JPH0580517B2 - - Google Patents
Info
- Publication number
- JPH0580517B2 JPH0580517B2 JP60147605A JP14760585A JPH0580517B2 JP H0580517 B2 JPH0580517 B2 JP H0580517B2 JP 60147605 A JP60147605 A JP 60147605A JP 14760585 A JP14760585 A JP 14760585A JP H0580517 B2 JPH0580517 B2 JP H0580517B2
- Authority
- JP
- Japan
- Prior art keywords
- overbased
- salicylic acid
- metal
- weight
- aliphatic hydrocarbon
- 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.)
- Expired - Fee Related
Links
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 16
- 229960004889 salicylic acid Drugs 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229960001860 salicylate Drugs 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000003819 basic metal compounds Chemical class 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000010688 mineral lubricating oil Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 238000006114 decarboxylation reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 7
- 238000005486 sulfidation Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- -1 sebacic acid ester Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003870 salicylic acids Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- XOJRBTBFGUKLPU-UHFFFAOYSA-N 2,5-ditert-butyl-4-[(2,5-ditert-butyl-4-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(CC=2C(=CC(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C XOJRBTBFGUKLPU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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)
Description
本発明は、硫化された過塩基性脂肪族炭化水素
置換サリチル酸金属塩の製造方法に関するもので
ある。
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1287812号明細書から既に公知である。
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素、アルカリ土類塩
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二酸化炭素とさらに反応さ
せることを開示している。英国特許第1194503号
明細書に同様な方法が開示されている。
しかしながら、この公知方法は硫黄との反応に
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。
今回、同種類の脂肪族炭化水素置換サリチル酸
またはその金属塩を二酸化炭素で過塩基化した後
に硫黄と反応させることにより、優れた洗剤特性
および摩耗防止特性を失うことなく、脱カルボキ
シル化の程度をずつと低くしうることを突き止め
た。
したがつて、本発明は脂肪族炭化水素置換サリ
チル酸を塩基性金属化合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脂肪族炭化
水素置換サリチル酸金属塩の製造方法に関するも
のである。
本発明によつて製造される、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は、
単純に化学構造式で示すことができない複雑な物
質群であり、上記製法によつてその製造物は特定
化されている。
適する金属はたとえばLi，Cs，NaおよびＫの
ようなアルカリ金属、たとえば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ZnおよびCrのような多価金属である。
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が好適である。
適する脂肪族炭化水素置換サリチル酸は上記英
国特許明細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。
たとえば英国特許第786167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基性金属
化合物、好ましくは水酸化物および二酸化炭素と
反応させることにより、過塩基化工程を行なうこ
とができる。
得られた反応混合物に軽質鉱油を添加し、次い
で炭化水素溶剤および生成した水を全て蒸留によ
り除去することができる。
金属対サリチル酸の当量比として定義される過
塩基サリチル酸塩の塩基度指数（BI）は少なく
とも1.5、好ましくは少なくとも３である。硫化
工程に際し相当量の脱カルボキシル化を防止する
ためにこのことが重要であることが判明した。
好ましくは溶剤の存在下で、100〜250℃、好ま
しくは150〜225℃の範囲の温度にて得られた過塩
基塩の油溶液を硫黄元素と接触させて硫化工程を
行なうことができ、その際最終温度は少なくとも
175℃、好ましくは少なくとも195℃にすべきであ
る。
得られる硫化生成物の油溶液を所望に応じて
過し、次いでたとえば潤滑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。
上記英国特許第1287812号および第1194503号各
明細書に開示されているように、硫化工程の上記
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キルモノエ
ーテルである。
英国特許第1194503号明細書に記載されている
ように、カルボン酸またはその金属塩のような促
進剤も硫化工程に存在させることができる。
Ｓ：置換サリチル酸のモル比はたとえば0.25〜
３、好ましくは0.5〜２である。
同時係属中の英国特許出願第8330441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。
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は濃厚物もしくは燃
料、たとえば自動車クランクケース油中へ、全組
成物重量に対し0.001〜65重量％、特に0.1〜15重
量％の範囲の濃度で配合することができる。
本発明の添加物を添加しうる潤滑油は、鉱物潤
滑油だけでなく、合成油をも包含する。合成炭化
水素潤滑油も使用することができ、さらにたとえ
ばジ−２−エチルヘキシルセバシン酸エステル、
炭酸エステル、燐酸エステル、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
ルエステルたとえばテトラエチレングリコールの
C13オキソ酸ジエステルなどの二塩基性酸エステ
ルを包含する非炭化水素合成油も使用することが
できる。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。
ガソリンまたは燃料油、たとえばデイーゼル燃
料などに使用する場合、一般に全組成物重量に対
し0.001〜0.5重量％の反応生成物が使用される。
通常取り扱いを容易にするため、たとえば15〜65
重量％の炭化水素希釈剤中の前記反応生成物と、
85〜35重量％の鉱物潤滑油とからなる濃厚物が製
造される。
たとえば染料、流動点降下剤、摩耗防止剤たと
えば燐酸トリクレシル、ジチオ燐酸亜鉛、酸化防
止剤たとえばフエニル−α−ナフチル−アミン、
ビス−フエノール類たとえば４，4′−メチレンビ
ス（３，６−ジ−ｔ−ブチルフエノール）、粘度
指数向上剤たとえば共役ジエンと必要に応じスチ
レンとの水素化（共）重合体、エチレン−高級オ
レフィン共重合体、ポリメチルアクリレート、ポ
リイソブチレンなど、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およ
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金属
サリチル酸塩などの他の添加物も上記組成物中に
存在させることができる。
アミンとホルムアルデヒドとアルキルフエノー
ルとの反応生成物（マンニツヒ塩基）も存在させ
ることができる。
以下、本発明を実施例につき説明する。
実施例 １
水酸化カルシウムと二酸化炭素とによりC14-18
−アルキルサリチル酸からBIが３の過塩基の
C14-18−アルキルサリチル酸カルシウム（生成物
Ａ）を作成し、これを鉱物潤滑油中へ導入した。
33重量％の鉱物潤滑油中の過塩基性C14-18−ア
ルキルサリチル酸カルシウム67重量％の濃厚物
2500ｇ（2530ミリ当量の酸）と、硫黄元素80ｇ
（2500ミリ当量）と、20ｇのエチレングリコール
とを反応容器（５）に入れた。攪拌しながらこ
の混合物を125℃まで加熱し、この温度に１時間
保つた。次いで、温度を150℃まで上昇させ、約
550mmHgの圧力下にて、この温度に１時間保つ
た。次いで、温度を195℃まで上昇させかつ圧力
を50〜60mmHgまで低下させ、これら条件を２時
間維持した。次いで、反応生成物を約100℃まで
冷却した後、過助剤を通して過し、暗色の粘
性生成物を得た（収量：2500ｇ、Ｓ：1.6重量％）
（生成物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
が判つた。
さらに、硫化に際し極く少量の脱カルボキシル
化しか生じないことも判明した（９％；出発物質
の酸価1.06および生成物の酸化0.96；酸価（ミリ
当量の酸／ｇ）は、HClで酸性化し、ジエチルエ
ーテルで抽出し、相分離し、溶剤を蒸発させた後
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）。
実施例 ２
実施例１に記載した方法に従い、アルキルサリ
チル酸と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BIを有するC14-18−アルキルサ
リチル酸カルシウム（1625ミリ当量）の50重量％
の50重量％鉱物油中の濃厚物2500ｇを、51.3ｇの
元素硫黄（1603ミリ当量）および13ｇのエチレン
グリコールにより硫化した。収量：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
とが判つた（出発物質の酸価0.79ミリ当量／ｇお
よび生成物の酸価0.77ミリ当量／ｇ）。
実施例 ３
実施例１に記載の方法に従い、38重量％鉱物潤
滑油中の62重量％の7.2のBIを有する過塩基性
C14-18−アルキルサリチル酸マグネシウム（213.5
ミリ当量）濃厚物250ｇを、6.58ｇの元素硫黄
（205.6ミリ当量）および1.7ｇのエチレングリコ
ールにより硫化した。収量：243.6ｇ、Ｓ：0.94
重量％
硫化に際し３％の脱カルボキシル化が生じたこ
とが判つた（出発物質の酸化1.02ミリ当量／ｇお
よび生成物の酸価1.00ミリ当量／ｇ）。
比較実験 １
純C14-18−アルキルサリチル酸97.6ｇ（205ミリ
当量）に、37.9ｇ（1025ミリ当量）のCa（OH）2
と69.5ｇの鉱物潤滑油とを加えて1.0ミリ当量／
ｇの酸混合物を得た。この混合物133.2ｇ（133.2
ミリ当量）と4.26ｇのＳ（133.2ミリ当量）と1.0ｇ
のエチレングリコールとを攪拌しながら125℃ま
で加熱し、この温度に１時間保つた。温度をさら
に150℃まで上昇させ（１時間、圧力：550mm
Hg）、さらに195℃まで上昇させた（２時間、50
−60mmHg）。この反応混合物を冷却し、ｎ−ヘキ
サンで希釈し、過助剤を通して過し、最終的
に蒸発させ、極めて粘性の暗色物質を得た。収
量：112.3ｇ、Ｓ：1.6％。
硫化に際し20％の脱カルボキシル化が生じたこ
とが判つた（出発物質の酸価1.22ミリ当量／ｇお
よび生成物の酸価0.95ミリ当量／ｇ）。
比較実験 ２
実施例１に記載の方法に従い、42重量％鉱物潤
滑油中の58重量％の1.28のBIを有する過塩基性
C14-18−アルキルサリチル酸カルシウムの濃厚物
2500ｇ（2300ミリ当量）を、77ｇの元素硫黄
（2406ミリ当量）および19ｇのエチレングリコー
ルにより硫化した。収量：2496ｇ、Ｓ：1.3重量
％。
硫化に際し28％の脱カルボキシル化が生じたこ
とが判つた（出発物質の酸価0.92ミリ当量／ｇお
よび生成物の酸化0.66ミリ当量／ｇ）。
試 験
市販の分散剤、洗剤及び酸化防止剤添加物を含
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。
組成物は、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重量％（Caとして）の生成物Ｂとを含有し
た。組成物およびはそれぞれ生成物Ａおよび
ＢをCaとして0.19重量％含む潤滑油２で構成し
た。
組成物およびをCRC L38試験（ASTM
STP 509A、第部）にて試験した。この試験で
はベアリング重量損失を測定する。これらの結果
を第表に示す：
The present invention relates to a method for producing a sulfurized overbased aliphatic hydrocarbon-substituted salicylic acid metal salt. Products of this type and oil compositions containing these products as surfactants and antiwear agents are already known from GB 1287812.
In this specification, aliphatic hydrocarbon-substituted salicylic acid or a metal salt thereof is reacted with elemental sulfur, an alkaline earth base (e.g., hydroxide), and a solvent (e.g., ethylene glycol) at at least 150°C, and if necessary, carbon dioxide is produced. Further reaction with carbon is disclosed. A similar method is disclosed in GB 1194503. However, it has been found that this known process has the disadvantage that a considerable degree of decarboxylation occurs during the reaction with sulfur. Now, by overbasing the same class of aliphatic hydrocarbon-substituted salicylic acids or their metal salts with carbon dioxide and then reacting them with sulfur, the degree of decarboxylation can be increased without losing the excellent detergent and antiwear properties. We have discovered that it is possible to lower the Therefore, the present invention involves converting an aliphatic hydrocarbon-substituted salicylic acid with a basic metal compound and carbon dioxide into an overbased metal salicylate having a basicity index of at least 1.5, and then converting the overbased metal salicylate into an overbased metal salicylate with a basicity index of at least 1.5. The present invention relates to a method for producing a sulfurized overbased aliphatic hydrocarbon-substituted salicylic acid metal salt, which is characterized by sulfurizing it by heating at the same time. The sulfurized overbased aliphatic hydrocarbon-substituted salicylic acid metal salts produced according to the present invention are:
It is a complex group of substances that cannot be simply expressed by a chemical structural formula, and its products are specified using the above manufacturing method. Suitable metals are, for example, alkali metals such as Li, Cs, Na and K, alkaline earth metals such as Ca, Ba, Sr and Mg, and polyvalent metals such as Zn and Cr. Alkaline earth metals such as calcium barium and magnesium are suitable. Suitable aliphatic hydrocarbon-substituted salicylic acids are described in the above-mentioned British patent specification. What is suitable is
C 8-30 -alkyl salicylic acid. For example, as described in GB 786167, a hydrocarbon-substituted salicylic acid is combined with a basic metal compound, preferably water, in a solvent such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent such as xylene. The overbasing step can be carried out by reacting with oxides and carbon dioxide. Light mineral oil can be added to the resulting reaction mixture and then any hydrocarbon solvent and water produced can be removed by distillation. The basicity index (BI) of the overbased salicylate, defined as the equivalent ratio of metal to salicylic acid, is at least 1.5, preferably at least 3. This has been found to be important in order to prevent significant decarboxylation during the sulfurization step. The sulfidation step can be carried out by contacting the obtained oil solution of the overbased salt with elemental sulfur, preferably in the presence of a solvent, at a temperature in the range 100-250°C, preferably 150-225°C, when the final temperature is at least
It should be 175°C, preferably at least 195°C. The resulting oil solution of the sulfided product can be filtered if desired and then added to, for example, a lubricating oil or a fuel oil such as gasoline. As disclosed in GB 1287812 and GB 1194503, the solvent for the sulfurization step is preferably an alkylene or polyalkylene glycol or a lower alkyl monoether thereof. Accelerators such as carboxylic acids or metal salts thereof may also be present in the sulfurization step, as described in GB 1194503. S: The molar ratio of substituted salicylic acid is, for example, 0.25 to
3, preferably 0.5-2. The product can be reacted with a boron compound, for example boric acid, before or after the sulfurization step, as described in co-pending British Patent Application No. 8330441. The reaction products of the invention and mixtures thereof can be incorporated into oil compositions, in particular lubricating oil compositions or concentrates or fuels, such as motor vehicle crankcase oils, in an amount of 0.001 to 65% by weight, in particular 0.1 to 15% by weight, based on the weight of the total composition. %. Lubricating oils to which the additives of the present invention can be added include not only mineral lubricating oils but also synthetic oils. Synthetic hydrocarbon lubricating oils can also be used, as well as di-2-ethylhexyl sebacic acid ester,
Carbonate esters, phosphate esters, halogenated hydrocarbons, polysilicone, polyglycols, glycol esters such as tetraethylene glycol
Non-hydrocarbon synthetic oils including dibasic acid esters such as C 13 oxo acid diesters can also be used. Mixtures of these oils can also be used, especially mixtures of mineral and synthetic lubricating oils, including hydrogenated oils. When used in gasoline or fuel oils, such as diesel fuel, generally 0.001 to 0.5% by weight of the reaction product, based on the total weight of the composition, is used.
Typically, for ease of handling, e.g. 15-65
% by weight of said reaction product in a hydrocarbon diluent;
A concentrate consisting of 85-35% by weight mineral lubricating oil is produced. dyes, pour point depressants, anti-wear agents such as tricresyl phosphate, zinc dithiophosphate, antioxidants such as phenyl-alpha-naphthyl-amine,
Bis-phenols such as 4,4'-methylenebis(3,6-di-t-butylphenol), viscosity index improvers such as hydrogenated (co)polymers of conjugated dienes and optionally styrene, ethylene-higher olefins copolymers, polymethyl acrylate, polyisobutylene, etc., as well as ashless dispersants such as reaction products of polyisobutyl and maleic anhydride with amines and/or polyols, or other metal-containing surfactants such as overbased metal salicylic acids. Other additives such as salts may also be present in the composition. Reaction products of amines, formaldehyde, and alkylphenols (Mannitz bases) may also be present. Hereinafter, the present invention will be explained with reference to examples. Example 1 C 14-18 with calcium hydroxide and carbon dioxide
- Overbased alkylsalicylic acid with BI of 3
Calcium C14-18 -alkyl salicylate (Product A) was prepared and introduced into mineral lubricating oil. Overbased C14-18 -alkyl salicylate calcium 67% by weight concentrate in 33% by weight mineral lubricating oil
2500 g (2530 meq. acid) and 80 g elemental sulfur.
(2500 milliequivalents) and 20 g of ethylene glycol were placed in the reaction vessel (5). The mixture was heated to 125° C. with stirring and kept at this temperature for 1 hour. The temperature was then increased to 150°C and approx.
This temperature was maintained for 1 hour under a pressure of 550 mmHg. The temperature was then increased to 195°C and the pressure decreased to 50-60 mmHg and these conditions were maintained for 2 hours. The reaction product was then cooled to about 100°C and filtered through a filter aid to obtain a dark viscous product (yield: 2500g, S: 1.6% by weight).
(Product B). It has been found that carrying out the sulfidation at lower temperatures (175°C) produces some dissolved unreacted sulfur which tends to precipitate on standing. Furthermore, it was found that only a very small amount of decarboxylation occurred upon sulfidation (9%; acid number of starting material 1.06 and oxidation of product 0.96; acid number (milliequivalent acid/g) (determined after conversion, extraction with diethyl ether, phase separation and evaporation of the solvent) (the same method is used in the examples below). Example 2 50% by weight of calcium C 14-18 -alkyl salicylate (1625 meq) made from alkyl salicylic acid, calcium hydroxide and carbon dioxide according to the method described in Example 1 and having a BI of 7.72.
2500 g of concentrate in 50% by weight mineral oil was sulfided with 51.3 g elemental sulfur (1603 meq.) and 13 g ethylene glycol. Yield: 2453g, S:
1.2% by weight It was found that 2% decarboxylation occurred upon sulfidation (acid value of starting material 0.79 meq/g and acid value of product 0.77 meq/g). Example 3 Overbased with a BI of 7.2 at 62% by weight in 38% by weight mineral lubricating oil according to the method described in Example 1
C 14-18 - Magnesium alkylsalicylate (213.5
250 g of concentrate (milliequivalent) was sulfurized with 6.58 g elemental sulfur (205.6 meq) and 1.7 g ethylene glycol. Yield: 243.6g, S: 0.94
Weight % It was found that 3% decarboxylation occurred upon sulfidation (1.02 meq/g oxidation of starting material and 1.00 meq/g acid number of product). Comparative experiment 1 97.6 g (205 meq.) of pure C 14-18 -alkyl salicylic acid was added to 37.9 g (1025 meq.) Ca(OH) 2
and 69.5g of mineral lubricating oil to make 1.0 milliequivalent/
g of acid mixture were obtained. 133.2g (133.2g) of this mixture
milliequivalent) and 4.26 g S (133.2 milliequivalent) and 1.0 g
of ethylene glycol was heated to 125° C. with stirring and kept at this temperature for 1 hour. The temperature was further increased to 150℃ (1 hour, pressure: 550mm)
Hg) and further raised to 195°C (2 hours, 50
-60mmHg). The reaction mixture was cooled, diluted with n-hexane, passed through a supernatant and finally evaporated to give a very viscous dark material. Yield: 112.3g, S: 1.6%. It was found that 20% decarboxylation occurred upon sulfidation (acid value of starting material 1.22 meq/g and acid value of product 0.95 meq/g). Comparative Experiment 2 Following the method described in Example 1, 58% by weight of overbased with a BI of 1.28 in 42% by weight mineral lubricating oil
C 14-18 - Calcium alkyl salicylate concentrate
2500 g (2300 meq) were sulfided with 77 g elemental sulfur (2406 meq) and 19 g ethylene glycol. Yield: 2496g, S: 1.3% by weight. It was found that 28% decarboxylation occurred upon sulfidation (acid value of starting material 0.92 meq/g and oxidation of product 0.66 meq/g). Test Two 15W40 mineral lubricating oils (1 and 2) containing commercially available dispersants, detergents and antioxidant additives.
Products A and B (see Example 1) were tested in . The composition is 0.14% by weight of Ca in lubricating oil 1.
The composition contains lubricating oil 1 and product A in an amount of
0.14% by weight (as Ca) of product B. Compositions and were comprised of Lubricating Oil 2 containing 0.19% by weight as Ca of Products A and B, respectively. The composition and the CRC L38 test (ASTM
STP 509A, Part). This test measures bearing weight loss. These results are shown in table:
【表】
硫化生成物の使用によりベアリング重量損失が
減少することが判明した。
組成物およびをMSシーケンス
（Sequence）Ｄエンジン試験にて試験した。こ
の試験ではカムおよびリフタの摩耗および浄化性
能を測定した。
これらの結果を第表に示す：[Table] It has been found that the use of sulfurized products reduces bearing weight loss. The compositions were tested in the MS Sequence D engine test. This test measured cam and lifter wear and cleaning performance. These results are shown in table:
【表】
硫化生成物の使用により、カムおよびリフタの
摩耗が減少することが判つた。浄化率はほぼ同程
度に留まつた。[Table] It has been found that the use of sulfurized products reduces cam and lifter wear. The purification rate remained at about the same level.
Claims (1)
化合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。 ２ 金属がアルカリ土類金属である特許請求の範
囲第１項に記載の方法。 ３ 脂肪族炭化水素置換サリチル酸がC8-30−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。 ４ 過塩基サリチル酸塩の塩基度指数が少なくと
も３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。 ５ 少なくとも175℃で硫化を行なう特許請求の
範囲第１項乃至第４項のいずれかに記載の方法。 ６ Ｓ：置換サリチル酸のモル比が0.25〜３であ
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。 ７ 硫化前または硫化後の生成物を硼素化合物と
反応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。[Claims] 1. Converting an aliphatic hydrocarbon-substituted salicylic acid with a basic metal compound and carbon dioxide into an overbased metal salicylate having a basicity index of at least 1.5, and then converting the overbased metal salicylate into an overbased metal salicylate having a basicity index of at least 1.5. 1. A method for producing a sulfurized overbased metal salt of aliphatic hydrocarbon-substituted salicylic acid, the method comprising sulfurizing the metal salt by heating with a sulfurized aliphatic hydrocarbon. 2. The method according to claim 1, wherein the metal is an alkaline earth metal. 3. The method according to claim 1 or 2, wherein the aliphatic hydrocarbon-substituted salicylic acid is C8-30 -alkyl salicylic acid. 4. The method according to any one of claims 1 to 3, wherein the overbased salicylate has a basicity index of at least 3. 5. The method according to any one of claims 1 to 4, wherein the sulfurization is carried out at at least 175°C. 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. 7. The method according to any one of claims 1 to 6, wherein the product before or after sulfurization is reacted with a boron compound.
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 JPS6124560A (en) | 1986-02-03 |
| JPH0580517B2 true 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) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63266424A (en) * | 1987-04-24 | 1988-11-02 | Alps Electric Co Ltd | Liquid crystal display element |
| 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 |
| JPH083767Y2 (en) * | 1992-07-09 | 1996-01-31 | 日本ピラー工業株式会社 | Shaft seal device |
| 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 |
| JP2005220197A (en) * | 2004-02-04 | 2005-08-18 | Nippon Oil Corp | Lubricating oil composition to be brought into contact with lead-containing metal material |
| US7956022B2 (en) * | 2005-07-29 | 2011-06-07 | Chevron Oronite Company Llc | Low sulfur metal detergent-dispersants |
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 ZA ZA855048A patent/ZA855048B/en unknown
- 1985-07-04 JP JP14760585A patent/JPS6124560A/en active Granted
- 1985-07-04 EP EP85201083A patent/EP0168880B1/en not_active Expired
- 1985-07-04 DE DE8585201083T patent/DE3564570D1/en not_active Expired
- 1985-07-04 BR BR8503201A patent/BR8503201A/en not_active IP Right Cessation
-
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1253873A (en) | 1989-05-09 |
| BR8503201A (en) | 1986-03-25 |
| ZA855048B (en) | 1986-02-26 |
| EP0168880B1 (en) | 1988-08-24 |
| GB8417297D0 (en) | 1984-08-08 |
| JPS6124560A (en) | 1986-02-03 |
| SG7090G (en) | 1990-07-13 |
| EP0168880A1 (en) | 1986-01-22 |
| DE3564570D1 (en) | 1988-09-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |