JPH0580519B2 - - Google Patents
Info
- Publication number
- JPH0580519B2 JPH0580519B2 JP60147607A JP14760785A JPH0580519B2 JP H0580519 B2 JPH0580519 B2 JP H0580519B2 JP 60147607 A JP60147607 A JP 60147607A JP 14760785 A JP14760785 A JP 14760785A JP H0580519 B2 JPH0580519 B2 JP H0580519B2
- Authority
- JP
- Japan
- Prior art keywords
- product
- sulfurized
- weight
- meq
- salicylic acid
- 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 - Lifetime
Links
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- -1 alkali metal salicylate salt Chemical class 0.000 claims description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 11
- 229960004889 salicylic acid Drugs 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 229960001860 salicylate Drugs 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 150000003463 sulfur Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000011575 calcium Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 239000010688 mineral lubricating oil Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 4
- 150000003873 salicylate salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PIMNDJYXVOQVSP-UHFFFAOYSA-N 1-o-ethyl 10-o-hexyl decanedioate Chemical compound CCCCCCOC(=O)CCCCCCCCC(=O)OCC PIMNDJYXVOQVSP-UHFFFAOYSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 238000006612 Kolbe reaction Methods 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002319 Poly(methyl acrylate) 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003819 basic metal compounds Chemical class 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 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
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical class ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent 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
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
- C10L1/2418—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides containing a carboxylic substituted; derivatives thereof, e.g. esters
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
【発明の詳細な説明】
本発明は、硫化されかつ必要に応じ過塩基化さ
れた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。
英国特許第1287812号明細書から、この種の生
成物およびこれら生成物を洗剤および摩耗防止剤
として含有する油組成物が既に知られている。こ
の明細書は、脂肪族炭化水素置換サリチル酸また
はその金属塩を硫黄元素、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）と少なくともと150℃の温度にて反
応させ、必要に応じさらに二酸化炭素と反応させ
ることを開示している。英国特許第1194503号明
細書にも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、サリチル酸も
しくは金属塩と硫黄との反応に際し相当程度の脱
カルボキシル化が生じるという欠点を有すること
が判明した。
今回、最初に脂肪族炭化水素置換フエノールを
硫化し、次いで反応生成物をサリチル酸またはそ
の金属塩に変換することによりこの問題は回避し
うることが判明した。
したがつて、本発明は脂肪族炭化水素置換フエ
ノールを硫化し、得られた生成物をアルカリ金属
水酸化物および二酸化炭素によりサリチル酸アル
カリ金属塩に変換することを特徴とする、硫化さ
れた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。このように得られた生成物を必要
に応じ過塩基サリチル酸金属塩に変換する。
本発明によつて製造される所定のサリチル酸金
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。
適する脂肪族炭化水素置換フエノールは上記英
国特許明細書に記載されている。好適なものは
C8〜30−アルキルフエノールである。
これらフエノールはハロゲン化硫黄、好ましく
は塩化硫黄たとえばSCl2特にS2Cl2により硫化す
ることができる。硫黄元素も使用することができ
る。
好ましくは脂肪族炭化水素（たとえばｎ−ヘキ
サン）のような溶剤中でハロゲン化硫黄による硫
化を行なう。キシレンのような芳香族溶剤の使用
は避けるべきである。何故なら、これら溶剤もハ
ロゲン化硫黄で硫化されうるからである。
反応は室温で行なうこともできるが、或る程度
の加熱を行なつて、たとえば60℃まで加熱するこ
ともできる。
エチレングリコールのような溶剤および石灰
（Ca（OH）2）のような塩基性触媒の存在下で100
〜250℃の範囲、好ましくは150〜225℃の範囲の
温度にてフエノールを硫黄と接触させることによ
り硫黄元素による硫化を行なうことができる。こ
の場合、最終温度は好ましくは少なくとも175℃、
特に好ましくは少なくとも195℃とすべきである。
上記英国特許第1287812号および第1194503号各
明細書に記載されているように、硫化工程に使用
する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。溶剤はエチレングリコール
であるのが最も好ましい。
英国特許第1194503号明細書に記載されたよう
に、たとえば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：置換フエノールのモル比はたとえば0.25〜
３好ましくは0.5〜２である。
得られる生成物を必要に応じ酸性化して、石灰
酸をフエノールに変換させる。
上記英国特許明細書におよび英国特許出願第
786167号明細書に記載されているように、硫化フ
エノールからサリチル酸塩への変換は好ましくは
水酸化ナトリウムおよび二酸化炭素との反応によ
り、コルベ合成を介して行なわれる。
この硫化サリチル酸塩は対応の過塩基サリチル
酸塩を製造するのに有用な中間体である。過塩基
サリチル酸塩は潤滑油組成物中で洗剤特性が良好
であると同時に摩耗が少ない。過塩基サリチル酸
金属塩の適する金属はたとえばLi，Cs，Na及び
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。
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。したがつ
て、硫化サリチル酸アルカリ金属塩を好適には対
応するサリチル酸まで変換し、次いでこれを塩基
性アルカリ土類金属化合物（好ましくは水酸化
物）および二酸化炭素により過塩基サリチル酸ア
ルカリ土類金属塩まで変換する。過塩基化の程度
は、金属対サリチル酸の等量比として定義される
塩基度指数（B.I.）として表わされる。
たとえば英国特許第786167号明細書に記載され
ているように、酸性化及びたとえば炭化水素溶剤
（好ましくはキシレンのような芳香族炭化水素溶
剤）などの溶剤中での塩基性金属化合物および二
酸化炭素との反応により硫化サリチル酸アルカリ
金属塩を過塩基化することができる。
得られた反応混合物に軽質鉱物油を加え、次い
で炭化水素溶剤および生成した水を全て留去する
ことができる。
得られた硫化生成物の油溶液を必要に応じ過
し、次いでたとえば潤滑油またはガソリンを包含
する燃料油のような油へ添加することができる。
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、硫化前または硫化後
に、生成物を硼素化合物たとえば硼酸と反応させ
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に全組成
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。
本発明の添加物を加える潤滑油は鉱物潤滑油だ
けでなく合成油も包含する。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、テトラエチレングリ
コールのC13オキソ酸ジエステルのようなグリコ
ールエステルなど、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、特に水素化油
を包含する鉱物潤滑油および合成潤滑油の混合物
も使用することができる。
ガソリンもしくは燃料油、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。一般に、炭化水素希釈剤中の前記反応生成物
15〜65重量％と、鉱物潤滑油85〜35重量％とから
なる濃厚物が取り扱いの容易さのため製造され
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、
４，4′−メチレンビス（３，６−ジ−ｔ−ブチル
フエノール）のようなビスフエノール類、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
ポリイソブチレンと無水マレイン酸とアミンおよ
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、実施例により本発明をさらに説明する。
実施例 １
硫化アルキルフエノールの製造
2000ｇのテトラプロペニルフエノール（7520ミ
リ当量）と122ｇの水酸化カルシウム（3300ミリ
当量）と364ｇの元素硫黄（11375ミリ当量）と74
ｇ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、50〜60mmHgで２時間保つた。反応
生成物を冷却し、溶剤を加え、混合物を過し
た。溶剤を除去して、暗色かつ粘性の生成物を得
た（収量：2266ｇ、Ｓ：8.2重量％）（生成物Ａ）。
実施例 ２
硫化アルキルフエノールの製造
524ｇのテトラプロペニルフエノール（2002ミ
リ当量）と520ｇのｎ−ヘキサンとを含有する反
応容器（２）へ、温度が20〜40℃の一定に保た
れるような速度でｎ−ヘキサン70ｇ中のS2Cl2
67.5ｇ（1000ミリ当量の硫黄）の溶液を滴加し
た。S2Cl2の添加が完了した後（２〜３時間）、こ
の反応混合物を窒素でゆすぎ、溶剤を減圧下で除
去した（収量：557ｇ、Ｓ：5.0重量％）（生成物
Ｂ）。
これらの実施例は元素硫黄およびS2Cl2による
硫化が可能であることを示している。
実施例 ３
実施例２からの生成物を500ｇのキシレンで希
釈し、次いで窒素雰囲気中で135℃まで加熱した。
水酸化ナトリウム100ｇ（OH吸収において25％
過剰）の水120ｇ中の水溶液を発泡しないよう注
意しながら加え、水を留去した。この溶液を140
℃、14バールのCO2圧力にてカルボキシル化し
た。酸性化しかつ水洗した後、硫化サリチル酸の
収量は587ｇ、酸価は1.98ミリ当量／ｇ、硫黄含
有量は4.72重量％であつた（生成物Ｃ）。
実施例 ４
200ｇのキシレンと120ｇのメタノールとにおけ
る実施例３の硫化アルキルサリチル酸塩200ｇ
（396ミリ当量）の溶液を59ｇのCa（OH）2（1595
ミリ当量）で55℃にて１時間処理した。この反応
生成物を過し、溶剤を減圧下で蒸発させて6.8
重量％のCaと3.9重量％のＳと1.5のB.I.とを有す
る生成物（223ｇ）を得た（生成物Ｄ）。
実施例 ５
200ｇのキシレンと120ｇのメタノールとにおけ
る実施例３の硫化アルキルサリチル酸塩200ｇ
（396ミリ当量）の溶液を59ｇのCa（OH）2（1595
ミリ当量）で55℃にて１時間処理した。次いで、
13.9ｇのCO2（632ミリ当量）を導入した。後処理
により、11.5重量％のCaと3.7重量％のＳと3.0の
B.I.とを有する生成物253.5ｇを得た（生成物Ｅ）。
生成物E170ｇを155ｇの鉱物潤滑油と混合して、
6.0重量％のCaと1.9重量％のＳと3.0のB.I.とを有
する油濃厚物を得た（生成物Ｆ）。
比較実験
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、1.0
ｇ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。さらに温
度を150℃まで上昇させ（１時間、圧力：550mm
Hg）、さらに195℃まで加熱した（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、最後に蒸
発させて極めて粘性の暗色物質を得た。収率：
112.3ｇ、Ｓ：1.6重量％。
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、これはHCl
による酸性化、ジエチルエーテルによる抽出、相
分離および溶剤の蒸発の後に測定した）。
試 験
２種のCRC L38試験（ASTM STP 509A、第
部）において、生成物Ｆ（実施例５参照）の性
能を非硫化過塩基C14〜18−アルキルサリチル酸カ
ルシウムの性能と比較した。このために２種の組
成物を作成した。組成物は市販の分散剤と洗剤
と酸化防止剤添加物を含有する15W40鉱物潤滑油
および0.14重量％（Caとして）の過塩基C14〜18−
アルキルサリチル酸カルシウム（B.I.＝３）から
なり、組成物は同じ15W40潤滑油と0.14重量％
（Caとして）の生成物Ｆとからなる。ベアリング
重量損失を測定したCRC L38試験の結果を下記
第表に示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing sulfurized and optionally overbased aliphatic hydrocarbon-substituted metal salicylic acid salts. Products of this kind and oil compositions containing these products as detergents and antiwear agents are already known from GB 1287812. This specification describes the reaction of an aliphatic hydrocarbon-substituted salicylic acid or a metal salt thereof with elemental sulfur, an alkaline earth base (e.g. hydroxide) and a solvent (e.g. ethylene glycol) at a temperature of at least 150°C. Accordingly, further reaction with carbon dioxide is disclosed. A similar method is also 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 of salicylic acid or metal salts with sulfur. It has now been found that this problem can be avoided by first sulfiding the aliphatic hydrocarbon-substituted phenol and then converting the reaction product to salicylic acid or its metal salt. Therefore, the present invention provides a method for preparing sulfurized aliphatic phenols, characterized in that the aliphatic hydrocarbon-substituted phenols are sulfurized and the resulting product is converted into alkali metal salicylate salts with an alkali metal hydroxide and carbon dioxide. The present invention relates to a method for producing a hydrocarbon-substituted salicylic acid metal salt. The product thus obtained is converted into an overbased metal salicylate if necessary. The predetermined salicylic acid metal salt produced by the present invention is a complex substance that cannot be simply represented by a chemical structural formula, and the product is specified by the above-mentioned production method. Suitable aliphatic hydrocarbon substituted phenols are described in the above-mentioned British patent specifications. What is suitable is
It is a C8-30 -alkylphenol. These phenols can be sulfurized with sulfur halides, preferably sulfur chlorides such as SCl 2 especially S 2 Cl 2 . Elemental sulfur can also be used. Sulfidation with sulfur halide is preferably carried out in a solvent such as an aliphatic hydrocarbon (eg n-hexane). The use of aromatic solvents such as xylene should be avoided. This is because these solvents can also be sulfurized with halogenated sulfur. The reaction can be carried out at room temperature or with some heating, for example up to 60°C. 100 in the presence of a solvent such as ethylene glycol and a basic catalyst such as lime (Ca(OH) 2 )
Elemental sulfur sulfidation can be carried out by contacting the phenol with sulfur at a temperature in the range -250<0>C, preferably in the range 150-225<0>C. In this case the final temperature is preferably at least 175°C,
Particularly preferably it should be at least 195°C. As described in GB 1287812 and GB 1194503, the solvent used in the sulfurization step is preferably an alkylene or polyalkylene glycol or a lower alkyl monoether thereof. Most preferably the solvent is ethylene glycol. Accelerators, such as carboxylic acids or metal salts thereof, may also be present in the sulfurization step, as described in GB 1194503. The molar ratio of S:substituted phenol is, for example, 0.25 to
3, preferably 0.5 to 2. The resulting product is optionally acidified to convert lime acid to phenol. The above UK patent specification and UK patent application no.
As described in 786167, the conversion of sulfurized phenols to salicylates is carried out via Kolbe synthesis, preferably by reaction with sodium hydroxide and carbon dioxide. This sulfurized salicylate is a useful intermediate for making the corresponding overbased salicylate. Overbased salicylates have good detergent properties in lubricating oil compositions as well as low wear. Suitable metals for overbased metal salicylates include alkali metals such as Li, Cs, Na and K, such as Ca, Ba, Sr.
and alkaline earth metals such as Mg and polyvalent metals such as Zn and Cr. Alkaline earth metals such as calcium, barium and magnesium are preferred. Therefore, the sulfurized alkali metal salicylate salt is preferably converted to the corresponding salicylic acid, which is then converted to the overbased alkaline earth metal salicylate salt with a basic alkaline earth metal compound (preferably a hydroxide) and carbon dioxide. Convert. The degree of overbasing is expressed as the basicity index (BI), defined as the equivalent ratio of metal to salicylic acid. Acidification and treatment of basic metal compounds and carbon dioxide in a solvent such as a hydrocarbon solvent (preferably an aromatic hydrocarbon solvent such as xylene), as described for example in GB 786167. A sulfurized alkali metal salicylate salt can be overbased by the reaction. Light mineral oil can be added to the resulting reaction mixture and then all the hydrocarbon solvent and water produced can be distilled off. The resulting oil solution of the sulfided product can be filtered if necessary and then added to an oil, such as a lubricating oil or a fuel oil, including gasoline. The product can be reacted with a boron compound, such as boric acid, either before or after sulfurization, as described in co-pending British Patent Application No. 8330441. The reaction products of the invention and mixtures thereof are present in 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 relative to the total composition weight. It can be blended in a concentration range of . Lubricating oils to which the additives of the present invention are added include not only mineral lubricating oils but also synthetic oils. Synthetic hydrocarbon lubricating oils may also be used, as well as e.g.
Non-hydrocarbon synthetic oils can also be used, such as ethylhexyl sebacate, carbonate, phosphate, halogenated hydrocarbons, polysilicone, polyglycol, glycol esters such as the C 13 oxoacid diester of tetraethylene glycol. Mixtures of these oils may 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 is used, based on the total weight of the composition. Generally, the reaction product in a hydrocarbon diluent
Concentrates of 15-65% by weight and 85-35% by weight of mineral lubricating oil are produced for ease of handling. dyes, pour point depressants, anti-wear agents such as tricresyl phosphate, zinc dithiophosphate, antioxidants such as phenyl-alpha-naphthyl-amine,
Bisphenols 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 Olefin copolymers, polymethyl acrylate, polyisobutylene, etc., as well as ashless dispersants such as reaction products of polyisobutylene and maleic anhydride with amines and/or polyols, or other metal-containing surfactants such as overbased metals. Salicylates and the like may also be present in the compositions. Reaction products of amines, formaldehyde, and alkylphenols (Mannitz bases) may also be present. The present invention will be further explained below with reference to Examples. Example 1 Preparation of sulfurized alkylphenol 2000 g of tetrapropenylphenol (7520 meq), 122 g of calcium hydroxide (3300 meq), 364 g of elemental sulfur (11375 meq) and 74
g of ethylene glycol was placed in the reaction vessel (5). While stirring, the mixture was heated to 125°C and kept at this temperature for 1 hour. The temperature was then increased to 150°C and held at this temperature for 1 hour at a pressure of approximately 550 mmHg. The temperature was then increased to 195°C and maintained at 50-60 mmHg for 2 hours. The reaction product was cooled, solvent was added and the mixture was filtered. Removal of the solvent gave a dark and viscous product (yield: 2266 g, S: 8.2% by weight) (Product A). Example 2 Preparation of sulfurized alkylphenols 524 g of tetrapropenylphenol (2002 meq.) and 520 g of n-hexane are charged into a reaction vessel (2) at such a rate that the temperature is kept constant between 20 and 40°C. S 2 Cl 2 in 70 g of n-hexane at
A solution of 67.5 g (1000 meq. sulfur) was added dropwise. After the S 2 Cl 2 addition was complete (2-3 hours), the reaction mixture was rinsed with nitrogen and the solvent was removed under reduced pressure (yield: 557 g, S: 5.0% by weight) (Product B). These examples show that sulfurization with elemental sulfur and S 2 Cl 2 is possible. Example 3 The product from Example 2 was diluted with 500 g of xylene and then heated to 135° C. in a nitrogen atmosphere.
100g of sodium hydroxide (25% in OH absorption)
An aqueous solution of (excess) in 120 g of water was added, taking care not to foam, and the water was distilled off. Add this solution to 140
Carboxylation was carried out at °C and 14 bar CO2 pressure. After acidification and washing with water, the yield of sulfurized salicylic acid was 587 g, the acid value was 1.98 meq/g and the sulfur content was 4.72% by weight (product C). Example 4 200g sulfurized alkyl salicylate of Example 3 in 200g xylene and 120g methanol
(396 meq) solution of 59 g Ca(OH) 2 (1595
milliequivalent) at 55°C for 1 hour. The reaction product was filtered and the solvent was evaporated under reduced pressure to 6.8
A product (223 g) with weight % Ca, 3.9 weight % S and 1.5 BI was obtained (Product D). Example 5 200g sulfurized alkyl salicylate of Example 3 in 200g xylene and 120g methanol
(396 meq) solution of 59 g Ca(OH) 2 (1595
milliequivalent) at 55°C for 1 hour. Then,
13.9 g of CO2 (632 meq) was introduced. Post-treatment resulted in 11.5 wt% Ca, 3.7 wt% S and 3.0 wt%
253.5 g of product with BI were obtained (product E).
Mix 170 g of product E with 155 g of mineral lubricating oil,
An oil concentrate with 6.0% by weight Ca, 1.9% by weight S and 3.0 BI was obtained (Product F). Comparative experiment C 97.6 g (205 meq.) of 14-18 -alkyl salicylic acid was mixed with 37.9 g (1025 meq.) of Ca(OH) 2 .
1.0 meq/g with 69.5g of mineral lubricating oil
A mixture of acids was obtained. 133.2 g (133.2 meq.) of this mixture, 4.26 g S (133.2 meq.), and 1.0
g of ethylene glycol at 125°C with stirring.
and kept at this temperature for 1 hour. Further increase the temperature to 150℃ (1 hour, pressure: 550mm
Hg) and further heated 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% by weight. 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, which corresponds to HCl
(measured after acidification with diethyl ether, extraction with diethyl ether, phase separation and evaporation of the solvent). Testing The performance of Product F (see Example 5) was compared to that of non-sulfurized overbased calcium C14-18 -alkyl salicylate in two CRC L38 tests (ASTM STP 509A, Part). Two compositions were created for this purpose. The composition is a 15W40 mineral lubricating oil containing a commercially available dispersant and detergent and antioxidant additives and 0.14% by weight (as Ca) overbased C14-18−
Composed of calcium alkyl salicylate (BI = 3), the composition is the same as 15W40 lubricating oil and 0.14% by weight
(as Ca) and product F. The results of the CRC L38 test, which measured bearing weight loss, are shown in the table below. 【table】
Claims (1)
られた生成物をアルカリ金属水酸化物および二酸
化炭素によりサリチル酸アルカリ金属塩に変換す
ることを特徴とする、硫化された脂肪族炭化水素
置換サリチル酸金属塩の製造方法。 ２ サリチル酸アルカリ金属塩を対応のサリチル
酸に変換し、これを塩基性アルカリ土類金属化合
物および二酸化炭素により過塩基サリチル酸アル
カリ土類金属塩に変換す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フエノールがC8〜30−ア
ルキルフエノール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 ハロゲン化硫黄により硫化を行なう特許請求
の範囲第１項乃至第３項のいずれかに記載の方
法。 ５ Ｓ：置換フエノールのモル比が0.25〜３であ
る特許請求の範囲第１項乃至第４項のいずれかに
記載の方法。 ６ 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５項のい
ずれかに記載の方法。[Claims] 1. A sulfurized aliphatic product, characterized in that an aliphatic hydrocarbon-substituted phenol is sulfurized and the resulting product is converted into an alkali metal salicylate salt with an alkali metal hydroxide and carbon dioxide. A method for producing a hydrocarbon-substituted salicylic acid metal salt. 2. The process according to claim 1, wherein an alkali metal salicylate is converted into the corresponding salicylic acid, which is then converted into an overbased alkaline earth metal salicylate with a basic alkaline earth metal compound and carbon dioxide. 3. The method according to claim 1 or 2, wherein the aliphatic hydrocarbon-substituted phenol is a C8-30 -alkylphenol. 4. The method according to any one of claims 1 to 3, wherein sulfurization is carried out using halogenated sulfur. 5. The method according to any one of claims 1 to 4, wherein the molar ratio of 5S:substituted phenol is 0.25 to 3. 6. The method according to any one of claims 1 to 5, wherein the product before or after sulfurization is reacted with a boron compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8417299 | 1984-07-06 | ||
| GB848417299A GB8417299D0 (en) | 1984-07-06 | 1984-07-06 | Preparation of sulphurized salicylates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6124562A JPS6124562A (en) | 1986-02-03 |
| JPH0580519B2 true JPH0580519B2 (en) | 1993-11-09 |
Family
ID=10563525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14760785A Granted JPS6124562A (en) | 1984-07-06 | 1985-07-04 | Manufacture of sulfide salicylate |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0168111B1 (en) |
| JP (1) | JPS6124562A (en) |
| BR (1) | BR8503203A (en) |
| CA (1) | CA1253872A (en) |
| DE (1) | DE3564262D1 (en) |
| GB (1) | GB8417299D0 (en) |
| SG (1) | SG6890G (en) |
| ZA (1) | ZA855051B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8714922D0 (en) * | 1987-06-25 | 1987-07-29 | Shell Int Research | Lubricating oil composition |
| US6235688B1 (en) | 1996-05-14 | 2001-05-22 | Chevron Chemical Company Llc | Detergent containing lithium metal having improved dispersancy and deposit control |
| 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 |
| CN113026528A (en) * | 2021-03-10 | 2021-06-25 | 浙江中天恒筑钢构有限公司 | Method for mounting mountain forest space curve steel structure plank road |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60147497A (en) * | 1984-01-09 | 1985-08-03 | Cosmo Co Ltd | Preparation of salicylate-containing basic alkaline earth metal sulfide phenate type detergent |
| JPS60168793A (en) * | 1984-02-13 | 1985-09-02 | Cosmo Co Ltd | Production of basic sulfurized alkaline earth metal phenate detergent |
Family Cites Families (12)
| 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 |
| 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 |
| 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 |
| US3595791A (en) * | 1969-03-11 | 1971-07-27 | Lubrizol Corp | Basic,sulfurized salicylates and method for their preparation |
| US3595790A (en) * | 1969-10-22 | 1971-07-27 | Lubrizol Corp | Oil soluble highly basic metal salts of organic acids |
| GB1443329A (en) * | 1973-10-22 | 1976-07-21 | Exxon Research Engineering Co | Thio bisalkylphenols and their use as anti-oxidants in lubricating oils |
| SU644811A1 (en) * | 1975-07-14 | 1980-02-05 | Всесоюзный научно-исследовательский институт по переработке нефти | Method of preparing sulfide alkylphenolate additive to lubricating oils |
| GB2031422B (en) * | 1978-09-14 | 1983-05-11 | Mitsui Toatsu Chemicals | Preparation of 2,2'-bis(4-substituted-phenol sulfides |
-
1984
- 1984-07-06 GB GB848417299A patent/GB8417299D0/en active Pending
-
1985
- 1985-06-17 CA CA000484166A patent/CA1253872A/en not_active Expired
- 1985-07-04 DE DE8585201084T patent/DE3564262D1/en not_active Expired
- 1985-07-04 EP EP85201084A patent/EP0168111B1/en not_active Expired
- 1985-07-04 ZA ZA855051A patent/ZA855051B/en unknown
- 1985-07-04 JP JP14760785A patent/JPS6124562A/en active Granted
- 1985-07-04 BR BR8503203A patent/BR8503203A/en not_active IP Right Cessation
-
1990
- 1990-02-05 SG SG68/90A patent/SG6890G/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60147497A (en) * | 1984-01-09 | 1985-08-03 | Cosmo Co Ltd | Preparation of salicylate-containing basic alkaline earth metal sulfide phenate type detergent |
| JPS60168793A (en) * | 1984-02-13 | 1985-09-02 | Cosmo Co Ltd | Production of basic sulfurized alkaline earth metal phenate detergent |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1253872A (en) | 1989-05-09 |
| GB8417299D0 (en) | 1984-08-08 |
| EP0168111B1 (en) | 1988-08-10 |
| ZA855051B (en) | 1986-02-26 |
| DE3564262D1 (en) | 1988-09-15 |
| SG6890G (en) | 1990-07-13 |
| EP0168111A1 (en) | 1986-01-15 |
| JPS6124562A (en) | 1986-02-03 |
| BR8503203A (en) | 1986-03-25 |
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