JPS6124560A - Manufacture of sulfide perbasic salicylate - Google Patents
Manufacture of sulfide perbasic salicylateInfo
- Publication number
- JPS6124560A JPS6124560A JP14760585A JP14760585A JPS6124560A JP S6124560 A JPS6124560 A JP S6124560A JP 14760585 A JP14760585 A JP 14760585A JP 14760585 A JP14760585 A JP 14760585A JP S6124560 A JPS6124560 A JP S6124560A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- metal
- salicylate
- aliphatic hydrocarbon
- overbased
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は、硫化された過塩基性脂肪族炭化水素置換ザリ
チル酸金屈塩の製造方法、この方法により製造される生
成物、並びにこれらを含有する油組成物に関づ−るもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing sulfurized overbased aliphatic hydrocarbon-substituted salicylic acid gold salts, products produced by this process, and oil compositions containing them. It is something that can be done.
この種の生成物およびこれら生成物を表面活性剤および
摩耗防止剤として含有する油組成物は英国特許第１，２
８７．・８１２号明ＷＡ書から既に公知ｅある。Products of this type and oil compositions containing these products as surfactants and antiwear agents are described in British Patents Nos. 1 and 2.
87.・It is already publicly known from the Meiwa book No. 812.
この明細書中には、脂肪族炭化水素置換サリチル酸また
はその金属塩と硫黄元系、アルカリ上類塩基（たとえば
水酸化物）および溶剤（たとえばエチレングリコール）
とを少なくとも１５０℃において反応させ必要に応じ７
二酸化炭素とざらに反応させることを開示している。英
国特許第１，１９４，５０３号明細書に同様な方法が開
示されている。In this specification, aliphatic hydrocarbon-substituted salicylic acid or a metal salt thereof, a sulfur base, an alkali base (e.g. hydroxide) and a solvent (e.g. ethylene glycol) are used.
and react at at least 150°C and optionally 7
It discloses that it is reacted with carbon dioxide. A similar method is disclosed in GB 1,194,503.
しかしながら、この公知方法は硫黄どの反応に際し相当
程度の脱カルボキシル化が生ずるという欠点を有するこ
とが判明した。However, it has been found that this known process has the disadvantage that a considerable degree of decarboxylation occurs during the sulfur reaction.
今回、同種類の脂肪族炭化水素置換サリチル酸まｌ、二
はぞの金属塩を、、ｖ化炭素で過塩基化した後に硫黄と
反応ざＵることにより、優れた洗剤特性おＪ、σ摩耗防
止特性を失うことなく、脱カルボにシル化の稈１哀をｆ
つと低くしうることを突き止めた９゜
しｌ二がつ（、本発明（、Ｌ脂肪ＦＡ炭化水素霞換号す
ブール酸を塩基性金属化合物とニー酸化炭素とにより少
なくど−ｔ）１．！ｌの塩基度指数を右する過塩基Ｉナ
リｆル酸金属珈に変換し、次いでこの過塩基→ノリチル
義金屈珈を硫黄元素と共に加熱して硫化ツること’ｉ
’ｒ：ｊ ｍと覆る、硫化された過塩基竹脂肪族炭化水
ｉＡ質換りリブール酸金属塩の製造方法に関°ツるもの
Ｃある。This time, by overbasing the same type of aliphatic hydrocarbon-substituted salicylic acid and two metal salts with vitreous carbon and then reacting with sulfur, we have developed excellent detergent properties, J, and abrasion. Decarboxylation of culm 1 to decarboxylate without losing the preventive properties
It has been found that the present invention can reduce the oxidation of boric acid by converting L-fatty FA hydrocarbon into a basic metal compound and dicarbonate.1. The basicity index of !l is converted to the right overbased metal fluoride, and then this overbased → noritylic acid metal is heated with sulfur element to form sulfidation.
``r:j m'' There is C related to a method for producing a sulfurized overbased bamboo aliphatic hydrocarbon iA substituted liburic acid metal salt.
さらに本発明は、この方法により製造された生成物おＪ
、びこれら生成物を含有する油組成物に関するらのｅあ
る。。Furthermore, the present invention provides products manufactured by this method and
and related to oil compositions containing these products. .
適する金属亀よＩＣとえばＬｉ、Ｃｓ、ＮａおよびＫの
Ｊ：うなアルカリ金属、たとえばＣａ、Ｂａ。Suitable metal ICs include alkali metals such as Li, Cs, Na and K, such as Ca, Ba.
ＳｒおよびＭｇのようなアルカリ土類金属、並びにたと
えば７ｎおよびＣｒのような多価金属ｅある。Alkaline earth metals such as Sr and Mg, and polyvalent metals such as 7n and Cr.
たとえばカルシウム、バリウムおよびマグネシウムのよ
うなアルカリ土類金属かに好適である。Alkaline earth metals such as calcium, barium and magnesium are suitable.
適する脂肪族炭化水素置換サリチル酸は［記英国特許明
Ｉ書に記載されている。好適なものはＣ８−３０−アル
キルサリチル酸である。。Suitable aliphatic hydrocarbon-substituted salicylic acids are described in British Patent No. I. Preferred are C8-30-alkylsalicylic acids. .
たとえば英国特許第７８６，１６７号明細書に記載され
たように、たとえば炭化水素溶剤、好ましくはたとえば
キシレンのような芳香族炭化水素溶剤などの溶剤中で炭
化水素置換サリチル酸を塩す性金属化合物、好ましくは
水酸化物ａ３よび二酸化炭素と反応させることにより、
過塩基化コニ程を行なうことができる。a hydrocarbon-substituted salicylic acid in a solvent such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent such as xylene, as described, for example, in British Patent No. 786,167; Preferably by reacting with hydroxide a3 and carbon dioxide,
An overbasing step can be performed.
得られた反応混合１に軽質鉱油を添加し、次いで炭化水
Ａ溶剤および生成した水を全一（蒸留により除去覆るこ
とができる。Light mineral oil is added to the resulting reaction mixture 1, and then the hydrocarbon water A solvent and the water produced are completely removed (can be removed by distillation).
企ｋＡ対すリヂル酸の当量比として定義されろ過３′、
Ａ基リリブル酸」ｎの塩基度指数（Ｂｌ’）は少なくと
＝ｂ１．．５、好ましくは少なくとも３である。硫化］
稈に際し相当４１の脱カルボキシル化を防止づ゛るｌこ
めにこのことが重要Ｃあることが判明した。Filtration 3' is defined as the equivalent ratio of lydylic acid to plankA;
The basicity index (Bl') of "A-group lillibric acid" n is at least = b1. ．． 5, preferably at least 3. Sulfurization]
This has been found to be of great importance in preventing decarboxylation of 41% during the culm process.
ｌｌｆましく番、Ｌ溶剤の存在下で、１００〜２５０℃
、好ましくは １！１０〜２２５℃の範凹の温度にて得
られた過」福！ｉＵ２．１の油溶液を硫黄元素と接触さ
せ′Ｃ硫化工程を行なうことができ、その際最終温度は
少なくとし１７５℃、好ましくは少なくとも１９５℃に
すべさＣある１、
１ｑられる硫化生成物の油溶液を所望に応じて濾過し、
次いで！ことえばｍＷＩ油またはガソリンのような燃料
油へ添加することができる。100-250°C in the presence of L solvent
, preferably at temperatures in the range of 10 to 225°C. A sulfurization step can be carried out by contacting an oil solution of 2.1 with elemental sulfur, the final temperature being at least 175° C., preferably at least 195° C. 1,1q. Filter the oil solution as desired;
Next! For example, it can be added to fuel oils such as mWI oil or gasoline.
」−配英国１４訂第１，２８７，８１２号および第１，
１９４゜５０３号各明ｌｌＩ書に開示されているように
、線化工程の上記溶剤は、好ましくはアルキレンもしく
はポリアルキレングリコールまたはその低級アル−１−
ル亡ノエーテルである。” - Distribution UK 14th edition No. 1,287,812 and No. 1,
As disclosed in No. 194.503, the solvent for the linearization step is preferably an alkylene or polyalkylene glycol or its lower alkyl-1-
It is an aether.
英（３ｉｌ特許第１．１９４．５０３号明Ｉ書に記載さ
れているように、カルボン酸またはその金属Ｊ３のよう
な促進剤も硫化］、程に存在させることかできる。A promoter such as a carboxylic acid or its metal J3 may also be present (as described in 3IL Patent No. 1.194.503).
Ｓ：置換リーリチル酸のモル比はたとえば０．２！］−
３、好ましくは０，５〜２である。The molar ratio of S:substituted lilycylic acid is, for example, 0.2! ]−
3, preferably 0.5-2.
同時係属中の英国特許出願第８，３３０，４４１号明細
書に記載されているように、硫化工程の前または後に生
成物をたとえば硼酸のような硼素化合物と反応させるこ
とができる。The product can be reacted with a boron compound, such as boric acid, before or after the sulfurization step, as described in co-pending British Patent Application No. 8,330,441.
本発明の反応生成物およびその混合物は油組成物、特に
潤滑油組成物また【よ濃厚物もしくは燃料、たとえば自
動車クランクケース油中へ、全組成物重祉に対し０．０
０１〜６５重呈％、特に０．１〜１５重け％の範囲のＷ
Ｊ度で配合することができる。The reaction products of the present invention and mixtures thereof can be added to oil compositions, especially lubricating oil compositions, or into concentrates or fuels, such as automobile crankcase oils, at a concentration of 0.0% relative to the total composition weight.
W in the range of 01 to 65%, especially 0.1 to 15%
It can be blended at J degree.
本発明の添加物を添加しうる潤滑油は、鉱物側６°１油
だ１ノでなく、合成油をも包含する。合成炭化水素潤滑
油−ｂ使用することができ、さらにたとえばジー ２−
エチルへキシルセバシン酸ニスデル、ｆｆｌ酪１１−ス
Ｊル、燐酸エスラル、ハロゲン化炭化水素、ポリシリコ
ーン、ポリグリコール、グリコールしスノルたとえばノ
ー１〜ラエチレングリ−コールのＣ１３／ＩＩソ酸ジ］
ニスラルなどの−、 ｒｉＡ基１１．１７１１コスデル
を包含りる非炭化水素合成油も使用することができる。Lubricating oils to which the additives of the present invention can be added include not only mineral oils but also synthetic oils. Synthetic hydrocarbon lubricating oils can be used, as well as e.g.
Nisder ethylhexyl sebacate, ffl butylene glycol, esral phosphate, halogenated hydrocarbons, polysilicone, polyglycol, glycol snorl, e.g.
Non-hydrocarbon synthetic oils containing -, riA groups 11.1711 cosdel, such as Nisral, can also be used.
これら油の混合物、特に水素添加油を含む鉱物潤滑油及
び合成潤滑油の混合物も使用することができる。Mixtures of these oils can also be used, especially mixtures of mineral and synthetic lubricating oils, including hydrogenated oils.
ガソリンまたは燃料油、たとえばディーゼル燃わ１など
（Ｌ二使用りる揚台、−・般に全組成物５１＠ｔ Ｃ二
対し０．００１−０．４１重量％の反応生成物が使用さ
れる。Gasoline or fuel oils, such as diesel fuel 1 (L2) are used - generally 0.001-0.41% by weight of the reaction product, based on the total composition 51@tC2, is used. .
通常取り扱いを容易にするため、たどえば１５〜６５臣
量％の炭化水素界釈剤中の前記反応生成物と、８５〜３
５重量％の鉱物潤滑油とからなる濃厚物が製造される。Usually, for ease of handling, the reaction product is prepared in a hydrocarbon binder of 15-65% and 85-3%
A concentrate consisting of 5% by weight mineral lubricating oil is produced.
たとえば染料、流動照降゛ト剤、摩耗防止剤Ｉことえば
燐酸［・リクレシル、ジチオ燐酸亜鉛、酸化防止剤たと
えば）、にルーα−ナフチル−アミン。For example, dyes, fluid illumination agents, anti-wear agents such as phosphoric acids (such as recresyl, zinc dithiophosphate, antioxidants), alpha-naphthyl-amines, etc.
ビス−フェノール類たとえば４．４′ −メチレンビ
ス（３，６−ジーｔ−ブチルフェノール）、粘変指数向
上剤たとえば共役ジエンど必要に応じメチレンとの水糸
化（共）重合体、エチレン−高級オレフィンｊｔ［合体
、ポリメチルアクリレート、ポリイソメチレンなど、並
びに無灰分分散剤たとえばポリイソブチルと無水マレイ
酸とアミン１３．Ｊ、び／またはポリオールとの反応生
成物、またはその他の金属含有表面活性剤たとえば過塩
基性全屈ザリチル酸塩などの他の添加物も、Ｌ記組成物
中に存在させることかできる。Bis-phenols, such as 4,4'-methylenebis(3,6-di-t-butylphenol), viscosity index improvers, such as conjugated dienes, water-forming (co)polymers with methylene as required, ethylene-higher olefins. jt [combined, polymethyl acrylate, polyisomethylene, etc., as well as ashless dispersants such as polyisobutyl and maleic anhydride and amines 13. Other additives may also be present in the composition, such as reaction products with J, and/or polyols, or other metal-containing surfactants, such as overbased diabetic salicylates.
アミンとホルムアルデヒドとアルキルフェノールとの反
応生成物（マンニッヒ塩基）も存在さヒることがぐきる
。The reaction products of amines, formaldehyde, and alkylphenols (Mannich bases) are also likely to be present.
以１；、本発明を実施例につき説明づ°る。In the following, the present invention will be explained with reference to examples.
及亀見ユ
水酸化カルシウムと二酸化炭素とによりＣＩＬ １Ｂ’
アル＝１）レリ°リプル酸からＢｌが３の過ｊ！晶ｌｔ
のＣ−アルキルサリチル
１ ４ − ’＋ ８
（／１成物Δ）を作成し、これを鉱物潤滑油中ｌ＼導入
した。CIL 1B' with calcium hydroxide and carbon dioxide
Al = 1) Bl is 3 from Leli° ripple acid! crystal lt
C-alkylsalicyl 14-'+8 (/1 product Δ) was prepared and introduced into mineral lubricating oil.
３３重量％の鉱物潤滑油中の過塩基性Ｃ １４−１８−
アル−１ル４ノリプル酸カルシウム６７１ｉｉ１％のｍ
厚物２！’ｉ００ｇ（２！ｉ３’０ミリ当吊の酸）と、
硫黄元素８０ｇ（２５００ミリ当ｆｌｆｔ ）と、２０
０のエチレングリコールとを反応容器（！１１）に入れ
た。撹拌しながらこの混合物を１２５℃まで加熱し、こ
の温度に１時間保った。33% by weight of overbased C 14-18- in mineral lubricating oil
Calcium Al-1-4 Noripurate 671ii 1% m
Thick material 2! 'i00g (2!i3'0ml of acid) and
80 g of elemental sulfur (2500 mm/flft) and 20
0 of ethylene glycol was placed in the reaction vessel (!11). The mixture was heated to 125° C. with stirring and kept at this temperature for 1 hour.
次いで、４度を１５０℃まで１桿さＵ１約５ＳＯｍｍｌ
ｆ（］の圧力Ｆにて、この温度に１時間保った。次いで
、温度を１９５℃まで４−昇ざぜかつ圧力を５０〜ＧＯ
ｍｍｌ１ｇまで低下させ、これら条件を２時間維持しに
０次いで、反応生成物を約１００℃まで冷却した後、濾
過助剤を通してＰ遇し、暗色の粘性生成物を得たく収量
： ２５０００ 、 Ｓ ： １．６重量％）（住放
物Ｂ）。Next, 4 degrees up to 150 degrees Celsius U1 about 5 SO mml
This temperature was maintained for 1 hour at a pressure of f().The temperature was then increased to 195°C and the pressure was
The reaction product was then cooled to about 100° C. and filtered through a filter aid to give a dark viscous product. Yield: 25000, S: 1.6% by weight) (Jubanmono B).
より低い温度（１７５℃）において硫化を行なうと溶解
した未反応硫黄がいくらかでき、これは静置すると沈澱
する傾向を有することが判った。It has been found that carrying out the sulfidation at lower temperatures (175°C) creates some dissolved unreacted sulfur which tends to precipitate on standing.
さらに、硫化に際し極く少量の脱カルポー１−シル化し
か生じないことも判明した（ ９％；出発物質の酸価１
．θＧおよび生成物の酸化０．９６：酸価（ミリ当量の
酸／（＋１は、ＨＣｐで酸性化し、ジエチルエーテルで
抽出し、相分離し、溶剤を蒸発させＩこ後に測定される
）（下記の実施例においても同じ方法を用いる）。Furthermore, it was found that only a very small amount of decarpo-1-sylation occurred during sulfidation (9%; acid value of starting material 1
．． θG and oxidation of the product 0.96: Acid number (milliequivalents of acid/(+1 determined after acidification with HCp, extraction with diethyl ether, phase separation, and evaporation of the solvent) (see below) The same method is used in the Examples).
χ舊」（？
実／１１！１例１に記載した方法に従い、アルキルサリ
ブル酸ど水酸化カルシウムと二、酸化炭素とから作成さ
れかつ７．７２の［３１を有するＣ −アルキルリ
リヂル酸カルシウム（１６２５ミリ当量）の５０償吊％
の５０・Ｆ吊％鉱物油中の濃厚物２５００（］を、５１
．３０の元止）売黄（１６０３ミリ当量）＋１３よび１
３０のエチレングリコールにより硫化した。収ａｔ ：
２４５３ｇ 。According to the method described in Example 1, a C-alkylilydylate calcium hydroxide (C-alkyllylydylate prepared from calcium hydroxide and carbon dihydroxide and having a [31 of 7.72) was prepared according to the method described in Example 1. 1625 milliequivalent)
Concentrates in mineral oil with a concentration of 2500% at 50 F and 51
．． 30 yuan) Yellow (1603 milliquivalent) + 13 and 1
30 ethylene glycol. Collection:
2453g.
Ｓ：１．２重量％
硫化に際し２％の脱カルボキシル化が生じたことが判−
）たく出発物質の酸価０．１９ミリ当量／ｇおＪ、びｌ
［酸物の酸１１ｉ０．７７ミリ当量／ｇ）。S: 1.2% by weight It was found that 2% decarboxylation occurred during sulfurization.
) Acid value of starting material: 0.19 meq/g, J, bil
[0.77 meq/g of acid 11i).
話ね
実施例゛ｌに記載の方法に従い、３８重量％鉱物潤滑油
中の６２千吊％の７，２のＢＴを有する過塩基性Ｃ１４
−１８−アルキルナリチル酸マグネシウム（２１３，５
ミリ当吊）濃厚物２５０ｇを６．ｂ８ｇの元素硫黄（２
０５，６ミリ当量）および１．７ｇのエヂレングリ丁」
−ルに−一り硫化した。収量： ２４３．６ｇ、 Ｓ
： ０．９４巾Ｗ％。Overbased C14 with 62,000% 7,2 BT in 38% by weight mineral lubricating oil according to the method described in Example 1.
-18-alkylnaritylic acid magnesium (213,5
6. 250g of concentrate) b8g of elemental sulfur (2
05.6 milliequivalent) and 1.7 g
sulfided. Yield: 243.6g, S
: 0.94 width W%.
硫化に際し３％の脱カルボキシル化が生じたことが判っ
た（出発物質の酸化１．０２ミリ当＠／ｇおよび生成物
の酸価ｉ、ｏｏミリ当量１０）。It was found that 3% decarboxylation occurred upon sulfidation (oxidation of starting material 1.02 meq@/g and acid number i, oo meq. of product 10).
比較実験１
純Ｃ１４−１８−アルＶルサリチル酸９７．６！Ｊ（２
０５ミリ当量）に、３７．９（］（１０２５ミリ当ｆｆ
１）（７）Ｃａ（ＯＨ）２ど６９．５ｇの鉱物潤滑ａｌ
ｌ トラ加工Ｔ １．０ミリ当量／ｇの酸混合物を得た
。この２１ｔ合物１３３．２（１（１３３，２ミ！Ｊ当
ｆｉ ）と４．２６（ｌｉ／） Ｓ （１３３，２ミＩ
Ｊ当遣）と１．ｏｇのエチレングリコールとを撹拌しな
がら １２５℃まで加熱し、この温度に１１１４間保っ
た。温度をざらにｉ ｓ Ｏ”Ｃまで上昇さｌ！（１時
間、圧カニ ５５０ｍ１１１ＨＯ）、さら１１９５℃マ
チ上９７ ’ｉ：５ ｆ ｔ、：く２時間、５０−ｆ３
Ｏｍｉｌｌ向〕。この反応混合物を冷却し、旧へ１リン
で希釈し、濾過助剤を通しＵ濾過し、最終的に蒸発させ
、極め（粘性の暗色物質を得た。Comparative experiment 1 Pure C14-18-al Vrusalicylic acid 97.6! J(2
05 milliequivalent), 37.9(](1025 milliequivalent ff
1) (7) 69.5g of Ca(OH)2 mineral lubricant al
l Tora Processing T An acid mixture of 1.0 meq/g was obtained. This 21t compound 133.2 (1 (133,2 mi! J tofi) and 4.26 (li/) S (133,2 mi I
J) and 1. of ethylene glycol was heated to 125° C. with stirring and held at this temperature for 1114 hours. Raise the temperature roughly to i s O"C (1 hour, pressure crab 550 m 111 HO), and then increase to 1195 ° C.
For Omill]. The reaction mixture was cooled, diluted with dichloromethane, filtered through filter aid and finally evaporated to give a viscous dark material.
収Ｆｆ４： １１２．３Ｌ Ｓ ：１．ｅ％、。Accommodation Ff4: 112.3L S: 1. e%.
１％ｉ化（、−際し２０％の脱カルボ：１−シル化が生
じたことが判〕た（出発物質の“酸価１．２２ミリ当量
／ｇおよび勺放物の酸価０．９５ミリ当量／（＋）。It was found that 20% decarboxylation and 1-sylation had occurred (the acid value of the starting material was 1.22 meq/g and the acid value of the monomer was 0.1%). 95 milliequivalents/(+).
ル激〜尖周ノ
実施例１に記載の方法に従い、４２重量％鉱物潤ｉ１’
ｌ １ｌｌｌ中のＳ）即（ｉ ＋ｆｆｉ％の１．２８の
Ｂｌを右りる過塩基ＰＩＣ１４−１８−アルキルリ−リ
チル酸カルシウムの濃厚物２！ｉｏＯｇ （２３００
ミ！Ｊ当量）ヲ、７７ｇノ元素硫黄（２４０Ｇミリ当用
）および１９ｇの１ヂレングリコールにより硫化した。According to the method described in Example 1, 42% by weight mineral moisture i1'
Concentrate of overbased PIC14-18-alkyl ly-calcium ricylate 2!ioOg (2300
Mi! J equivalent) was sulfided with 77 g of elemental sulfur (240 G mm equivalent) and 19 g of 1-dilene glycol.
収ＩＩ ： ２４９６ｇ、 Ｓ ： １．３重足％０
硫化に際し２８％の脱カルボキシル化が生じたことが判
っ１．：（出発物質の酸価ｏ、９２ミリ当け／りおＪ、
び生成物の酸化０．６６ミリ当量／（］）。Yield II: 2496g, S: 1.3% 0. It was found that 28% decarboxylation occurred during sulfurization.1. : (Acid value o of starting material, per 92 mm/Rio J,
and 0.66 meq/(]) of oxidation of product.
■
市販の分散剤、洗剤及び酸化防１剤添加物を含有する２
種の１５Ｗ４０の鉱物潤滑油（１および２）において、
生成物ＡおよびＢ（実施例１参照）を試験した。■ Contains commercially available dispersants, detergents, and antioxidant additives.
In species 15W40 mineral lubricating oils (1 and 2),
Products A and B (see Example 1) were tested.
組成物工は、潤滑油１中にＣａとして０．１４重量％の
量で生成物Ａを含有し、組成物■は潤滑油１と０．１４
重φ％（Ｃａとして）の生成物Ｂとを含有した。組成物
■およびＩＶはそれぞれ生成物Ａ Ｊ−３Ｊ：びＢをＧ
ａとして０．１９重世％含む潤滑油２で構成した。Composition II contains product A in an amount of 0.14% by weight as Ca in lubricating oil 1, and composition II contains lubricating oil 1 and 0.14% by weight of Ca.
weight φ% (as Ca) of product B. Compositions ■ and IV represent products A J-3J and B, respectively.
It was composed of lubricating oil 2 containing 0.19% by mass as a.
組成物■および■をＣＲＣＬ３８試験（八Ｓ’ｌＨ５Ｔ
Ｐ５０９Ａ、第■部）にて試験した。この試験ではべ）
′リング重量損失を測定する。これらの結果を第１表に
示づ一：
第 １ 表
組 成 物 Ｉ
Ｉ［ベアリング重量損失（１１ｇ）
４５．４ ３３．６硫化り酸物の使用によりベ
アリング重量り失が減少りることが判明した。Compositions ■ and ■ were tested in the CRCL38 test (8S'lH5T
P509A, Part 2). In this exam)
´Measure the ring weight loss. These results are shown in Table 1: Table 1 Composition I
I [bearing weight loss (11g)
45.4 33.6 It has been found that the use of sulfuric acid reduces bearing weight loss.
組成物１１１ ｉ１３よ□び■をＭＳシーケンス（Ｓ
ｃｑｕｃｎｃｃ） ｍ ｌ）エンジン試験にで試験した
。この試験で【、１カムＪ５よびリフタの摩耗および浄
化性ｆｌｕを測定した。。Composition 111 i13 and ■ were subjected to MS sequence (S
cqucncc) m l) Tested in engine test. In this test, the wear and purification properties of the cam J5 and lifter were measured. .
これらの結果を第■表に示す：
第■表
試 験 １ ２
３ ４組 成 物 ＩＩ
ＩＩＩＩ ■ ＩＶ最人のノｊムおＪ、びリフ
タの摩耗（ｍｍ） ０．５５ ０．７７
０．３８ ０．５０平均のカムおよびリフタの摩耗
（ｎ＋ｍ） ０．２６ ０．２４ ０，
１４ ０．１２平均汚れ率（１０が奇麗である）
９．６６ ９．５８ ９．６３
９．５８硫化１−成１カの使用により、カムおよびリフ
タの１９’耗が減少りることが判つ１〔。浄化率（、Ｌ
はぼ同程１良に留まつＩこ。These results are shown in Table ■Table ■Test 1 2
3 4 Composition II
III ■ IV Wear of No. 1 and lifter (mm) 0.55 0.77
0.38 0.50 Average cam and lifter wear (n+m) 0.26 0.24 0,
14 0.12 average dirt rate (10 is clean)
9.66 9.58 9.63
9.58 It has been found that the use of sulfurized 1-former 1 reduces 19' wear on cams and lifters. Purification rate (, L
It's still at 1st grade.
判judgment
Claims (9)
物と二酸化炭素とにより少なくとも１．５の塩基度指数
を有する過塩基サリチル酸金属塩に変換し、次いでこの
過塩基サリチル酸金属塩を硫黄元素と共に加熱して硫化
することを特徴とする、硫化された過塩基性の脂肪族炭
化水素置換サリチル酸の金属塩の製造方法。(1) Converting aliphatic hydrocarbon-substituted salicylic acid to an overbased metal salicylate having a basicity index of at least 1.5 with a basic metal compound and carbon dioxide, and then heating the overbased metal salicylate with elemental sulfur. 1. A method for producing a sulfurized overbased metal salt of aliphatic hydrocarbon-substituted salicylic acid, the method comprising sulfurizing the metal salt with an aliphatic hydrocarbon.
１項に記載の方法。(2) The method according to claim 1, wherein the metal is an alkaline earth metal.
＿０−アルキルサリチル酸である特許請求の範囲第１項
または第２項に記載の方法。(3) Aliphatic hydrocarbon substituted salicylic acid is C_8_-_3
_0-Alkylsalicylic acid, the method according to claim 1 or 2.
である特許請求の範囲第１項乃至第３項のいずれかに記
載の方法。(4) the basicity index of the overbased salicylate is at least 3;
The method according to any one of claims 1 to 3.
囲第１項乃至第４項のいずれかに記載の方法。(5) The method according to any one of claims 1 to 4, wherein the sulfurization is carried out at at least 175°C.
る特許請求の範囲第１項乃至第５項のいずれかに記載の
方法。(6) The method according to any one of claims 1 to 5, wherein the molar ratio of S:substituted salicylic acid is 0.25 to 3.
させる特許請求の範囲第１項乃至第６項のいずれかに記
載の方法。(7) The method according to any one of claims 1 to 6, in which the product before or after sulfurization is reacted with a boron compound.
載の方法により製造された生成物。(8) A product produced by the method according to any one of claims 1 to 7.
０１〜６５重量％とからなる油組成物、特に潤滑油組成
物または濃縮物もしくは燃料。(9) Oil and the product according to claim 8 0.0
01-65% by weight, especially lubricating oil compositions or concentrates or fuels.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8417297 | 1984-07-06 | ||
| GB848417297A GB8417297D0 (en) | 1984-07-06 | 1984-07-06 | Preparation of sulphurized overbased salicylates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6124560A true JPS6124560A (en) | 1986-02-03 |
| JPH0580517B2 JPH0580517B2 (en) | 1993-11-09 |
Family
ID=10563523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14760585A Granted JPS6124560A (en) | 1984-07-06 | 1985-07-04 | Manufacture of sulfide perbasic salicylate |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0168880B1 (en) |
| JP (1) | JPS6124560A (en) |
| BR (1) | BR8503201A (en) |
| CA (1) | CA1253873A (en) |
| DE (1) | DE3564570D1 (en) |
| GB (1) | GB8417297D0 (en) |
| SG (1) | SG7090G (en) |
| ZA (1) | ZA855048B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4805995A (en) * | 1987-04-24 | 1989-02-21 | Alps Electric Co., Ltd. | Liquid crystal display with small carbon particles in its mark |
| JPH068869U (en) * | 1992-07-09 | 1994-02-04 | 日本ピラー工業株式会社 | Shaft seal device |
| JP2005220197A (en) * | 2004-02-04 | 2005-08-18 | Nippon Oil Corp | Lubricating oil composition to be brought into contact with lead-containing metal material |
| JP2007039457A (en) * | 2005-07-29 | 2007-02-15 | Chevron Oronite Co Llc | Low-sulfur metal-based detergent-dispersant |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8714922D0 (en) * | 1987-06-25 | 1987-07-29 | Shell Int Research | Lubricating oil composition |
| JPH0676589B2 (en) * | 1987-07-24 | 1994-09-28 | コスモ石油株式会社 | Process for the preparation of alkaline earth metal sulphurised mixtures of hydroxyalkylbenzoic acids and alkylphenols |
| MX9305120A (en) * | 1992-09-04 | 1994-03-31 | Lubrizol Corp | SULFURATED OVERBASED COMPOSITIONS. |
| TW278098B (en) * | 1992-09-18 | 1996-06-11 | Cosmo Sogo Kenkyusho Kk | |
| US6828415B2 (en) | 1993-02-19 | 2004-12-07 | Zentaris Gmbh | Oligopeptide lyophilisate, their preparation and use |
| JPH1161165A (en) * | 1997-06-12 | 1999-03-05 | Tonen Corp | Friction reducing agent comprising metallic salicylate and lubricating oil composition containing the same |
| US7136522B2 (en) * | 2002-10-09 | 2006-11-14 | Xerox Corporation | Systems for spectral multiplexing of source images to provide a composite image, for rendering the composite image, and for spectral demultiplexing of the composite image to animate recovered source images |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB786167A (en) * | 1954-09-27 | 1957-11-13 | Shell Res Ltd | Improvements in or relating to the preparation of basic oil-soluble polyvalent metalsalts of organic acids and solutions of said basic salts in oils, and the resultingsalts |
| US3595791A (en) * | 1969-03-11 | 1971-07-27 | Lubrizol Corp | Basic,sulfurized salicylates and method for their preparation |
| JPS5676496A (en) * | 1979-11-07 | 1981-06-24 | Lubrizol Corp | Additive composition* additive condensate and lubricant |
| JPS58225197A (en) * | 1982-05-14 | 1983-12-27 | エクソン・リサ−チ・アンド・エンヂニアリング・コムパニ− | Lubricating oil additive |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2319662A (en) * | 1941-10-31 | 1943-05-18 | American Cyanamid Co | Lubricating oils |
| US2311931A (en) * | 1941-12-27 | 1943-02-23 | American Cyanamid Co | Lubricant |
| USRE22910E (en) * | 1941-12-31 | 1947-09-02 | E-oxcxs-m | |
| US2336074A (en) * | 1942-05-16 | 1943-12-07 | American Cyanamid Co | Lubricating oil |
| GB825315A (en) * | 1957-02-18 | 1959-12-16 | Socony Mobil Oil Co Inc | Complex carbonated metal salts of alkyl phenol sulphides |
| GB1094609A (en) * | 1965-08-23 | 1967-12-13 | Lubrizol Corp | Oil soluble basic alkaline earth metal salts of phenol sulfides |
| SU644811A1 (en) * | 1975-07-14 | 1980-02-05 | Всесоюзный научно-исследовательский институт по переработке нефти | Method of preparing sulfide alkylphenolate additive to lubricating oils |
| GB1597482A (en) * | 1977-01-28 | 1981-09-09 | Exxon Research Engineering Co | Metal phenates |
| US4228022A (en) * | 1979-06-28 | 1980-10-14 | Chevron Research Company | Sulfurized alkylphenol-olefin reaction product lubricating oil additive |
| US4320016A (en) * | 1979-09-24 | 1982-03-16 | Texaco Inc. | Carbon dioxide-blown overbased calcium alkylphenolate lubricating compositions |
-
1984
- 1984-07-06 GB GB848417297A patent/GB8417297D0/en active Pending
-
1985
- 1985-06-17 CA CA000484253A patent/CA1253873A/en not_active Expired
- 1985-07-04 JP JP14760585A patent/JPS6124560A/en active Granted
- 1985-07-04 BR BR8503201A patent/BR8503201A/en not_active IP Right Cessation
- 1985-07-04 EP EP85201083A patent/EP0168880B1/en not_active Expired
- 1985-07-04 ZA ZA855048A patent/ZA855048B/en unknown
- 1985-07-04 DE DE8585201083T patent/DE3564570D1/en not_active Expired
-
1990
- 1990-02-05 SG SG70/90A patent/SG7090G/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB786167A (en) * | 1954-09-27 | 1957-11-13 | Shell Res Ltd | Improvements in or relating to the preparation of basic oil-soluble polyvalent metalsalts of organic acids and solutions of said basic salts in oils, and the resultingsalts |
| US3595791A (en) * | 1969-03-11 | 1971-07-27 | Lubrizol Corp | Basic,sulfurized salicylates and method for their preparation |
| JPS5676496A (en) * | 1979-11-07 | 1981-06-24 | Lubrizol Corp | Additive composition* additive condensate and lubricant |
| JPS58225197A (en) * | 1982-05-14 | 1983-12-27 | エクソン・リサ−チ・アンド・エンヂニアリング・コムパニ− | Lubricating oil additive |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4805995A (en) * | 1987-04-24 | 1989-02-21 | Alps Electric Co., Ltd. | Liquid crystal display with small carbon particles in its mark |
| JPH068869U (en) * | 1992-07-09 | 1994-02-04 | 日本ピラー工業株式会社 | Shaft seal device |
| JP2005220197A (en) * | 2004-02-04 | 2005-08-18 | Nippon Oil Corp | Lubricating oil composition to be brought into contact with lead-containing metal material |
| JP2007039457A (en) * | 2005-07-29 | 2007-02-15 | Chevron Oronite Co Llc | Low-sulfur metal-based detergent-dispersant |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1253873A (en) | 1989-05-09 |
| ZA855048B (en) | 1986-02-26 |
| DE3564570D1 (en) | 1988-09-29 |
| JPH0580517B2 (en) | 1993-11-09 |
| EP0168880A1 (en) | 1986-01-22 |
| BR8503201A (en) | 1986-03-25 |
| EP0168880B1 (en) | 1988-08-24 |
| SG7090G (en) | 1990-07-13 |
| GB8417297D0 (en) | 1984-08-08 |
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