KR900004216B1 - Preparation method for zinc salts dithio phosphoric acids - Google Patents
Preparation method for zinc salts dithio phosphoric acids Download PDFInfo
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- KR900004216B1 KR900004216B1 KR1019870015468A KR870015468A KR900004216B1 KR 900004216 B1 KR900004216 B1 KR 900004216B1 KR 1019870015468 A KR1019870015468 A KR 1019870015468A KR 870015468 A KR870015468 A KR 870015468A KR 900004216 B1 KR900004216 B1 KR 900004216B1
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- Prior art keywords
- alcohol
- zinc salt
- preparation
- reaction
- zinc salts
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- 235000011007 phosphoric acid Nutrition 0.000 title 1
- 238000002360 preparation method Methods 0.000 title 1
- -1 zinc salts dithio phosphoric acids Chemical class 0.000 title 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 150000003751 zinc Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 5
- 230000003078 antioxidant effect Effects 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000002199 base oil Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
본 발명은 윤활유첨가제중 산화방지제 및 마모방지제로 사용되는 디알킬디티오인산아연염을 제조함에 있어서, P2S5에 탄소수 4 내지 8개의 알콜을 반응시켜 디알킬디티오인산을 합성할때 촉매로 트리에틸아민을 첨가함을 특징으로 하는 디알킬디티오인산아연염의 제조방법에 관한 것이다.The present invention is to prepare a dialkyldithiophosphate zinc salt used as an antioxidant and abrasion inhibitor in lubricating oil additives, the reaction of P 2 S 5 with 4 to 8 carbon atoms alcohol to synthesize dialkyldithiophosphoric acid as a catalyst It relates to a method for producing a dialkyldithiophosphate zinc salt characterized by adding triethylamine.
현대 기계공업의 발달과 함께 내연기관의 열효율 증대를 위하여 기관 내부에는 고온고압의 가혹한 조건이 요구되고 있으며 이같은 고온고압하의 내연기관에 대한 윤활작용을 증가시키고 윤활유 자체의 산화를 극소화시킬수 있는 산화방지제가 요구되어 진다.In order to increase the thermal efficiency of internal combustion engines with the development of modern machinery, harsh conditions of high temperature and high pressure are required inside the engines. Required.
윤활유는 고온에서 용존산소와 기관내의 금속성분에 의해 과산화물이 생성되며 이 과산화물이 연쇄반응에 의해 산화반응이 진행되면서 윤활유 자체의 열화현상이 일어난다. 따라서 이와같은 산화반응의 진행을 억제하기 위해 생성되는 과산화물을 분해시키는 과산화물 분해제로서의 새로운 산화방지제가 필요하게 되었으며 이것이 본 발명의 디알킬디티오인산아연염이다.Lubricating oils are produced at high temperatures by peroxides caused by dissolved oxygen and metal components in the engine. As the peroxides are oxidized by a chain reaction, deterioration of the lubricant itself occurs. Therefore, in order to suppress the progress of the oxidation reaction, a new antioxidant as a peroxide decomposing agent that decomposes the produced peroxide is required, which is the dialkyldithiophosphate zinc salt of the present invention.
또한 디알킬디티오인산아연염은 내연기관내의 금속과 금속간의 마찰에 의한 마모를 감소시키는 마모방지제로서의 기능도 가지고 있는 다목적 윤활유 첨가제이다. 디알킬디티오인산아연염이 산화방지제와 마모방지제의 역활을 하기 위해서 윤활유중에 첨가되어 쉽게 용해되면서 온도가 올라감에 따라 쉽게 분해되어야 한다.In addition, dialkyldithiophosphate zinc salt is a multipurpose lubricating oil additive which also functions as an antiwear agent to reduce abrasion by friction between metals in an internal combustion engine. Dialkyldithiophosphate zinc salts must be added to the lubricant to act as antioxidants and antiwear agents, and dissolve easily as the temperature rises.
디알킬디티오인산아연염은 산화방지제 역할뿐아니라 엔진내에 존재하는 여러 금속에 의해 생길 수 있는 부식을 방지하는 역할과 내연기관내의 개폐장치, 오일펌프, 타이밍 기어등은 그 접촉면의 과중한 하중과 쉬어(shear)가 작용하여 과도한 마모가 발생한다는 문제를 안고 있는데 이러한 마모를 방지하는 역할을 한다.Dialkyldithiophosphate zinc salt not only acts as an antioxidant, but also prevents corrosion caused by the various metals present in the engine. (shear) acts to cause excessive wear, which prevents such wear.
디알킬디티오인산아연염은 일반식(I)로 표기되는 구조를 가진다.The dialkyl dithiophosphate zinc salt has a structure represented by general formula (I).
R1R2: 알킬기이다.R 1 R 2 is an alkyl group.
결합된 알킬기는 1차 혹은 2차 알콜로부터 유도되며 합성경로는 다음과 같다.The bound alkyl group is derived from a primary or secondary alcohol and the synthetic route is as follows.
본 발명을 상세히 설명하면, 포스포러스펜타설파이드에 알콜을 반응시켜 디알킬디티오인산을 합성한다. 이때 사용되는 알콜은 탄소수 4 내지 8개의 이차알콜을 사용된다. 본 발명에서는 이소부틸알콜과 이소옥탄올을 혼합하여 반응에 사용하였다. 본 반응에 사용되는 알콜은 P2S5에 대해 0.2 내지 0.3mole로 주입하고 반응온도는 100℃ 이하의 온도에서 실시하였으며 반응시간은 1 내지 6시간이다.DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail to synthesize dialkyldithiophosphoric acid by reacting phosphorus pentasulphide with alcohol. At this time, the alcohol used is a secondary alcohol having 4 to 8 carbon atoms. In the present invention, isobutyl alcohol and isooctanol were mixed and used for the reaction. Alcohol used in this reaction was injected at 0.2 to 0.3 mole with respect to P 2 S 5 and the reaction temperature was carried out at a temperature of 100 ℃ or less and the reaction time is 1 to 6 hours.
또한 촉매로서 트리에틸아민을 알콜에 대해 0.6중량%를 사용하여 디알킬디티오인산을 합성한 다음 온도를 내려 미반응의 P2S5을 여과하여 제거한다. 여기에 중화제인 ZnO를 첨가하여 중화시킨다. 이때 사용된ZnO는 산에 대해 0.5 내지 0.65mole비로 첨가한다. 반응온도는 60° 내지 90℃가 적당하다. 반응시간은 1내지 6시간정도 반응시킨다. 중화반응후 5 내지 20중량%의 윤활기유로 희석시킨다. 그런다음 미반응의 고형물을 제거하고 N2을 주입하여 H2O을 제거하고 미반응의 알콜도 제거하여 디알킬디티오인산아연염을 제조한다.In addition, diethyldithiophosphoric acid was synthesized using 0.6% by weight of triethylamine as alcohol as a catalyst, and then the temperature was lowered to remove unreacted P 2 S 5 by filtration. It is neutralized by adding ZnO which is a neutralizing agent. The ZnO used at this time is added at a ratio of 0.5 to 0.65 mole relative to the acid. The reaction temperature is suitably 60 ° to 90 ° C. The reaction time is about 1 to 6 hours. After neutralization, the mixture is diluted with 5 to 20% by weight of lubricating base oil. Then, unreacted solids are removed and N 2 is injected to remove H 2 O and unreacted alcohol to prepare dialkyldithiophosphate zinc salt.
실시예를 들어 본 발명을 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.
[실시예 1]Example 1
환류냉각기와 질소주입기를 장치한 3구 둥근바닥 플라스크에 톨루엔 29.8g, 이소옥탄올 44.8g, 이소부탄올 25.6g, 트리에틸아민 0.62g을 넣고 가열, 교반하면서 P2S536.3g을 서서히 주입하여 온도를 80℃로 유지한다. 1시간동안 반응한 다음 온도를 내려 미반응의 P2S5를 제거한 디알킬디티오인산을 합성하고 여기에 ZnO 14.0g을 서서히 주입하여 온도를 60℃ 유지하면서 1시간정도 반응시킨다. 반응완료후 윤활기유 6.0g을 가하여 희석한 다음 미반응의 고형물을 제거하고 N2개스를 주입하여 생성된 H2O과 미반응의 알콜을 증류하여 엷은 노란색의 생성물인 디알킬디티오인산아연염을 얻었다. 수율은 91%이었다.A reflux condenser, and a 3-neck round bottom flask equipped with nitrogen injector unit 29.8g of toluene, iso-octane ol 44.8g, 25.6g of isobutanol, triethyl amine 0.62g into heat, stirring P 2 S 5 36.3g slowly inject temperature Is maintained at 80 ° C. After reacting for 1 hour, the temperature was lowered to synthesize dialkyldithiophosphoric acid from which unreacted P 2 S 5 was removed, and 14.0 g of ZnO was slowly added thereto, followed by reaction for 1 hour while maintaining the temperature at 60 ° C. After completion of the reaction, 6.0 g of lubricating base oil was added to the mixture to dilute it. Then, unreacted solids were removed, N 2 gas was injected, distilled H 2 O and unreacted alcohol were distilled off to give a pale yellow product of dialkyldithiophosphate zinc salt. Got it. Yield 91%.
분석결과는 다음과 같다.The analysis results are as follows.
동점도(100℃)12.73 cSt, P 8.8%, S 17.6%, Zn 9.1%이었다.Kinematic viscosity (100 ° C.) was 12.73 cSt, P 8.8%, S 17.6%, Zn 9.1%.
[실시예 2]Example 2
환류냉각기와 질소주입기를 3구 둥근바닥 플라스크에 톨루엔 29.8g, 이소옥탄올 44.8g, 이소부탄올 25.6g을 넣고 가열, 교반하면서 P2S536.3g을 서서히 주입하여 온도를 80℃로 유지한다.3시간동안 반응한 다음 온도를 내려 미반응의 P2S5를 제거한 디알킬디티오인산을 합성하고 여기에 ZnO 14.Og을 서서히 주입하여 온도를 60℃로 유지하면서 1시간정도 반응시킨다. 반응완료후 윤활기유 6.0g을 가하여 희석한 다음 미반응의 고형물을 제거하고 N2개스를 주입하여 생성된 H2O과 미반응의 알콜을 증류하여 엷은 노란색의 생성물인 디알킬디티오인산아연염을 얻었다. 수율은 1시간 반응하였을때에는 78.3%이었고, 3시간에는 85%이었다.A reflux condenser and nitrogen injector were charged with 29.8 g of toluene, 44.8 g of isooctanol, and 25.6 g of isobutanol in a three-necked round bottom flask, followed by heating and stirring to gradually inject 36.3 g of P 2 S 5 to maintain the temperature at 80 ° C. After reacting for a period of time, the temperature was lowered to synthesize dialkyldithiophosphoric acid from which unreacted P 2 S 5 was removed, and then ZnO 14.Og was slowly added thereto, followed by reaction for about 1 hour while maintaining the temperature at 60 ° C. After completion of the reaction, 6.0 g of lubricating base oil was added to the mixture to dilute it. Then, unreacted solids were removed, N 2 gas was injected, distilled H 2 O and unreacted alcohol were distilled off to give a pale yellow product of dialkyldithiophosphate zinc salt. Got it. The yield was 78.3% when reacted for 1 hour, 85% at 3 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019870015468A KR900004216B1 (en) | 1987-12-30 | 1987-12-30 | Preparation method for zinc salts dithio phosphoric acids |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019870015468A KR900004216B1 (en) | 1987-12-30 | 1987-12-30 | Preparation method for zinc salts dithio phosphoric acids |
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| Publication Number | Publication Date |
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| KR900004216B1 true KR900004216B1 (en) | 1990-06-18 |
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| KR890009949A (en) | 1989-08-05 |
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