metal reagent used.
It is 0 mol. When water is externally added to the reaction system to carry out the metal addition reaction, the reaction proceeds smoothly as compared with the case where the reaction is performed under the same conditions except that water is not added. If too little water is added to the reaction system, its effect will be diminished. On the contrary, if the amount is too large, the advantage that the distillation step after the reaction is simplified is lost.
【００１７】硫黄の使用量は、極少量から大多量の広い
範囲にわたって使用できる。通常の使用量は、アルカリ
土類金属試薬１モル当たり０．１〜４．０モル、好まし
くは０．２〜３．０モル、さらに好ましくは０．２〜
１．５モルを用いる。硫黄の使用量を低減するにつれ製
品の粘度は低下するが、使用量が少なすぎると製品中の
硫化物が減少し、油溶性が低下してしまう。また多すぎ
ると製品の塩基性が低下するため塩基価の高い製品が得
にくくなるばかりでなく、製品の粘度が著しく高くなっ
てしまう。The amount of sulfur used can be a wide range from a very small amount to a large amount. Usually, the amount used is 0.1-4.0 mol, preferably 0.2-3.0 mol, and more preferably 0.2-4.0 mol, per 1 mol of alkaline earth metal reagent.
Use 1.5 moles. Although the viscosity of the product decreases as the amount of sulfur used decreases, the amount of sulfide in the product decreases and the oil solubility decreases when the amount of sulfur used is too small. On the other hand, if the amount is too large, the basicity of the product is lowered, so that it becomes difficult to obtain a product having a high base number, and the viscosity of the product is significantly increased.
【００１８】硫化反応の際使用する不活性ガスとして
は、窒素、ヘリウムなどが挙げられるが、好ましくは窒
素ガスを用いる。Examples of the inert gas used in the sulfurization reaction include nitrogen and helium, but nitrogen gas is preferably used.
【００１９】本発明において、反応物、反応中間体、あ
るいは製品等の取扱いを容易にするために適当な粘度を
有する希釈剤もしくは溶剤（以下、「希釈剤」とい
う。）を加えることができる。たとえば硫化反応を終え
たのちの反応生成物中から過剰の未反応フェノール類を
蒸留で回収する際、高沸点で、かつ適当な粘度を有する
希釈剤の存在下で行うことによって反応塔底物を液状の
望ましい状態で得ることができる。なお、通常は未反応
フェノール類の留出に伴って希釈剤の一部も留出する。
したがって、回収フェノール類を繰り返し反応に供する
という目的の為には希釈剤としては反応に直接悪影響を
与えないものが望ましい。また希釈剤の存在下に反応を
行ってもよい。好ましい希釈剤の例としては、パラフィ
ン系、ナフテン系、芳香族系、あるいは混合系の基油な
どの適当な粘度の石油留分、例えば沸点約２２０〜５５
０℃で粘度が１００℃で約０．５〜４０ｃＳｔの潤滑油
留分を挙げることができる。その他の有機溶媒でも疎水
性、かつ、親油性を示し、反応時や製品の用途面におい
て無害であれば希釈剤として用いることができる。In the present invention, a diluent or solvent (hereinafter referred to as "diluent") having an appropriate viscosity can be added to facilitate the handling of the reaction product, reaction intermediate, product or the like. For example, when recovering excess unreacted phenols from the reaction product after completion of the sulfurization reaction by distillation, the reaction tower bottoms can be obtained by performing it in the presence of a diluent having a high boiling point and an appropriate viscosity. It can be obtained in the desired liquid state. In addition, usually, a part of the diluent is also distilled along with the distillation of unreacted phenols.
Therefore, for the purpose of repeatedly supplying the recovered phenols to the reaction, it is desirable that the diluent not directly affect the reaction. The reaction may be carried out in the presence of a diluent. Examples of preferable diluents are petroleum fractions having a suitable viscosity, such as paraffinic, naphthenic, aromatic or mixed base oils, for example, boiling points of about 220 to 55.
Mention may be made of lubricating oil fractions having a viscosity at 0 ° C. of 100 ° C. of about 0.5-40 cSt. It can be used as a diluent as long as it shows hydrophobicity and lipophilicity even in other organic solvents and is harmless during the reaction and in the use of the product.
【００２０】本発明におけるサリチル酸類およびフェノ
ール類のアルカリ土類金属塩硫化混合物の主なる製造工
程および運転条件は下記のとおりである。The main production steps and operating conditions of the alkaline earth metal salt sulfide mixture of salicylic acids and phenols in the present invention are as follows.
【００２１】（イ）金属付加工程 所定量のフェノール類、二価アルコール類、アルカリ土
類金属試薬、および必要により希釈剤および／または前
記所定量の水からなる反応原料混合物を反応温度６０〜
２００℃、好ましくは約９０〜１９０℃の範囲で反応さ
せる。その際、反応は約０．０１〜１０atmの減圧、常
圧、もしくは加圧の条件下にて行う。上記金属付加反応
工程において生成する水および添加した水は次のカルボ
キシル化工程前に全量の約９９．９％以上、好ましくは
全量を、二価アルコールは系内に残存する量がアルカリ
土類金属試薬１モル当たり通常約０．６モル以下、好ま
しくは約０．３モル以下になるように留去する。水およ
び二価アルコールが系内に多量に残存すると次のカルボ
キシル化工程で、カルボキシル化率が低下し、ヒドロキ
シベンゾエート生成量が減少する。本反応は通常約１〜
９時間の範囲内でほぼ終了する。(A) Metal addition step A reaction raw material mixture consisting of a predetermined amount of phenols, dihydric alcohols, alkaline earth metal reagents, and if necessary a diluent and / or the predetermined amount of water is reacted at a reaction temperature of 60 to 60 ° C.
The reaction is carried out at 200 ° C, preferably in the range of about 90 to 190 ° C. At that time, the reaction is carried out under reduced pressure, normal pressure or increased pressure of about 0.01 to 10 atm. The water produced in the metal addition reaction step and the added water are about 99.9% or more of the total amount before the next carboxylation step, preferably the total amount, and the amount of the dihydric alcohol remaining in the system is alkaline earth metal. It is distilled off so that it is usually about 0.6 mol or less, preferably about 0.3 mol or less, per mol of the reagent. If a large amount of water and dihydric alcohol remain in the system, the carboxylation rate will decrease in the next carboxylation step, and the amount of hydroxybenzoate produced will decrease. This reaction is usually about 1
It is almost finished within 9 hours.
【００２２】（ロ）カルボキシル化工程 本工程は、前記の金属付加反応生成物をカルボキシル化
し、ヒドロキシベンゾエート成分を得る工程である。す
なわち、前記の金属付加反応生成物を反応温度約１５０
〜２４０℃、好ましくは約１６０〜２３０℃、反応圧力
は、約０．０５〜１００atm、好ましくは約０．１〜５
０atmの減圧、常圧もしくは加圧条件下で二酸化炭素と
反応させる。本反応は通常約１〜１０時間の範囲内でほ
ぼ終了する。(B) Carboxylation step This step is a step of carboxylating the above-mentioned metal addition reaction product to obtain a hydroxybenzoate component. That is, the metal addition reaction product is treated at a reaction temperature of about 150.
~ 240 ° C, preferably about 160-230 ° C, the reaction pressure is about 0.05-100 atm, preferably about 0.1-5.
It is reacted with carbon dioxide under reduced pressure of 0 atm, normal pressure or increased pressure. This reaction is usually completed within about 1 to 10 hours.
【００２３】（ハ）硫化工程 この硫化工程は最終製品の性質、特に油溶性、粘度特
性、貯蔵安定性などの物性を改善する工程で、この硫化
反応を常圧または加圧の開放系にて二価アルコールを特
定量、すなわち加圧開放系ではアルカリ土類金属試薬１
モル当たり二価アルコール２．０モル以上、そして常圧
開放系ではアルカリ土類金属試薬１モル当たり二価アル
コール０．５モル以上、存在させる条件下で行うことに
より、製品の色相が明るくなり、さらに回収フェノール
類の白濁現象が防止できる。前記のカルボキシル化工程
生成物を反応温度１６０℃以上、好ましくは１６０〜２
００℃、圧力１．０〜１０atmにて反応を行う。好まし
くは不活性ガス雰囲気下に行うのがよい。本反応は通常
約１〜２０時間でほぼ終了する。反応温度が高過ぎる
と、カルボキシル化工程で生成したヒドロキシベンゾエ
ートのカルボキシル基が脱カルボキシル化してしまう。
また、低過ぎると、製品の色相は明るくなるが、回収フ
ェノール類の白濁現象は改善されなくなる。また、白濁
現象は改善されても、製品の粘度が高くなってしまう。
粘度の低い製品を得るためには１６０℃以上の温度条件
とすることが好ましい。(C) Sulfurization step This sulfurization step is a step of improving the properties of the final product, particularly physical properties such as oil solubility, viscosity characteristics and storage stability. Specific amount of dihydric alcohol, that is, alkaline earth metal reagent 1 under pressure release system
When the dihydric alcohol is used in an amount of 2.0 mol or more per mol, and in an atmospheric pressure open system, the dihydric alcohol is 0.5 mol or more per 1 mol of the alkaline earth metal reagent, the hue of the product is lightened by carrying out under the condition that the dihydric alcohol is present. Furthermore, the clouding phenomenon of the recovered phenols can be prevented. The product of the carboxylation step is reacted at a temperature of 160 ° C. or higher, preferably 160 to 2
The reaction is carried out at 00 ° C and a pressure of 1.0 to 10 atm. It is preferable to carry out under an inert gas atmosphere. This reaction is usually completed in about 1 to 20 hours. If the reaction temperature is too high, the carboxyl group of hydroxybenzoate produced in the carboxylation step will be decarboxylated.
On the other hand, if it is too low, the hue of the product becomes bright, but the clouding phenomenon of the recovered phenols cannot be improved. Moreover, although the white turbidity phenomenon is improved, the viscosity of the product is increased.
In order to obtain a product having a low viscosity, it is preferable to set the temperature condition to 160 ° C. or higher.
【００２４】硫化反応後の反応生成物にアルカリ土類金
属試薬と二価アルコールとを添加し、さらに上記のよう
な金属付加反応を繰り返して行うことも可能である。そ
の際、金属付加反応後に下記（ニ）のような二酸化炭素
処理工程を繰り返して行うことも可能で、二酸化炭素処
理することにより、最終製品の性質、特に油溶性、粘度
特性、貯蔵安定性などを改善することができる。これに
より生成物の塩基価を上げることが可能となる。It is also possible to add an alkaline earth metal reagent and a dihydric alcohol to the reaction product after the sulfurization reaction, and further repeat the above-mentioned metal addition reaction. At that time, it is possible to repeat the following carbon dioxide treatment step (d) after the metal addition reaction, and by treating with carbon dioxide, the properties of the final product, particularly oil solubility, viscosity characteristics, storage stability, etc. Can be improved. This makes it possible to increase the base number of the product.
【００２５】（ニ）二酸化炭素処理工程 前記のごとく複数回金属付加反応を行う場合、金属付加
反応後に、反応温度約１５０〜２４０℃、好ましくは約
１６０〜２３０℃、反応圧力は約０．０５〜１００at
m、好ましくは０．１〜５０atmの減圧、常圧、加圧条件
下で二酸化炭素と反応させる。(D) Carbon dioxide treatment step When the metal addition reaction is carried out a plurality of times as described above, after the metal addition reaction, the reaction temperature is about 150 to 240 ° C., preferably about 160 to 230 ° C., and the reaction pressure is about 0.05. ~ 100at
It is reacted with carbon dioxide under reduced pressure, normal pressure, and pressure of m, preferably 0.1 to 50 atm.
【００２６】硫化反応後の反応生成物中の未反応フェノ
ール類は経済上などの面から、これらの１部もしくは大
部分を回収することが好ましく、この回収フェノール類
は原料として再使用され得る。ここで、未反応フェノー
ル類の蒸留を高沸点の鉱油など、通常の希釈剤の存在下
で行うと、蒸留残留物は液状の好ましい状態で得ること
ができる。残存する少量の不溶解性物質は、フェノール
類の回収前、あるいは回収後にろ過または遠心分離など
の操作により除去することができる。Unreacted phenols in the reaction product after the sulfurization reaction are preferably recovered in part or in large part from the viewpoint of economy, and the recovered phenols can be reused as a raw material. When the unreacted phenols are distilled in the presence of a usual diluent such as high boiling mineral oil, the distillation residue can be obtained in a liquid state. The remaining small amount of insoluble substance can be removed by an operation such as filtration or centrifugation before or after the phenols are collected.
【００２７】本発明方法の反応生成物の正確な構造の詳
細は不明であるが、反応生成物を加水分解し、加水分解
物をヘキサンのような溶剤で抽出して得られる油層にサ
リチル酸類とフェノール類の両者が検出されることから
原料フェノール類は、その一部が二酸化炭素との反応に
よりサリシレートに転化したものと考えられる。また、
反応生成物はフェノール類およびサリチル酸類の合計グ
ラム当量当たり理論量以上のアルカリ土類金属元素を含
有することから生成物は、塩基性アルカリ土類金属サリ
シレートもしくは塩基性硫化アルカリ土類金属サリシレ
ートと塩基性硫化アルカリ土類金属フェネートの骨格を
有するものと考えられる。一方、反応生成物はサリシレ
ート骨格のみよりなる分子とフェネート骨格のみよりな
る分子との混合物であるのか、１分子中にサリシレート
骨格とフェネート骨格との両者を有する化合物なのか、
または両者を含んだ混合物なのか詳細は不明であり、ま
た反応したアルカリ土類金属元素、反応した硫黄および
反応した二価アルコールとサリシレート骨格とフェネー
ト骨格との結合様式については詳細不明であり、さらに
反応した二酸化炭素のうちサリシレートへの転化に費や
された以外の二酸化炭素の生成物中における結合様式は
詳細不明である。いずれにせよ本発明の反応生成物は、
塩基性アルカリ土類金属フェネートと塩基性アルカリ土
類金属サリシレートの硫化混合物である。Although the exact structure of the reaction product of the method of the present invention is not clear, the reaction product is hydrolyzed, and the hydrolyzate is extracted with a solvent such as hexane to obtain an oil layer containing salicylic acids. Since both of the phenols were detected, it is considered that a part of the raw material phenols was converted into salicylate by the reaction with carbon dioxide. Also,
Since the reaction product contains more than the theoretical amount of alkaline earth metal element per total gram equivalent of phenols and salicylic acids, the product is a basic alkaline earth metal salicylate or a basic alkaline earth metal salicylate and a basic sulfide. It is considered to have the skeleton of the alkaline sulfide alkaline earth metal phenate. On the other hand, whether the reaction product is a mixture of a molecule consisting only of salicylate skeleton and a molecule consisting only of phenate skeleton, or a compound having both salicylate skeleton and phenate skeleton in one molecule,
Or it is unclear whether it is a mixture containing both, and it is unclear about the reaction pattern of the reacted alkaline earth metal element, the reacted sulfur and the reacted dihydric alcohol and the salicylate skeleton and the phenate skeleton. The mode of binding of carbon dioxide in the product other than that of the reacted carbon dioxide that has not been spent for conversion to salicylate is unknown. In any case, the reaction product of the present invention is
It is a sulfurized mixture of a basic alkaline earth metal phenate and a basic alkaline earth metal salicylate.
【００２８】[0028]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、これらは単に例示であって本発明を制限す
るものではない。以下の実施例ならびに比較例におい
て、圧力は特記しない限りゲージ圧である。EXAMPLES The present invention will now be described in more detail with reference to examples, but these are merely examples and do not limit the present invention. In the following examples and comparative examples, the pressure is a gauge pressure unless otherwise specified.
【００２９】実施例１ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５lオートクレーブに純度９４．４％のドデシルフェ
ノール２９１７．８ｇ（１０．５モル）、純度９５．８
％の酸化カルシウム１７５．７ｇ（３．０モル）を送入
し、撹拌した。この懸濁液にエチレングリコール２５
１．５ｇ（４．０５モル）にイオン交換水５．４ｇ
（０．３モル）を混合した溶液を、窒素気流中２．０at
m の加圧下、１３０℃、３０分で全量添加し、終了後こ
れを３．０atm まで窒素で加圧し、１３０℃で３時間反
応させた。その後、該反応系を徐々に減圧しながら、添
加した水、生成水、添加した大部分のエチレングリコー
ル、および少量のドデシルフェノール（５１０．５ｇ）
を留去して、カラシ色の液状の蒸留残留物２８３０．９
ｇが得られた。その際の塔底物の温度は１７３℃、留出
物温度は１３９℃（２mmHg）であった。Example 1 A 5 l autoclave equipped with a stirrer, a cooling tube, a nitrogen gas introducing tube and a thermometer was charged with 2917.8 g (10.5 mol) of dodecylphenol having a purity of 94.4% and a purity of 95.8.
% Calcium oxide (175.7 g, 3.0 mol) was fed in and stirred. Add ethylene glycol 25 to this suspension.
Ion-exchanged water 5.4g to 1.5g (4.05mol)
(0.3 mol) mixed solution, in a nitrogen stream 2.0at
The entire amount was added under a pressure of m 3 at 130 ° C. for 30 minutes, and after the completion, this was pressurized to 3.0 atm with nitrogen and reacted at 130 ° C. for 3 hours. Then, while gradually depressurizing the reaction system, added water, produced water, most of added ethylene glycol, and a small amount of dodecylphenol (510.5 g).
Was distilled off to give a mustard colored liquid distillation residue 2830.9
g was obtained. At that time, the temperature of the bottom product was 173 ° C, and the distillate temperature was 139 ° C (2 mmHg).
【００３０】次に該蒸留残留物２８３０．９ｇに１７８
℃、３mmHgの状態から二酸化炭素を吹き込み５．０atm
まで昇圧し、昇圧後その状態のまま４時間保持して、暗
い灰黄赤色の液状反応生成物２９４０ｇを得た。Next, 178 was added to 2830.9 g of the distillation residue.
5.0 atm by injecting carbon dioxide from the condition of ℃, 3mmHg
After pressurization, the pressure was maintained for 4 hours after the pressurization to obtain 2940 g of a dark gray yellow red liquid reaction product.
【００３１】次に、このカルボキシル化反応生成物を１
l オートクレーブに４９０．０ｇ移し、硫黄１７．７ｇ
（０．５５モル、アルカリ土類金属試薬１モル当たり
１．１モル）を１０５℃で添加し、次いで１５０℃まで
昇温し、窒素で２．０atm まで加圧した後、エチレング
リコール６２．１ｇ（１．０モル、アルカリ土類金属試
薬１モル当たり２．０モル）を３０分で全量添加し、次
いで１６５℃まで昇温し、その後窒素で５．０atm まで
加圧し開放系（反応容器の圧力が５atm を越えると５at
m になるまで減圧し、５atm を下回ると５atm まで加圧
する系）で４時間撹拌した。Next, 1 part of this carboxylation reaction product is obtained.
l Transferred 490.0g to an autoclave, sulfur 17.7g
(0.55 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 105 ° C., then heated to 150 ° C., pressurized with nitrogen to 2.0 atm, and then ethylene glycol 62.1 g (1.0 mol, 2.0 mol per 1 mol of alkaline earth metal reagent) was added in 30 minutes, then the temperature was raised to 165 ° C., and the pressure was increased to 5.0 atm with nitrogen. 5at when pressure exceeds 5atm
The pressure was reduced to m, and when it was lower than 5 atm, the pressure was increased to 5 atm) and the mixture was stirred for 4 hours.
【００３２】次に、該反応生成物に１５０ニュートラル
油（１００℃の粘度が５．２７cStのパラフィン系潤滑
油、以下の例においても、用いた１５０ニュートラル油
はこれと同じである）１６５．５ｇを添加し、撹拌した
後、１l三口梨型フラスコに６４９．５ｇ移しとり、大
部分のエチレングリコールとドデシルフェノールおよび
少量の潤滑油留分３５５．９ｇを留去して、蒸留残留物
２８６．８ｇを得た。その際の最終留出物温度は２００
℃（２．５mmHg）であった。この後、蒸留残留物中に含
まれる極少量の不溶解物をろ過により除去し、極暗い黄
赤色透明粘稠な液状の最終製品２８４．８ｇを得た。こ
の最終製品の一般的性状を表１に示す。回収フェノール
類の濁りは目視にて判定した（以下の例も同様）。Next, 165.5 g of 150 neutral oil (a paraffin type lubricating oil having a viscosity of 5.27 cSt at 100 ° C., the same 150 neutral oil was used in the following examples) as the reaction product. Was added and stirred, and then 649.5 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil fraction 355.9 g were distilled off to obtain 286.8 g of distillation residue. Got The final distillate temperature at that time is 200
It was ℃ (2.5 mmHg). After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 284.8 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 1. The turbidity of the recovered phenols was visually determined (the same applies to the following examples).
【００３３】なお、色相はASTM D1500に従って測定した
（以下の例も同様）。すなわち、試料１５容量部を白灯
油８５容量部に溶解させ、それをＡＳＴＭ比色管に移
し、ＡＳＴＭ比色計にて測定した。このときの色相が８
以上となる場合は、再度その灯油溶液１５容量部を８５
容量部の白灯油に溶解させ、色相を測定する。それでも
なお色相が８以上の場合は８以内になるまで同様の操作
により測定を繰り返す。The hue was measured according to ASTM D1500 (the same applies to the following examples). That is, 15 parts by volume of a sample was dissolved in 85 parts by volume of white kerosene, transferred to an ASTM colorimetric tube, and measured by an ASTM colorimeter. The hue at this time is 8
In the case of the above, again add 15 parts by volume of the kerosene solution
Dissolve in a volume of white kerosene and measure the hue. If the hue is still 8 or more, repeat the measurement by the same operation until it falls within 8.
【００３４】また、この反応生成物２．００ｇを分液ロ
ートにとり、６０ｍｌのエーテルに溶解させ、１Ｎの硫
酸１５ｍｌを添加して加水分解し（振とう機にて６０分
撹拌）、十分水洗後エーテル層を分離し、次いでエーテ
ルをロータリーエバポレーターにて除去したところ、褐
色の液状物１．８０ｇを得た。この液状物の酸価は２７
ｍｇＫＯＨ／ｇであった（以下の例においても酸価の測
定は、上記と全く同じ手法で行った）。Further, 2.00 g of this reaction product was taken in a separating funnel, dissolved in 60 ml of ether and hydrolyzed by adding 15 ml of 1N sulfuric acid (stirring for 60 minutes on a shaker), followed by thorough washing with water The ether layer was separated, and then the ether was removed by a rotary evaporator to obtain 1.80 g of a brown liquid material. The acid value of this liquid is 27.
It was mgKOH / g (in the following examples, the acid value was measured by the same method as above).
【００３５】比較例１ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５l オートクレーブに純度９４．４％のドデシルフェ
ノール２５０１．０ｇ（９．０モル）、１５０ニュート
ラル油３３６．６ｇ、純度９３．２％の酸化カルシウム
１８０．６ｇ（３．０モル）を送入し、撹拌した。この
懸濁液にエチレングリコール２５１．５ｇ（４．０５モ
ル）にイオン交換水５．４ｇ（０．３モル）を混合した
溶液を、窒素気流中１．５atm の加圧下、１３０℃、３
０分で全量添加し、終了後これを３．０atm まで窒素で
加圧し、１３０℃で３時間反応させた。その後、該反応
系を徐々に減圧しながら、添加した水、生成水、添加し
た大部分のエチレングリコール、および少量のドデシル
フェノール（６７２．１ｇ）を留去して、カラシ色の液
状の蒸留残留物２６００．０ｇが得られた。その際の塔
底物の温度は１７８℃、留出物温度は１３６℃（１mmH
g）であった。Comparative Example 1 2501.0 g (9.0 mol) of 94.4% pure dodecylphenol and 336.6 g of 150 neutral oil were placed in a 5 l autoclave equipped with a stirrer, a cooling tube, a nitrogen gas introducing tube and a thermometer. 180.6 g (3.0 mol) of calcium oxide having a purity of 93.2% was fed and stirred. A solution prepared by mixing 251.5 g (4.05 mol) of ethylene glycol with 5.4 g (0.3 mol) of ion-exchanged water was added to this suspension at 130 ° C. under a pressure of 1.5 atm in a nitrogen stream.
The whole amount was added at 0 minutes, and after the completion, this was pressurized to 3.0 atm with nitrogen and reacted at 130 ° C for 3 hours. Then, while gradually reducing the pressure of the reaction system, the added water, the produced water, most of the added ethylene glycol, and a small amount of dodecylphenol (672.1 g) were distilled off to leave a mustard-colored liquid distillation residue. 2600.0 g of the product was obtained. At that time, the temperature of the bottom product was 178 ° C, and the temperature of the distillate was 136 ° C (1 mmH
g).
【００３６】次に該蒸留残留物２６００．０ｇに１７８
℃、１mmHgの状態から攪拌しながら二酸化炭素を１．３
５l／minの流速で３０分吹き込み、その後さらに二酸化
炭素で５．０atm まで昇圧し、昇圧後その状態のまま４
時間保持して、暗い灰黄赤色の液状反応生成物２７２
０．０ｇを得た。Then, 2600.0 g of the distillation residue is added to 178
℃ 1mmHg from the state of stirring while stirring carbon dioxide 1.3
Blow for 30 minutes at a flow rate of 5 l / min, then further pressurize with carbon dioxide to 5.0 atm, and after pressurizing, keep that state 4
Hold for time, dark gray yellow red liquid reaction product 272
0.0 g was obtained.
【００３７】次に、このカルボキシル化反応生成物を１
l オートクレーブに４５１．０ｇ移し、硫黄１７．６ｇ
（０．５５モル、アルカリ土類金属試薬１モル当たり
１．１モル）を１０５℃で添加し、次いで１５０℃まで
昇温し、窒素で２atm まで加圧し、エチレングリコール
４６．３ｇ（０．７５モル、アルカリ土類金属試薬１モ
ル当たり１．５モル）を３０分で全量添加し、次いで１
６５℃まで昇温し、その後窒素で５．０atm まで加圧
し、開放系（反応容器の圧力が５atm を越えると５atm
になるまで減圧し、５atm を下回ると５atm まで加圧す
る系、以下の例においても開放系という語は、このよう
な系を示す）で４時間撹拌した。Next, 1 part of this carboxylation reaction product is obtained.
l Transferred 451.0g to an autoclave, sulfur 17.6g
(0.55 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 105 ° C., then heated to 150 ° C., pressurized with nitrogen to 2 atm, and ethylene glycol 46.3 g (0.75 mol). Mol, 1.5 mol per mol of alkaline earth metal reagent) in 30 minutes, and then 1
The temperature was raised to 65 ° C and then pressurized to 5.0 atm with nitrogen, and opened system (5 atm when the pressure in the reaction vessel exceeded 5 atm).
The system was stirred for 4 hours in a system in which the pressure was reduced to 5, and when the pressure was lower than 5 atm, the pressure was increased to 5 atm. In the following examples, the term "open system" refers to such a system).
【００３８】次に、該反応生成物に１５０ニュートラル
油１０８．８ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに５３０．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分２
４７．６ｇを留去して、蒸留残留物２７３．６８ｇを得
た。その際の最終留出物温度は１９８℃（１．５mmHg）
であった。この後、蒸留残留物中に含まれる極少量の不
溶解物をろ過により除去し、極暗い黄赤色透明粘稠な液
状の最終製品２７０．２ｇを得た。この最終製品の一般
的性状を表１に示す。Next, 108.8 g of 150 neutral oil was added to the reaction product, and after stirring, 530.9 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 2
47.6 g was distilled off to obtain 273.68 g of a distillation residue. The final distillate temperature at that time was 198 ° C (1.5 mmHg)
Met. After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 270.2 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 1.
【００３９】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３８ｍｇＫＯＨ／ｇであっ
た。An acid value obtained by taking 2.00 g of this reaction product in the same manner as in Example 1 was 38 mgKOH / g.
【００４０】この比較例１は、実施例１と比して二価ア
ルコールをアルカリ土類金属試薬１モル当たり１．５モ
ルと少なくした例である。表１を見ればわかるように色
相は実施例１とほぼ同じだが、回収フェノールに濁りを
生じている。Comparative Example 1 is an example in which the amount of the dihydric alcohol was reduced to 1.5 mol per mol of the alkaline earth metal reagent as compared with Example 1. As can be seen from Table 1, the hue is almost the same as in Example 1, but the recovered phenol is turbid.
【００４１】比較例２ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５lオートクレーブに純度９４．４％のドデシルフェ
ノール２６６７．７ｇ（９．６モル）、１５０ニュート
ラル油３３６．６ｇ、純度９５．８％の酸化カルシウム
１７５．７ｇ（３．０モル）を送入し、撹拌した。この
懸濁液にエチレングリコール２５１．５ｇ（４．０５モ
ル）にイオン交換水５．４ｇ（０．３モル）を混合した
溶液を、窒素気流中２．０atm の加圧下、１３０℃、３
０分で全量添加し、終了後これを３．０atm まで窒素で
加圧し、１３０℃で３時間反応させた。その後、該反応
系を徐々に減圧しながら、添加した水、生成水、添加し
た大部分のエチレングリコール、および少量のドデシル
フェノール（６７６．９ｇ）を留去して、カラシ色の液
状の蒸留残留物２７１２．０ｇが得られた。その際の塔
底物の温度は１７８℃、留出物温度は１３８℃（３mmH
g）であった。Comparative Example 2 In a 5 l autoclave equipped with a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a thermometer, dodecylphenol 2667.7 g (9.6 mol) having a purity of 94.4%, 150 neutral oil 336.6 g, 175.7 g (3.0 mol) of calcium oxide having a purity of 95.8% was fed and stirred. A solution prepared by mixing 251.5 g (4.05 mol) of ethylene glycol with 5.4 g (0.3 mol) of ion-exchanged water was added to this suspension under a pressure of 2.0 atm in a nitrogen stream at 130 ° C. for 3 days.
The whole amount was added at 0 minutes, and after the completion, this was pressurized to 3.0 atm with nitrogen and reacted at 130 ° C for 3 hours. Then, while gradually reducing the pressure of the reaction system, the added water, the produced water, most of the added ethylene glycol, and a small amount of dodecylphenol (676.9 g) were distilled off to leave a mustard-colored liquid distillation residue. 2712.0 g of the product was obtained. At that time, the temperature of the bottom product was 178 ° C, and the temperature of the distillate was 138 ° C (3 mmH
g).
【００４２】次に該蒸留残留物２８２０．５ｇに１７８
℃、３mmHgの状態から攪拌しながら二酸化炭素を１．３
５l／minの流速で３０分吹き込み、その後さらに二酸化
炭素で５．０atm まで昇圧し、昇圧後その状態のまま４
時間保持して、暗い灰黄赤色の液状反応生成物２８２
０．５ｇを得た。Then, 178 was added to 2820.5 g of the distillation residue.
℃, 3mmHg from the state of stirring while stirring carbon dioxide 1.3
Blow for 30 minutes at a flow rate of 5 l / min, then further pressurize with carbon dioxide to 5.0 atm, and after pressurizing, keep that state 4
Hold for a time to obtain a dark gray yellow red liquid reaction product 282
0.5 g was obtained.
【００４３】次に、このカルボキシル化反応生成物を１
l オートクレーブに４７３．４ｇ移し、硫黄１６．２ｇ
（０．５０モル、アルカリ土類金属試薬１モル当たり
１．０モル）を１０５℃で添加し、次いで１７０℃まで
昇温し、窒素で３atm まで加圧し、エチレングリコール
６２．４ｇ（１．０モル、アルカリ土類金属試薬１モル
当たり２．０モル）を３０分で全量添加し、次いで１７
０℃まで昇温し、その後窒素で５．０atm まで加圧し、
密閉系で４時間撹拌した。反応終了後の圧力は、６．７
atmとなった。Next, 1 part of this carboxylation reaction product is added.
l Transferred 473.4g to an autoclave, sulfur 16.2g
(0.50 mol, 1.0 mol per mol of alkaline earth metal reagent) was added at 105 ° C., then the temperature was raised to 170 ° C. and pressurized to 3 atm with nitrogen, and ethylene glycol 62.4 g (1.0 Mol, 2.0 mol per mol of alkaline earth metal reagent) was added in 30 minutes, then 17
Heat up to 0 ℃, pressurize with nitrogen to 5.0atm,
The mixture was stirred in a closed system for 4 hours. The pressure after the reaction is 6.7.
It became atm.
【００４４】次に、該反応生成物に１５０ニュートラル
油１１０．８ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６５９．０ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分２
９３．３ｇを留去して、蒸留残留物２９２．２ｇを得
た。その際の最終留出物温度は１８５℃（３mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２８８．１ｇを得た。この最終製品の一般的性
状を表１に示す。Next, 110.8 g of 150 neutral oil was added to the reaction product, and the mixture was stirred and transferred to 659.0 g in a 1-liter three-neck pear-shaped flask. Most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 2
By distilling off 93.3 g, 292.2 g of a distillation residue was obtained. The final distillate temperature at that time was 185 ° C. (3 mmHg). After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 288.1 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 1.
【００４５】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３３ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of this reaction product, obtained in the same manner as in Example 1, was 33 mgKOH / g.
【００４６】この比較例２は、実施例１と比して、硫化
反応を加圧密閉系で行った例である。表１を見ればわか
るように色相は実施例１と同じだが、回収フェノールに
濁りを生じている。Compared to Example 1, this Comparative Example 2 is an example in which the sulfurization reaction was carried out in a pressure-closed system. As can be seen from Table 1, the hue is the same as in Example 1, but the recovered phenol is turbid.
【００４７】実施例２ 実施例１で得たカルボキシル化反応生成物４９０．０ｇ
を１lオートクレーブに移し、硫黄１７．７ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０３℃で添加し、次いで１５０℃まで昇温し、
窒素で３atm まで加圧し、エチレングリコール６２．１
ｇ（１．０モル、アルカリ土類金属試薬１モル当たり
２．０モル）を３０分で全量添加し、次いで１７８℃ま
で昇温し、その後窒素で５．０atm まで加圧し、開放系
で４時間撹拌した。Example 2 490.0 g of the carboxylation reaction product obtained in Example 1.
Was transferred to a 1-liter autoclave, and 17.7 g of sulfur (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 103 ° C., then the temperature was raised to 150 ° C.,
Pressurize with nitrogen to 3 atm, ethylene glycol 62.1
g (1.0 mole, 2.0 moles per mole of alkaline earth metal reagent) was added in 30 minutes, then the temperature was raised to 178 ° C., and then nitrogen was pressurized to 5.0 atm. Stir for hours.
【００４８】次に、該反応生成物に１５０ニュートラル
油１６５．５ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６４９．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
５４．６ｇを留去して、蒸留残留物２９２．５ｇを得
た。その際の最終留出物温度は１９８℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２８８．４ｇを得た。この最終製品の一般的性
状を表１に示す。Next, 165.5 g of 150 neutral oil was added to the reaction product, and after stirring, 649.9 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 3
54.6 g was distilled off to obtain 292.5 g of a distillation residue. The final distillate temperature at that time was 198 ° C. (2 mmHg). Then, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 288.4 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 1.
【００４９】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は１７ｍｇＫＯＨ／ｇであっ
た。An acid value of 17 mgKOH / g was obtained by taking 2.00 g of this reaction product and carrying out in the same manner as in Example 1.
【００５０】この実施例２は、硫化反応を加圧開放系で
行い反応温度を１７８℃とした例である。表１よりわか
るように、反応温度が高いため酸価が低下しているが、
色相は明るく、回収フェノールは濁っていない。Example 2 is an example in which the sulfurization reaction was carried out in a pressure open system and the reaction temperature was 178 ° C. As can be seen from Table 1, since the reaction temperature is high, the acid value is low,
The hue is bright and the recovered phenol is not cloudy.
【００５１】比較例３ 実施例１で得たカルボキシル化反応生成物４９０．２ｇ
を１lオートクレーブに移し、硫黄１７．７ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで１５０℃まで昇温し、
窒素で１．０atmまで加圧し、エチレングリコール６
２．１ｇ（１．０モル、アルカリ土類金属試薬１モル当
たり２．０モル）を３０分で全量添加し、次いで窒素で
５．０atm まで加圧し、開放系で４時間撹拌した。Comparative Example 3 490.2 g of the carboxylation reaction product obtained in Example 1.
Was transferred to a 1-liter autoclave, and 17.7 g of sulfur (0.5
5 moles, 1.1 moles per mole of alkaline earth metal reagent) at 100 ° C., then heated to 150 ° C.,
Pressurize with nitrogen to 1.0 atm, ethylene glycol 6
2.1 g (1.0 mol, 2.0 mol per mol of alkaline earth metal reagent) was added in total over 30 minutes, then pressurized to 5.0 atm with nitrogen and stirred for 4 hours in an open system.
【００５２】次に、該反応生成物に１５０ニュートラル
油１６５．６ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６２８．８ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
４１．２ｇを留去して、蒸留残留物２８０．７ｇを得
た。その際の最終留出物温度は１９５℃（３mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２７７．２ｇを得た。この最終製品の一般的性
状を表１に示す。Next, 165.6 g of 150 neutral oil was added to the reaction product, and the mixture was stirred and transferred to 628.8 g in a 1-liter three-neck pear-shaped flask, where most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 3
41.2 g was distilled off to obtain 280.7 g of a distillation residue. The final distillate temperature at that time was 195 ° C. (3 mmHg). After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 277.2 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 1.
【００５３】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３２ｍｇＫＯＨ／ｇであっ
た。An acid value of 32 mg KOH / g was obtained by taking 2.00 g of this reaction product and carrying out the same procedure as in Example 1.
【００５４】この比較例３は、硫化反応を加圧開放系で
行い反応温度を１５０℃とした例である。表１よりわか
るように、硫化反応温度を低くすると、回収フェノール
は濁ってしまうばかりか、製品の色相は暗くなり、また
粘度の高い製品ができてしまう。Comparative Example 3 is an example in which the sulfurization reaction was carried out in a pressure open system and the reaction temperature was 150 ° C. As can be seen from Table 1, when the sulfurization reaction temperature is lowered, not only the recovered phenol becomes turbid, but also the hue of the product becomes dark and a product having a high viscosity is produced.
【００５５】[0055]
【表１】 [Table 1]
【００５６】実施例３ 撹拌器、冷却管、窒素ガス導入管および温度計を装着し
た５lオートクレーブに純度９４．４％のドデシルフェ
ノール２９１７．８ｇ（１０．５モル）、純度９３．２
％の酸化カルシウム１８０．６ｇ（３．０モル）を送入
し、撹拌した。この懸濁液にエチレングリコール２５
１．５ｇ（４．０５モル）にイオン交換水５．４ｇ
（０．３モル）を混合した溶液を、窒素気流中１．５at
m の加圧下、１３０℃、３０分で全量添加し、終了後こ
れを３．０atm まで窒素で加圧し、１３０℃で３時間反
応させた。その後、該反応系を徐々に減圧しながら、添
加した水、生成水、添加した大部分のエチレングリコー
ルおよび少量のドデシルフェノール（３８５．０ｇ）を
留去して、カラシ色の液状の蒸留残留物２９６５．２ｇ
が得られた。その際の塔底物の温度は１７３℃、留出物
温度は１０９℃（３mmHg）であった。Example 3 A 5 l autoclave equipped with a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a thermometer was charged with 2917.8 g (10.5 mol) of dodecylphenol having a purity of 94.4% and a purity of 93.2.
% Of calcium oxide (180.6 g, 3.0 mol) was fed in and stirred. Add ethylene glycol 25 to this suspension.
Ion-exchanged water 5.4g to 1.5g (4.05mol)
(0.3 mol) mixed solution in a nitrogen stream at 1.5 at
The entire amount was added under a pressure of m 3 at 130 ° C. for 30 minutes, and after the completion, this was pressurized to 3.0 atm with nitrogen and reacted at 130 ° C. for 3 hours. Then, while gradually reducing the pressure of the reaction system, the added water, the produced water, most of the added ethylene glycol and a small amount of dodecylphenol (385.0 g) were distilled off to give a mustard-colored liquid distillation residue. 2965.2g
was gotten. At that time, the temperature of the bottom product was 173 ° C, and the distillate temperature was 109 ° C (3 mmHg).
【００５７】次に該蒸留残留物２９６５．２ｇに１７８
℃、３mmHgの状態から二酸化炭素を吹き込み５．０atm
まで昇圧し、昇圧後その状態のまま４時間保持して、暗
い灰黄赤色の液状反応生成物３０８５ｇを得た。178 was then added to 2965.2 g of the distillation residue.
5.0 atm by injecting carbon dioxide from the condition of ℃, 3mmHg
After pressurization, the pressure was maintained for 4 hours, and 3085 g of a dark gray yellow red liquid reaction product was obtained.
【００５８】次に、このカルボキシル化反応生成物を１
l オートクレーブに４３８．８ｇ移し、硫黄１５．１ｇ
（０．４７モル、アルカリ土類金属試薬１モル当たり
１．１モル）を１０３℃で添加し、次いで窒素を１５ml
／minの流速で流しながら１５０℃まで昇温し、エチレ
ングリコール２６．５ｇ（０．４３モル、アルカリ土類
金属試薬１モル当たり１．０モル）を３０分で全量添加
し、次いで１６５℃まで昇温し、窒素を１５ml／minの
流速で流しながら常圧開放系で４時間撹拌した。Next, 1 part of this carboxylation reaction product is added.
l Transferred 438.8g to an autoclave and added 15.1g of sulfur.
(0.47 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 103 ° C., then 15 ml of nitrogen was added.
The temperature was raised to 150 ° C while flowing at a flow rate of 1 / min, 26.5 g of ethylene glycol (0.43 mol, 1.0 mol per 1 mol of alkaline earth metal reagent) was added in 30 minutes, and then the temperature was increased to 165 ° C. The temperature was raised, and the mixture was stirred for 4 hours in an atmospheric pressure open system while flowing nitrogen at a flow rate of 15 ml / min.
【００５９】次に、該反応生成物に１５０ニュートラル
油１４１．３ｇを添加し、撹拌した後、１l三口梨型フ
ラスコに５２３．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分２
７５．８ｇを留去して、蒸留残留物２４３．６ｇを得
た。その際の最終留出物温度は１９３℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２３９．５ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 141.3 g of 150 neutral oil was added to the reaction product, and after stirring, transferred to 523.9 g in a 1-liter three-neck pear-shaped flask, most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 2
75.8 g was distilled off to obtain 243.6 g of a distillation residue. The final distillate temperature at that time was 193 ° C. (2 mmHg). After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 239.5 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 2.
【００６０】また、この反応生成物２．００ｇを採り、
実施例１と同様にして得た酸価は３０ｍｇＫＯＨ／ｇで
あった。Further, 2.00 g of this reaction product was taken,
The acid value obtained in the same manner as in Example 1 was 30 mgKOH / g.
【００６１】実施例４ 実施例３で得たカルボキシル化反応生成物５０３．７ｇ
を１lオートクレーブに移し、硫黄１７．３ｇ（０．５
４モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０６℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール１５．２ｇ（０．２５モル、アルカリ土類金属試
薬１モル当たり０．５モル）を３０分で全量添加し、次
いで１６５℃まで昇温し、窒素を１５ml／minの流速で
流しながら、常圧開放系で４時間撹拌した。Example 4 503.7 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.3 g of sulfur (0.5
4 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 106 ° C., then the temperature was raised to 150 ° C. while nitrogen was bubbled at a flow rate of 15 ml / min, and ethylene glycol 15.2 g (0.1. 25 moles, 0.5 moles per mole of alkaline earth metal reagent) were added in 30 minutes in total, then the temperature was raised to 165 ° C. and nitrogen was flowed at a flow rate of 15 ml / min for 4 hours under an atmospheric pressure open system. It was stirred.
【００６２】次に、該反応生成物に１５０ニュートラル
油１６２．１ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに５８１．９ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
０１．１ｇを留去して、蒸留残留物２７４．２ｇを得
た。その際の最終留出物温度は１９１℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２６８．６ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 162.1 g of 150 neutral oil was added to the reaction product, and after stirring, 581.9 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 3
By distilling off 01.1 g, 274.2 g of a distillation residue was obtained. The final distillate temperature at that time was 191 ° C. (2 mmHg). Then, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 268.6 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 2.
【００６３】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３３ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of this reaction product, which was obtained in the same manner as in Example 1, was 33 mgKOH / g.
【００６４】この実施例４は、硫化反応を常圧開放系で
行いエチレングリコール添加量をアルカリ土類金属試薬
１モル当たり０．５モル添加して行った例である。Example 4 is an example in which the sulfurization reaction was carried out in an atmospheric pressure open system, and ethylene glycol was added in an amount of 0.5 mol per mol of the alkaline earth metal reagent.
【００６５】実施例５ 実施例３で得たカルボキシル化反応生成物５１０．３ｇ
を１lオートクレーブに移し、硫黄１７．５ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール６１．６ｇ（１．０モル、アルカリ土類金属試薬
１モル当たり２．０モル）を３０分で全量添加し、次い
で１７８℃まで昇温し、窒素を１５ml／minの流速で流
しながら、常圧開放系で４時間撹拌した。Example 5 510.3 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.5 g of sulfur (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 100 ° C., then the temperature was raised to 150 ° C. while nitrogen was bubbled at a flow rate of 15 ml / min, and 61.6 g (1. (0 mol, 2.0 mol per mol of alkaline earth metal reagent) was added in 30 minutes in total, then the temperature was raised to 178 ° C. and nitrogen was flowed at a flow rate of 15 ml / min for 4 hours under an atmospheric pressure open system. It was stirred.
【００６６】次に、該反応生成物に１５０ニュートラル
油１６４．２ｇを添加し、撹拌した後、１l三口梨型フ
ラスコに６３５．２ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
５４．９ｇを留去して、蒸留残留物２７８．０ｇを得
た。その際の最終留出物温度は１９７℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２６９．８ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 164.2 g of 150 neutral oil was added to the reaction product, and after stirring, 635.2 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 3
54.9 g was distilled off to obtain 278.0 g of a distillation residue. The final distillate temperature at that time was 197 ° C. (2 mmHg). Then, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 269.8 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 2.
【００６７】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は１８ｍｇＫＯＨ／ｇであっ
た。2.00 g of this reaction product was taken and the acid value obtained in the same manner as in Example 1 was 18 mgKOH / g.
【００６８】この実施例５は、硫化反応を常圧開放系で
行いエチレングリコール添加量をアルカリ土類金属試薬
１モル当たり２．０モル添加し、反応温度を１７８℃で
行った例である。回収フェノールに濁りは生じないが、
反応温度が若干高めのため、酸化が低下している。Example 5 is an example in which the sulfurization reaction was carried out in an atmospheric pressure open system, and the amount of ethylene glycol added was 2.0 mol per mol of the alkaline earth metal reagent, and the reaction temperature was 178 ° C. Turbidity does not occur in the recovered phenol,
Oxidation is reduced because the reaction temperature is slightly higher.
【００６９】実施例６ 実施例１で得たカルボキシル化反応生成物５３７．８ｇ
を１lオートクレーブに移し、硫黄１９．４ｇ（０．６
０モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１６５℃まで昇温し、エチレングリ
コール６８．２ｇ（１．１モル、アルカリ土類金属試薬
１モル当たり２．０モル）を３０分で全量添加し、窒素
を１５ml／minの流速で流したまま、常圧開放系、１６
５℃で４時間撹拌した。Example 6 537.8 g of the carboxylation reaction product obtained in Example 1
Was transferred to a 1-liter autoclave, and 19.4 g of sulfur (0.6
0 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 100 ° C., then the temperature was raised to 165 ° C. while nitrogen was bubbled at a flow rate of 15 ml / min, and 68.2 g (1. 1 mole, 2.0 moles per mole of alkaline earth metal reagent) was added in 30 minutes, and nitrogen was kept flowing at a flow rate of 15 ml / min while maintaining the atmospheric pressure open system, 16
The mixture was stirred at 5 ° C for 4 hours.
【００７０】次に、該反応生成物に１５０ニュートラル
油１８１．７ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに７０２．３ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
８５．４ｇを留去して、蒸留残留物３１２．０ｇを得
た。その際の最終留出物温度は２００℃（２．５mmHg）
であった。この後、蒸留残留物中に含まれる極少量の不
溶解物をろ過により除去し、極暗い黄赤色透明粘稠な液
状の最終製品３０８．１ｇを得た。この最終製品の一般
的性状を表２に示す。Next, 181.7 g of 150 neutral oil was added to the reaction product, and after stirring, 702.3 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 3
85.4 g was distilled off to obtain 312.0 g of a distillation residue. The final distillate temperature at that time is 200 ℃ (2.5mmHg)
Met. After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 308.1 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 2.
【００７１】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は２７ｍｇＫＯＨ／ｇであっ
た。2.00 g of this reaction product was taken and the acid value obtained in the same manner as in Example 1 was 27 mgKOH / g.
【００７２】この実施例６は、硫化反応を常圧開放系で
行いエチレングリコール添加量をアルカリ土類金属試薬
１モル当たり２．０モル添加し、反応温度を１６５℃で
行った例である。Example 6 is an example in which the sulfurization reaction was carried out in an atmospheric pressure open system, the amount of ethylene glycol added was 2.0 mol per mol of the alkaline earth metal reagent, and the reaction temperature was 165 ° C.
【００７３】比較例４ 実施例３で得たカルボキシル化反応生成物５１０．２ｇ
を１lオートクレーブに移し、硫黄１７．５ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１００℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール６１．６ｇ（１．０モル、アルカリ土類金属試薬
１モル当たり２．０モル）を３０分で全量添加し、窒素
を１５ml／minの流速で流しながら、常圧開放系、１５
０℃で４時間撹拌した。Comparative Example 4 510.2 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.5 g of sulfur (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 100 ° C., then the temperature was raised to 150 ° C. while nitrogen was bubbled at a flow rate of 15 ml / min, and 61.6 g (1. (0 mol, 2.0 mol per mol of alkaline earth metal reagent) was added in 30 minutes, and nitrogen was flowed at a flow rate of 15 ml / min.
The mixture was stirred at 0 ° C for 4 hours.
【００７４】次に、該反応生成物に１５０ニュートラル
油１６４．２ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６５９．８ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
６１．７ｇを留去して、蒸留残留物２８９．１ｇを得
た。その際の最終留出物温度は１９７℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２８５．９ｇを得た。この最終製品の一般的性
状を表２に示す。Next, 164.2 g of 150 neutral oil was added to the reaction product, and the mixture was stirred and transferred to 659.8 g in a 1-liter three-neck pear-shaped flask. Most of ethylene glycol, dodecylphenol and a small amount of lubricating oil were added. Fraction 3
61.7 g was distilled off to obtain 289.1 g of a distillation residue. The final distillate temperature at that time was 197 ° C. (2 mmHg). Then, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 285.9 g of an extremely dark yellow-red transparent viscous liquid final product. The general properties of this final product are shown in Table 2.
【００７５】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３９ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of this reaction product, which was obtained in the same manner as in Example 1, was 39 mgKOH / g.
【００７６】この比較例４は硫化反応を常圧開放系で行
いエチレングリコール添加量をアルカリ土類金属試薬１
モル当たり２．０モル添加し、反応温度を１５０℃で行
った例である。反応温度が若干低いため、酸化は高い値
だが、回収フェノールに濁りを生じている。また、色相
も若干高めである。In Comparative Example 4, the sulfurization reaction was carried out in an atmospheric pressure open system, and the amount of ethylene glycol added was changed to alkaline earth metal reagent 1.
In this example, 2.0 mol per mol was added and the reaction temperature was 150 ° C. Since the reaction temperature is slightly low, the oxidation value is high, but the recovered phenol is turbid. The hue is also slightly higher.
【００７７】[0077]
【表２】 [Table 2]
【００７８】実施例７ 実施例３で得たカルボキシル化反応生成物５１０．３ｇ
を１lオートクレーブに移し、硫黄１７．５ｇ（０．５
５モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０８℃で添加し、次いで窒素を１５ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール４６．２ｇ（０．７５モル、アルカリ土類金属試
薬１モル当たり１．５モル）を３０分で全量添加し、そ
の後１６５℃まで昇温し、窒素を１５ml／minの流速で
流しながら、常圧開放系、１６５℃で４時間撹拌した。Example 7 510.3 g of the carboxylation reaction product obtained in Example 3
Was transferred to a 1-liter autoclave, and 17.5 g of sulfur (0.5
5 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 108 ° C., then the temperature was raised to 150 ° C. while nitrogen was being bubbled through at a flow rate of 15 ml / min, and 46.2 g (0. (75 moles, 1.5 moles per mole of alkaline earth metal reagent) was added in 30 minutes, and the temperature was raised to 165 ° C. Nitrogen was allowed to flow at a flow rate of 15 ml / min. And stirred for 4 hours.
【００７９】次に、該反応生成物に１５０ニュートラル
油１６４．２ｇを添加し、撹拌した後、１l 三口梨型フ
ラスコに６５９．８ｇ移しとり、大部分のエチレングリ
コールとドデシルフェノールおよび少量の潤滑油留分３
３７．９ｇを留去して、蒸留残留物２７６．５ｇを得
た。その際の最終留出物温度は１９１℃（２mmHg）であ
った。この後、蒸留残留物中に含まれる極少量の不溶解
物をろ過により除去し、極暗い黄赤色透明粘稠な液状の
最終製品２７２．５ｇを得た。この最終製品の一般的性
状を表３示す。Next, 164.2 g of 150 neutral oil was added to the reaction product, and the mixture was stirred and transferred to 659.8 g in a 1-liter three-neck pear-shaped flask. Most of ethylene glycol and dodecylphenol and a small amount of lubricating oil were added. Fraction 3
37.9 g was distilled off to obtain 276.5 g of a distillation residue. The final distillate temperature at that time was 191 ° C. (2 mmHg). After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 272.5 g of an extremely dark yellow-red transparent viscous liquid final product. Table 3 shows the general properties of this final product.
【００８０】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３１ｍｇＫＯＨ／ｇであっ
た。2.00 g of this reaction product was taken and the acid value obtained in the same manner as in Example 1 was 31 mgKOH / g.
【００８１】実施例８ 比較例１で得たカルボキシル化反応生成物３４９．１ｇ
を１lオートクレーブに移し、硫黄１３．６ｇ（０．４
２モル、アルカリ土類金属試薬１モル当たり１．１モ
ル）を１０３℃で添加し、次いで窒素を３０ml／minの
流速で通気しながら１５０℃まで昇温し、エチレングリ
コール３５．９ｇ（０．５８モル、アルカリ土類金属試
薬１モル当たり１．５モル）を３０分で全量添加し、そ
の後、１６５℃まで昇温し、窒素を３０ml／minの流速
で流しながら、常圧開放系、１６５℃で４時間撹拌し
た。Example 8 349.1 g of the carboxylation reaction product obtained in Comparative Example 1
Was transferred to a 1-liter autoclave, and 13.6 g of sulfur (0.4
2 mol, 1.1 mol per mol of alkaline earth metal reagent) was added at 103 ° C., then the temperature was raised to 150 ° C. while nitrogen was being bubbled at a flow rate of 30 ml / min, and 35.9 g (0. (58 moles, 1.5 moles per mole of alkaline earth metal reagent) was added in 30 minutes, and then the temperature was raised to 165 ° C. and nitrogen was flowed at a flow rate of 30 ml / min, while maintaining a normal pressure open system, 165 Stirred at 4 ° C for 4 hours.
【００８２】次に、該反応生成物に１５０ニュートラル
油８４．２ｇを添加し、撹拌した後、１l 三口梨型フラ
スコに４２０．９ｇ移しとり、大部分のエチレングリコ
ールとドデシルフェノールおよび少量の潤滑油留分１９
６．７ｇを留去して、蒸留残留物２２１．２を得た。そ
の際の最終留出物温度は１９２℃（１．５mmHg）であっ
た。この後、蒸留残留物中に含まれる極少量の不溶解物
をろ過により除去し、極暗い黄赤色透明粘稠な液状の最
終製品２１７．９ｇを得た。この最終製品の一般的性状
を表３示す。Next, 84.2 g of 150 neutral oil was added to the reaction product, and after stirring, 420.9 g was transferred to a 1-liter three-neck pear-shaped flask, and most of ethylene glycol and dodecyl phenol and a small amount of lubricating oil were added. Fraction 19
6.7 g was distilled off to obtain a distillation residue 221.2. The final distillate temperature at that time was 192 ° C. (1.5 mmHg). After that, a very small amount of insoluble matter contained in the distillation residue was removed by filtration to obtain 217.9 g of an extremely dark yellow-red transparent viscous liquid final product. Table 3 shows the general properties of this final product.
【００８３】この反応生成物２．００ｇを採り、実施例
１と同様にして得た酸価は３２ｍｇＫＯＨ／ｇであっ
た。An acid value of 2.00 g of this reaction product, obtained in the same manner as in Example 1, was 32 mgKOH / g.
【００８４】[0084]
【表３】 [Table 3]
【００８５】[0085]
【発明の効果】本製造法によると、アルカリ土類金属サ
リシレートおよびフェネートの硫化混合物の製造法にお
いて、硫化反応を反応温度１６０℃以上、常圧または加
圧の開放系にて二価アルコールをそれぞれの系によって
定められる特定量以上存在させる条件下で行うことによ
り、従来品と比較してアルカリ土類金属サリシレート及
びフェネートの硫化混合物の色相を著しく明るくするこ
とができるばかりでなく、回収される未反応フェノール
類が白濁せずに再利用可能となる。フェノール類は高価
であり、溶媒として多量に使用するため回収されたフェ
ノール類が再利用できることにより大幅なコスト削減と
なる。According to the present production method, in the production method of a sulfurized mixture of an alkaline earth metal salicylate and a phenate, the sulfurization reaction is carried out at a reaction temperature of 160 ° C. or higher, and the dihydric alcohol is added in an open system at atmospheric pressure or pressure. In addition to not only being able to significantly lighten the hue of the sulfurized mixture of alkaline earth metal salicylate and phenate as compared with the conventional product, but also to be recovered The reaction phenols can be reused without clouding. Phenols are expensive, and since a large amount is used as a solvent, the recovered phenols can be reused, which leads to a significant cost reduction.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｎ 30:04 40:00 Ｚ 8217−4Ｈ 70:00 (72)発明者 上田 早苗 埼玉県幸手市権現堂1134−２ 株式会社コ スモ総合研究所研究開発センター内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display location C10N 30:04 40:00 Z 8217-4H 70:00 (72) Inventor Sanae Sanae Satte City, Saitama Prefecture Gongendo 1134-2 Cosmo Research Institute Co., Ltd. R & D Center
Claims (2)
カリ土類金属酸化物あるいは水酸化物またはそれらの混
合物（以下、「アルカリ土類金属試薬」と言う。）より
なる反応原料混合物またはこれらに水を加えたものを反
応させ、次いで水および二価アルコールを留去して得ら
れた蒸留塔底物に二酸化炭素を反応させ、得られた生成
物に二価アルコール類および元素硫黄を添加して硫化反
応を行うことからなるサリチル酸類およびフェノール類
のアルカリ土類金属塩硫化混合物の製法において、硫化
反応の際、反応温度を１６０℃以上、加圧開放系で反応
を行い、添加する二価アルコール類をアルカリ土類金属
試薬１モル当たり２．０モル以上とすることを特徴とす
るサリチル酸類およびフェノール類のアルカリ土類金属
塩硫化混合物の製法。1. A reaction raw material mixture comprising phenols, dihydric alcohols, alkaline earth metal oxides or hydroxides or a mixture thereof (hereinafter referred to as "alkaline earth metal reagent"), or water to these. Was reacted, then water and dihydric alcohol were distilled off and carbon dioxide was reacted with the bottom product of the distillation column obtained, and dihydric alcohol and elemental sulfur were added to the obtained product. In the method for producing a sulfurized mixture of an alkaline earth metal salt of salicylic acids and phenols, which comprises performing a sulfurization reaction, during the sulfurization reaction, the reaction temperature is 160 ° C. or higher, the reaction is performed in a pressure open system, and a dihydric alcohol is added. Of at least 2.0 mol per mol of alkaline earth metal reagent, and a process for producing an alkaline earth metal salt sulfide mixture of salicylic acids and phenols. .
カリ土類金属酸化物あるいは水酸化物またはそれらの混
合物（以下、「アルカリ土類金属試薬」と言う。）より
なる反応原料混合物またはこれらに水を加えたものを反
応させ、次いで水および二価アルコールを留去して得ら
れた蒸留塔底物に二酸化炭素を反応させ、得られた生成
物に二価アルコール類および元素硫黄を添加して硫化反
応を行うことからなるサリチル酸類およびフェノール類
のアルカリ土類金属塩硫化混合物の製法において、硫化
反応の際、反応温度を１６０℃以上、常圧開放系で反応
を行い、添加する二価アルコール類をアルカリ土類金属
試薬１モル当たり０．５モル以上とすることを特徴とす
るサリチル酸類およびフェノール類のアルカリ土類金属
塩硫化混合物の製法。2. A reaction raw material mixture consisting of phenols, dihydric alcohols, alkaline earth metal oxides or hydroxides or a mixture thereof (hereinafter referred to as “alkaline earth metal reagent”), or water to them. Was reacted, then water and dihydric alcohol were distilled off and carbon dioxide was reacted with the bottom product of the distillation column obtained, and dihydric alcohol and elemental sulfur were added to the obtained product. In a method for producing a sulfurized mixture of an alkaline earth metal salt of salicylic acids and phenols, which comprises performing a sulfurization reaction, a dihydric alcohol to be added by performing a reaction at a reaction temperature of 160 ° C. or higher in an atmospheric pressure open system during the sulfurization reaction. Of at least 0.5 mol per mol of alkaline earth metal reagent, and a process for producing a mixture of salicylic acids and phenols with alkaline earth metal salts. .
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9539493A JP2819491B2 (en) | 1993-03-30 | 1993-03-30 | Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols |
| TW082107528A TW278098B (en) | 1992-09-18 | 1993-09-14 | |
| KR1019930018784A KR100277413B1 (en) | 1992-09-18 | 1993-09-17 | Method for preparing a mixture of salicylic acid compound and sulfided alkaline earth metal salt of phenol |
| CN93119338A CN1035015C (en) | 1992-09-18 | 1993-09-18 | Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol |
| DE69318240T DE69318240T2 (en) | 1992-09-18 | 1993-09-20 | Process for the preparation of a mixture of sulfur-containing alkaline earth metal salts of salicylic acid compounds and phenol |
| SG1996005673A SG49060A1 (en) | 1992-09-18 | 1993-09-20 | Process for producing mixture of sulfurized alkaline earth metal salts of salicyclic acid compound and phenol |
| EP93115102A EP0588368B1 (en) | 1992-09-18 | 1993-09-20 | Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol |
| US08/424,566 US5538650A (en) | 1992-09-18 | 1995-04-17 | Process for producing mixture of sulfurized alkaline earth metal salts of salicylic acid compound and phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9539493A JP2819491B2 (en) | 1993-03-30 | 1993-03-30 | Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287580A true JPH06287580A (en) | 1994-10-11 |
| JP2819491B2 JP2819491B2 (en) | 1998-10-30 |
Family
ID=14136440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9539493A Expired - Lifetime JP2819491B2 (en) | 1992-09-18 | 1993-03-30 | Preparation of alkaline earth metal sulfide mixtures of salicylic acids and phenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819491B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4868183A (en) * | 1986-07-21 | 1989-09-19 | Otsuka Pharmaceutical Factory, Inc. | N-pyrazinyl substituted P-aminophenols |
| WO1999064481A1 (en) * | 1998-06-05 | 1999-12-16 | Idemitsu Kosan Co., Ltd. | Succinimide compound, process for producing the same, lubricating oil additive, and lubricating oil composition for internal combustion engine |
-
1993
- 1993-03-30 JP JP9539493A patent/JP2819491B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4868183A (en) * | 1986-07-21 | 1989-09-19 | Otsuka Pharmaceutical Factory, Inc. | N-pyrazinyl substituted P-aminophenols |
| WO1999064481A1 (en) * | 1998-06-05 | 1999-12-16 | Idemitsu Kosan Co., Ltd. | Succinimide compound, process for producing the same, lubricating oil additive, and lubricating oil composition for internal combustion engine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2819491B2 (en) | 1998-10-30 |
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