KR101827503B1 - Dicarboxylic acid derivatives containing dialkyldithiophosphate group and antiwear additives and lubricant compositions comprising the same - Google Patents
Dicarboxylic acid derivatives containing dialkyldithiophosphate group and antiwear additives and lubricant compositions comprising the same Download PDFInfo
- Publication number
- KR101827503B1 KR101827503B1 KR1020160035450A KR20160035450A KR101827503B1 KR 101827503 B1 KR101827503 B1 KR 101827503B1 KR 1020160035450 A KR1020160035450 A KR 1020160035450A KR 20160035450 A KR20160035450 A KR 20160035450A KR 101827503 B1 KR101827503 B1 KR 101827503B1
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- South Korea
- Prior art keywords
- oil
- formula
- compound represented
- lubricating oil
- present
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000000314 lubricant Substances 0.000 title abstract description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 title abstract description 4
- 239000007866 anti-wear additive Substances 0.000 title 1
- 239000010687 lubricating oil Substances 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- -1 dicarboxylic acid derivative compound Chemical class 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 101
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000002199 base oil Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 abstract description 48
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 16
- 239000000654 additive Substances 0.000 abstract description 11
- 230000000996 additive effect Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 7
- 239000010725 compressor oil Substances 0.000 abstract description 5
- 239000010730 cutting oil Substances 0.000 abstract description 5
- 239000010723 turbine oil Substances 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- DXECDJILNIXBML-UHFFFAOYSA-N bis(6-methylheptoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)CCCCCOP(S)(=S)OCCCCCC(C)C DXECDJILNIXBML-UHFFFAOYSA-N 0.000 description 11
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 5
- UQBPNKULKPVTMR-UHFFFAOYSA-N OS(O)=O.OS(O)=O.OS(O)=O.OS(O)=O.OS(O)=O.P Chemical compound OS(O)=O.OS(O)=O.OS(O)=O.OS(O)=O.OS(O)=O.P UQBPNKULKPVTMR-UHFFFAOYSA-N 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012208 gear oil Substances 0.000 description 3
- 239000003879 lubricant additive Substances 0.000 description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- XPRULOZMJZDZEF-UHFFFAOYSA-N dibutoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCOP(S)(=S)OCCCC XPRULOZMJZDZEF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- GXUZYWRVKRMDJC-UHFFFAOYSA-N dodecoxy-dodecylsulfanyl-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCOP(O)(=S)SCCCCCCCCCCCC GXUZYWRVKRMDJC-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- 150000004869 1,3,4-thiadiazoles Polymers 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- FMQXXHSBEMBFIM-UHFFFAOYSA-N C(CCCCC(=O)OCCC(OC(C(=C)C)=O)O)(=O)OCCC(OC(C(=C)C)=O)O Chemical compound C(CCCCC(=O)OCCC(OC(C(=C)C)=O)O)(=O)OCCC(OC(C(=C)C)=O)O FMQXXHSBEMBFIM-UHFFFAOYSA-N 0.000 description 1
- QWVUWEPWTZSQEU-UHFFFAOYSA-N CC=[O](NCCC=[O](=N)=N)=N Chemical compound CC=[O](NCCC=[O](=N)=N)=N QWVUWEPWTZSQEU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FHPXQPVECZXBGK-UHFFFAOYSA-N [Na].[Zn].[Na] Chemical compound [Na].[Zn].[Na] FHPXQPVECZXBGK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001509 aspartic acid derivatives Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- VUSXVXHHDLSLQJ-UHFFFAOYSA-N bis[3-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] undecanedioate Chemical compound C(CCCCCCCCCC(=O)OCCC(OC(C(=C)C)=O)O)(=O)OCCC(OC(C(=C)C)=O)O VUSXVXHHDLSLQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
-
- 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
- C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
-
- 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
- C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/16—Antiseptic; (micro) biocidal or bactericidal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/18—Anti-foaming property
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 및 이를 포함하는 내마모제 및 윤활제 조성물에 관한 것이다. 본 발명에 따른 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물을 포함하는 윤활유 조성물은 내마모성능이 종래 윤활유 조성물보다 우수할 뿐만 아니라, 종래 윤활유 조성물보다 적은 함량으로 사용하여도 보다 우수한 효과를 나타내고, 중금속을 사용하지 않아 친환경적이므로, 엔진유, 변속기용 윤활유, 기어-기름, 터빈유, 작동유, 냉동기유, 압축기유, 진공펌프유, 베어링유, 미끄럼면유, 작암유, 금속 절삭유, 소성가공유, 열처리유, 윤활유 또는 가공유의 첨가제로 유용하게 사용될 수 있다.The present invention relates to a dicarboxylic acid derivative containing a dialkyldithiophosphate group and a wear-resistant agent and a lubricant composition containing the same. The lubricating oil composition containing the dicarboxylic acid derivative compound containing a dialkyldithiophosphate group according to the present invention is superior in wear resistance performance to the conventional lubricating oil composition and has a superior effect even when it is used in a content lower than that of the conventional lubricating oil composition Oil, turbine oil, operating oil, refrigerator oil, compressor oil, vacuum pump oil, bearing oil, sliding oil, petroleum oil, metal cutting oil, petroleum oil, petroleum oil, and so on because it is eco-friendly because it does not use heavy metals. , Heat-treated oil, lubricating oil or processed oil additive.
Description
본 발명은 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 및 이를 포함하는 내마모제 및 윤활제 조성물에 관한 것이다.The present invention relates to a dicarboxylic acid derivative containing a dialkyldithiophosphate group and a wear-resistant agent and a lubricant composition containing the same.
내마모제는 윤활유에 포함되어 금속 표면에 필름을 형성하여 금속과 금속의 접촉에 의하여 생기는 마모를 방지함으로 내하중 능력을 발휘하는 첨가제이다. 금속과 금속의 접촉에 의해 생기는 마모를 줄임으로써 기계의 효율을 향상시키고 연료의 소비를 절감시키고 에너지를 줄이는 역할을 한다.An anti-wear agent is an additive exhibiting a load-bearing capacity by being contained in lubricating oil and forming a film on the metal surface to prevent wear caused by metal-metal contact. By reducing the wear caused by metal-to-metal contact, it improves machine efficiency, reduces fuel consumption and reduces energy.
최근 산업의 발전에 따라 정밀 기기나 각종 산업용 부품 등은 보다 가혹한 환경조건하에서 작동되도록 요구되고 있으며 이를 만족시키기 위해 기계들과 부품들에 사용되는 윤활제도 더 높은 성능이 요구되고 있다. BACKGROUND ART [0002] With the recent development of industry, precision instruments and various industrial parts are required to be operated under harsh environmental conditions, and lubricants used in machines and parts are required to have higher performance.
한편, 내마모성 향상을 위해 사용되는 내마모제는 금속 표면에서 필름을 형성하여 물리적 또는 화학적인 기능을 하기 때문에, 첨가제에 함유되어 있는 화학적 구조와 원소에 따라 내마모제로의 기능을 발휘하여 금속과의 마찰로 인하여 발생하는 에너지를 현저하게 절감하여 효과적이고 상용성이 우수한 내마모성을 나타낸다. 기존 내마모제의 경우 아연, 몰리브덴과 같은 중금속이 함유되어 있다. 이러한 중금속이 함유된 내마모제는 사용 중에 누유되어 토양 또는 해양의 중금속 함유량이 증가되며 이로 인하여 환경오염이 발생하고, 동식물, 나아가 인간에게까지 악영향을 미칠 수 있다. On the other hand, since the wear-resistant agent used for improving the abrasion resistance functions as a physical or chemical function by forming a film on the metal surface, it functions as an anti-wear agent according to the chemical structure and elements contained in the additive, The energy generated is remarkably reduced and exhibits excellent wear resistance and excellent compatibility. Existing wear resistance agents contain heavy metals such as zinc and molybdenum. Such heavy metal-containing abrasion resistance agents are leaked during use to increase the content of heavy metals in the soil or the ocean, thereby causing environmental pollution, adverse effects on animals, animals and even humans.
이에, 중금속의 함량을 줄이거나, 중금속이 함유되지 않은 내마모제의 개발이 절실히 요구되고 있다. Accordingly, it is urgently required to reduce the content of heavy metals or to develop wear resistant agents free of heavy metals.
중금속의 함량을 감소시킨 내마모제에 대한 연구가 수행되고 있는데, 구체적으로, 미국의 모빌 오일사의 다기능성 디멀캅토티아디아졸에서 파생된 유기 에스테르, 아마이드와 아민 염(미국등록특허 제 4,908,144호), 다기능성 첨가제 (미국등록특허 5,205,945), 항산화, 내마모성을 가진 다기능성 4차 암모늄 염 유래 티아디아졸 첨가제(미국등록특허 5,126,397), 연료와 윤활제를 위한 다기능성 분산제 (미국등록특허 5,160,649)등이 멀캅토티아디아졸 유도체나 암모늄 염을 사용하여 기유 중 중금속의 함유량을 낮추었다. Research has been conducted on a wear resistant agent having a reduced content of heavy metals, specifically, organic esters, amides, and amine salts (U.S. Patent No. 4,908,144) derived from multifunctional dimercaptothiadiazole of Mobil Oil of America Functional additive (U.S. Pat. No. 5,205,945), antioxidant, multifunctional quaternary ammonium salt-derived thiadiazole additive with abrasion resistance (US Pat. No. 5,126,397), and multifunctional dispersant for fuel and lubricant (US Pat. No. 5,160,649) The content of heavy metals in the base oil was lowered by using a diazole derivative or an ammonium salt.
또한, 아실레이트나 에스테르 화합물을 이용한 발명으로서, 엑손사의 윤활유를 위한 다기능성 첨가제(미국등록특허 4,978,464), 생분해가 가능한 무독성 기어 오일(미국등록특허 6,649,574), 미국 셰브론 화학사의 엔진 오일과 첨가제의 조성 (미국등록특허 5,596,450), 노르웨이의 킹산업사의 부식방지를 위한 아실-하이드로카보닐알킬 아스파틱산 에스테르(미국등록특허 5,527,749), 미국 텍사코사의 모노 혹은 비스 숙신이미드 아실레이트 마니쉬 염기 윤활유 첨가제 (미국등록특허 5,102,570), 미국 에틸사의 아실레이트 물질과 아미노구아니딘 반응물로 구성된 무연 분산제(미국등록특허 5,496,480) 등으로 이러한 연구 역시 중금속의 함량을 줄인 연구로 보고된 바 있다.In addition, as an invention using an acylate or an ester compound, a multifunctional additive (US Pat. No. 4,978,464) for Exxon's lubricating oil, a non-toxic gear oil capable of biodegradation (US Pat. No. 6,649,574), an engine oil of Chevron Chemie (U.S. Pat. No. 5,596,450), acyl-hydrocarbonylalkyl aspartic acid esters (US Pat. No. 5,527,749) for the corrosion protection of King Industries, Norway, mono or bis-succinimide acylate mannish base lubricant additives (US Pat. No. 5,102,570), a lead-free dispersant consisting of an acylate material of ethyl ethyl silane and aminoguanidine reactant (U.S. Patent No. 5,496,480), and this research has also been reported to reduce the content of heavy metals.
나아가, 노르웨이 반더빌트사의 폴리알킬레이티드 1,3,4-티아디아졸과 이것이 함유된 윤활유 조성(미국등록특허 4,904,403), 미국 유리로열 화학사의 디티오카바메이트 유도체와 이를 포함한 윤활유(미국등록특허 5,686,397), 1,3,4-옥사디아졸 윤활유 첨가제(미국등록특허 6,566,311), 인피니움사의 몰리브덴이 없는 저휘발성의 윤활유 조성(미국등록특허 6,333,298), 디티오카바밀 카르복실릭산과 이것들을 사용한 다기능성 윤활유 첨가제(미국등록특허 5,789,357) 등 티아디아졸과 디티오카바메이트를 활용하여, 중금속의 함량을 낮추거나 함유되지 않은 윤활유 첨가제가 연구되고 있다.Further, polyalkylated 1,3,4-thiadiazoles of Vanderbilt, Norway and lubricating oil compositions containing them (U.S. Pat. No. 4,904,403), dithiocarbamate derivatives of the U. S. Royal Chemical and their lubricating oils 5,686,397), 1,3,4-oxadiazole lubricating oil additives (US 6,566,311), low-volatile lubricating oil compositions without molybdenum from Infinium (US Patent No. 6,333,298), dithiocarbamylcarboxylic acids and their use A lubricating oil additive having a low or no heavy metal content is being studied using thiadiazole and dithiocarbamates such as multifunctional lubricant additives (US Pat. No. 5,789,357).
그러나, 상기 연구에 의해 개발된 내마모제 또는 윤활유 첨가제는 몰리브덴, 아연과 같은 중금속의 함량을 낮췄을 뿐, 완전히 사용하지 않는 경우는 없다. 이에, 여전히 중금속으로 인한 환경오염을 유발할 가능성을 배제할 수 없고, 내마모성능이 기존의 내마모제보다 떨어지기 때문에 중금속을 포함하지 않으면서도 내마모성이 우수한 새로운 내마모제의 개발이 요구되고 있다.However, the wear-resistant agent or lubricant additive developed by the above-mentioned study has a low content of heavy metals such as molybdenum and zinc, and is not completely used. Therefore, the possibility of inducing environmental pollution due to heavy metals can not be excluded, and since the abrasion resistance performance is lower than that of conventional wear resistance agents, it is required to develop new wear resistance agents having excellent abrasion resistance without containing heavy metals.
이에, 본 발명자들은 중금속이 포함되지 않으면서 내마모성능이 우수한 물질을 개발하기 위하여 노력하던 중, 본 발명에 따른 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물을 포함하는 윤활유 조성물이 내마모성능이 종래 윤활유 조성물보다 우수할 뿐만 아니라, 종래 윤활유 조성물보다 적은 함량으로 사용하여도 보다 우수한 효과를 나타내고, 중금속을 사용하지 않아 친환경적이므로, 엔진유, 변속기용 윤활유, 기어-기름, 터빈유, 작동유, 냉동기유, 압축기유, 진공펌프유, 베어링유, 미끄럼면유, 작암유, 금속 절삭유, 소성가공유, 열처리유, 윤활유 또는 가공유의 첨가제로 유용하게 사용될 수 있다는 것을 알아내어 본 발명을 완성하였다.Accordingly, the present inventors have made efforts to develop a material having excellent abrasion resistance without heavy metals, and have found that a lubricating oil composition containing a dicarboxylic acid derivative containing a dialkyldithiophosphate group according to the present invention has excellent abrasion- The lubricating oil composition of the present invention is superior to the conventional lubricating oil composition and exhibits superior effects even when used in a content lower than that of the conventional lubricating oil composition and is eco-friendly because no heavy metal is used. The present invention has been accomplished on the basis of the finding that it can be usefully used as an additive for oil, compressor oil, vacuum pump oil, bearing oil, sliding oil, petroleum oil, metal cutting oil, calcined oil, heat treatment oil, lubricating oil or processing oil.
본 발명의 목적은 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물을 제공하는 것이다.It is an object of the present invention to provide a dicarboxylic acid derivative compound containing a dialkyldithiophosphate group.
본 발명의 다른 목적은 상기 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a process for producing a dicarboxylic acid derivative compound containing the dialkyldithiophosphate group.
본 발명의 또 다른 목적은 상기 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물을 포함하는 내마모제를 제공하는 것이다.It is still another object of the present invention to provide an antiwear agent comprising a dicarboxylic acid derivative compound containing the dialkyldithiophosphate group.
본 발명의 다른 목적은 상기 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물을 포함하는 윤활유 조성물을 제공하는 것이다.Another object of the present invention is to provide a lubricating oil composition comprising a dicarboxylic acid derivative compound containing the dialkyldithiophosphate group.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by the following formula (1): < EMI ID =
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
A는 단일결합이거나, 직쇄 또는 측쇄의 C1-18 알킬렌이고;A is a single bond or a straight or branched C 1-18 alkylene;
R1은 각각 독립적으로 동일 또는 상이한 직쇄 또는 측쇄의 C3-20 알킬이고;R < 1 > are each independently the same or different straight or branched C 3-20 alkyl;
R2는 각각 독립적으로 수소 또는 메틸이고;R 2 are each independently hydrogen or methyl;
R3은 각각 독립적으로 수소 또는 메톡시메틸이다.R 3 is hydrogen or methoxymethyl, each independently.
또한, 본 발명은 하기 반응식 1에 나타낸 바와 같이,Also, as shown in the following Reaction Scheme 1,
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계를 포함하는 상기 화학식 1로 표시되는 화합물의 제조방법을 제공한다:Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to obtain a compound represented by the formula (1): < EMI ID =
[반응식 1][Reaction Scheme 1]
(상기 반응식 1에서, (In the above Reaction Scheme 1,
R1, R2, R3 및 A는 상기 화학식 1에서 정의한 바와 같다).R 1 , R 2 , R 3 and A are the same as defined in the above formula (1)).
나아가, 본 발명은 하기 반응식 2에 나타낸 바와 같이,Further, the present invention provides a compound represented by the following formula (2)
화학식 1a으로 표시되는 화합물과 화학식 6으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계를 포함하는 상기 화학식 1로 표시되는 화합물의 제조방법을 제공한다:Reacting a compound represented by the formula (1a) with a compound represented by the formula (6) to obtain a compound represented by the formula (1): < EMI ID =
[반응식 2][Reaction Scheme 2]
(상기 반응식 2에서, (In the above Reaction Scheme 2,
R1, R2, R3 및 A는 상기 화학식 1에서 정의한 바와 같되, R3이 수소인 경우는 제외하고; R 1 , R 2 , R 3 and A are the same as defined in the above formula (1), except when R 3 is hydrogen;
X는 할로겐이고; 및 X is halogen; And
상기 화학식 1a로 표시되는 화합물은 R3이 수소인 상기 화학식 1로 표시되는 화합물의 유도체이다).The compound represented by the formula (1a) is a derivative of the compound represented by the formula (1) wherein R 3 is hydrogen.
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 내마모제를 제공한다.Also, the present invention provides an anti-wear agent comprising the compound represented by Formula 1 above.
나아가, 본 발명은 기유; 및 Further, the present invention relates to a base oil composition comprising a base oil; And
상기 기유 100 질량부에 대하여, 상기 화학식 1로 표시되는 화합물을 0.0001 내지 10 질량부로 포함하는 윤활유 조성물을 제공한다.Wherein the lubricating oil composition contains 0.0001 to 10 parts by mass of the compound represented by the general formula (1) based on 100 parts by mass of the base oil.
본 발명에 따른 디알킬 디티오포스페이트 그룹을 포함하는 디카르복실산 유도체 화합물을 포함하는 윤활유 조성물은 내마모성능이 종래 윤활유 조성물보다 우수할 뿐만 아니라, 종래 윤활유 조성물보다 적은 함량으로 사용하여도 보다 우수한 효과를 나타내고, 중금속을 사용하지 않아 친환경적이므로, 엔진유, 변속기용 윤활유, 기어-기름, 터빈유, 작동유, 냉동기유, 압축기유, 진공펌프유, 베어링유, 미끄럼면유, 작암유, 금속 절삭유, 소성가공유, 열처리유, 윤활유 또는 가공유의 첨가제로 유용하게 사용될 수 있다.The lubricating oil composition containing the dicarboxylic acid derivative compound containing a dialkyldithiophosphate group according to the present invention is superior in wear resistance performance to the conventional lubricating oil composition and has a superior effect even when it is used in a content lower than that of the conventional lubricating oil composition Oil, turbine oil, operating oil, refrigerator oil, compressor oil, vacuum pump oil, bearing oil, sliding oil, petroleum oil, metal cutting oil, petroleum oil, petroleum oil, and so on because it is eco-friendly because it does not use heavy metals. , Heat-treated oil, lubricating oil or processed oil additive.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
A는 단일결합이거나, 직쇄 또는 측쇄의 C1-18 알킬렌이고;A is a single bond or a straight or branched C 1-18 alkylene;
R1은 각각 독립적으로 동일 또는 상이한 직쇄 또는 측쇄의 C3-20 알킬이고;R < 1 > are each independently the same or different straight or branched C 3-20 alkyl;
R2는 각각 독립적으로 수소 또는 메틸이고;R 2 are each independently hydrogen or methyl;
R3은 각각 독립적으로 수소 또는 메톡시메틸이다.R 3 is hydrogen or methoxymethyl, each independently.
바람직하게는,Preferably,
상기 상기 A는 직쇄 또는 측쇄의 C4-11 알킬렌이고;Wherein A is a straight or branched C 4-11 alkylene;
R1은 동일한 직쇄 또는 측쇄의 C4-16 알킬이고;R 1 is C 4-16 alkyl of the same straight or branched chain;
R2는 각각 독립적으로 수소 또는 메틸이고; 및R 2 are each independently hydrogen or methyl; And
R3은 각각 독립적으로 수소 또는 메톡시메틸이다.R 3 is hydrogen or methoxymethyl, each independently.
보다 바람직하게는,More preferably,
상기 화학식 1로 표시되는 화합물은The compound represented by the formula (1)
비스[3-(3'-(디알킬옥시포스포로티오닐)티오-2'-메틸프로판오일옥시)-2-메톡시메틸옥시프로필] 알칸디오에트; 또는Bis [3- (3 '- (dialkyloxyphosphorothioyl) thio-2'-methylpropanoyloxy) -2-methoxymethyloxypropyl] alkanedioate; or
비스[3-(3'-(디알킬옥시포스포로티오닐)티오-2'-프로판오일옥시)-2-메톡시메틸옥시프로필] 알칸디오에트;이다.Bis [3- (3 '- (dialkyloxyphosphorothioyl) thio-2'-propanoyloxy) -2-methoxymethyloxypropyl] alkanedioate.
또한, 본 발명은 하기 반응식 1에 나타낸 바와 같이,Also, as shown in the following Reaction Scheme 1,
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계를 포함하는 상기 화학식 1로 표시되는 화합물의 제조방법을 제공한다:Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to obtain a compound represented by the formula (1): < EMI ID =
[반응식 1][Reaction Scheme 1]
상기 반응식 1에서, In the above Reaction Scheme 1,
R1, R2, R3 및 A는 상기 화학식 1에서 정의한 바와 같다.R 1 , R 2 , R < 3 > and A are as defined in the above formula (1).
이하, 본 발명에 따른 상기 화학식 1로 표시되는 화합물의 제조방법을 상세히 설명한다.Hereinafter, a method for preparing the compound represented by Formula 1 according to the present invention will be described in detail.
본 발명에 따른 상기 화학식 1로 표시되는 화합물의 제조방법에 있어서, 상기 제조방법은 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계이며, 구체적으로, 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 아민 존재하에 반응시켜 화학식 1로 표시되는 화합물을 제조하는 단계이다.In the process for preparing the compound represented by the formula (1) according to the present invention, the compound represented by the formula (2) is obtained by reacting the compound represented by the formula (2) with the compound represented by the formula , The compound represented by the formula (2) and the compound represented by the formula (3) are reacted in the presence of an amine to prepare a compound represented by the formula (1).
이때, 상기 아민으로는 특히 한정되는 것은 아니나, 트리에틸아민, 메틸디이소프로필아민, 에틸 디이소프로필 아민, 트리메틸 아민 등의 삼차아민류를 사용할 수 있다.At this time, the amine is not particularly limited, but tertiary amines such as triethylamine, methyldiisopropylamine, ethyldiisopropylamine and trimethylamine can be used.
또한, 상기 반응 온도는 특히 한정되는 것은 아니나, 50 내지 150 ℃에서 수행할 수 있다.The reaction temperature is not particularly limited, but can be carried out at 50 to 150 ° C.
나아가, 본 발명은 하기 반응식 2에 나타낸 바와 같이,Further, the present invention provides a compound represented by the following formula (2)
화학식 1a으로 표시되는 화합물과 화학식 6으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계를 포함하는 상기 화학식 1로 표시되는 화합물의 제조방법을 제공한다.There is provided a process for preparing a compound represented by the formula (1), which comprises reacting a compound represented by the formula (1a) with a compound represented by the formula (6) to obtain a compound represented by the formula (1).
[반응식 2][Reaction Scheme 2]
상기 반응식 2에서, In the above Reaction Scheme 2,
R1, R2, R3 및 A는 상기 화학식 1에서 정의한 바와 같되, R3이 수소인 경우는 제외하고; R 1 , R 2 , R 3 and A are the same as defined in the above formula (1), except when R 3 is hydrogen;
X는 할로겐이고; 및 X is halogen; And
상기 화학식 1a로 표시되는 화합물은 R3이 수소인 제1항의 화학식 1로 표시되는 화합물의 유도체이다.The compound represented by the formula (1a) is a derivative of the compound represented by the formula (1) wherein R 3 is hydrogen.
상기 반응식 2로 표시되는 제조방법은 화학식 1로 표시되는 화합물의 R3이 수소일 때, 하이드록시기에 치환기를 도입하고자 할 경우 사용할 수 있다.The production method represented by the reaction formula 2 can be used when R 3 of the compound represented by the formula (1) is hydrogen and a substituent is to be introduced into the hydroxyl group.
출발물질의 제조방법Preparation method of starting material
상기 반응식 1로 표시되는 화학식 1로 표시되는 화합물의 출발물질 화학식 2로 표시되는 화합물은, 특히 한정되는 것은 아니나, 하기 반응식 3에 나타낸 바와 같이,The compound represented by the general formula (2) as the starting material of the compound represented by the general formula (1) shown in the above Reaction Scheme 1 is not particularly limited, but as shown in the following Reaction Scheme 3,
화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 반응시켜 화학식 2a로 표시되는 화합물을 얻는 단계(단계 a); 및Reacting a compound represented by the formula (4) with a compound represented by the formula (5) to obtain a compound represented by the formula (2a) (step a); And
상기 단계 1에서 얻은 화학식 2a로 표시되는 화합물과 화학식 6으로 표시되는 화합물을 반응시켜 화학식 2로 표시되는 화합물을 얻는 단계(단계 b)를 포함하는 포함하는 제조방법에 의해 제조될 수 있다.Comprising the step of reacting the compound represented by the formula (2a) and the compound represented by the formula (6) obtained in the above step 1 to obtain the compound represented by the formula (2) (step b).
[반응식 3][Reaction Scheme 3]
상기 반응식 3에서, In Scheme 3,
R2, R3 및 n은 상기 화학식 1에서 정의한 바와 같되, R3이 수소인 경우는 제외하고; R 2 , R 3 and n are the same as defined in the above formula (1), except when R 3 is hydrogen;
X는 할로겐이고; 및X is halogen; And
상기 화학식 2a로 표시되는 화합물은 R3이 수소인 화학식 2로 표시되는 화합물의 유도체이다.The compound represented by the above formula (2a) is a derivative of the compound represented by the formula (2) wherein R 3 is hydrogen.
이하, 본 발명에 따른 상기 화학식 2로 표시되는 화합물의 제조방법에 대하여 상세히 설명한다.Hereinafter, a method of preparing the compound represented by Formula 2 according to the present invention will be described in detail.
본 발명에 따른 상기 화학식 2로 표시되는 제조방법에 있어서, 상기 단계 a는 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 반응시켜 화학식 2로 표시되는 화합물을 얻는 단계이며, 구체적으로, 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물이 염기 및 중합방지제 존재하에 고리 열림 반응을 통하여 화학식 2로 표시되는 화합물을 제조하는 단계이다.In the production method of the present invention represented by Chemical Formula 2, the step (a) is a step of reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 to obtain a compound represented by Chemical Formula 2, 4 and the compound represented by the general formula (5) are subjected to a ring opening reaction in the presence of a base and a polymerization inhibitor to prepare a compound represented by the general formula (2).
이때, 상기 염기로는 특히 한정되는 것은 아니나, 트리페닐포스핀, 트리부틸포스핀, 아민 염, 암모늄 염 등과 같은 루이스 염기를 사용할 수 있다.At this time, the base is not particularly limited, but Lewis bases such as triphenylphosphine, tributylphosphine, amine salts, and ammonium salts can be used.
또한, 상기 반응 온도는 특히 한정되는 것은 아니나, 50 내지 140 ℃에서 수행할 수 있다.The reaction temperature is not particularly limited, but it can be carried out at 50 to 140 캜.
또한, 상기 반응식 1로 표시되는 화학식 1로 표시되는 화합물의 출발물질 화학식 3으로 표시되는 화합물은, 특히 한정되는 것은 아니나, 하기 반응식 4에 나타낸 바와 같이,The compound represented by the general formula (3) as the starting material of the compound represented by the general formula (1) shown in the above Reaction Scheme 1 is not particularly limited, but as shown in the following Reaction Scheme 4,
화학식 7로 표시되는 포스포러스(V) 설파이드 화합물과 화학식 8로 표시되는 알콜 화합물을 반응시켜 화학식 3으로 표시되는 화합물을 얻는 단계를 포함하는 제조방법에 의해 제조될 수 있다.Reacting a phosphorus (V) sulfide compound represented by the formula (7) with an alcohol compound represented by the formula (8) to obtain a compound represented by the formula (3).
[반응식 4][Reaction Scheme 4]
상기 반응식 4에서,In Scheme 4,
R1은 상기 화학식 1에서 정의한 바와 같다.R 1 is the same as defined in the above formula (1).
또한, 본 발명은 하기 화학식 1로 표시되는 화합물을 포함하는 내마모제를 제공한다.The present invention also provides an antiwear agent comprising a compound represented by the following general formula (1).
나아가, 본 발명은 기유; 및 Further, the present invention relates to a base oil composition comprising a base oil; And
상기 기유 100 질량부에 대하여, 상기 화학식 1로 표시되는 화합물을 0.0001 내지 10 질량부로 포함하는 윤활유 조성물을 제공한다.Wherein the lubricating oil composition contains 0.0001 to 10 parts by mass of the compound represented by the general formula (1) based on 100 parts by mass of the base oil.
본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 내마모제 및 윤활유 조성물에 있어서, 상기 화학식 1로 표시되는 화합물의 디알킬 포스페이트의 알킬기는 직쇄 또는 측쇄의 C3- 20알킬인 것이 바람직하다. C3 미만의 알킬일 경우, 소수성기의 부족으로 인하여 기유와의 혼합이 잘 안되는 문제가 있고, C20 초과의 알킬일 경우 점도가 높아져 기어나 베어링 같은 부품들의 움직임을 방해할 수 있으며, 원료의 가격이 높아 경제성이 낮아지는 문제가 있다.And antiwear agent in lubricating oil compositions comprising a compound represented by the general formula (1) according to the present invention, di-alkyl group of the alkyl phosphate of the compound represented by Formula 1 is preferably a C 3- 20 alkyl of straight or branched chain. When the alkyl is less than C 3 , there is a problem that mixing with the base oil is difficult due to the shortage of the hydrophobic group. When the alkyl exceeds C 20 , the viscosity becomes high and it may interfere with the movement of parts such as gears and bearings. There is a problem that the economic efficiency is lowered.
또한, 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 내마모제 및 윤활유 조성물에 있어서, 상기 화학식 1로 표시되는 화합물의 디카르복실산의 링커(A)는 단일결합 또는 C1-18의 알킬렌일 수 있으며, 바람직하게는 C2-18의 알킬렌일 수 있고, 보다 바람직하게는 C4-11 알킬렌일 수 있다. C1 미만일 경우 내마모성이 낮아지는 문제가 있고, C18 초과의 알킬렌일 경우 점도가 높아지고, 원료의 단가가 높아 경제성이 낮은 문제가 있다.The linker (A) of the dicarboxylic acid of the compound represented by the formula (1) is a single bond or a C 1-18 alkylene And may preferably be C 2-18 alkylene, more preferably C 4-11 alkylene. If it is less than C 1 , there is a problem that the abrasion resistance is lowered. In the case of alkylene having a carbon number of more than 18 , viscosity is increased and the cost of raw material is high.
본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 윤활유 조성물에 있어서, 화학식 1로 표시되는 화합물의 함량 비율에 따른 내마모성능을 평가한 결과, 본 발명에 따른 화학식 1로 표시되는 화합물의 함량 비율이 커질수록 마모흔 직경이 감소하고, 동일한 함량(0.05%)으로 사용하였을 때, 통상적으로 사용되는 상업용 내마모제인 징크디피피(비교예 1)와 비교하여 마모흔의 직경이 0.2 mm 이상 현저하게 감소한 것을 확인하였으며, 비교예 1을 0.10 %로 두배로 사용하였을 경우보다도 마모흔 직경이 감소한 것을 알 수 있었다(실험예 1 및 표 1 참조).In the lubricating oil composition containing the compound represented by the formula (1) according to the present invention, the abrasion resistance performance according to the content ratio of the compound represented by the formula (1) was evaluated. As a result, the content ratio of the compound represented by the formula , The abrasion shrinkage diameter was decreased and the abrasion shrinkage diameter was remarkably decreased by 0.2 mm or more as compared with the zinc abrasion product (Comparative Example 1), which is a commonly used commercial abrasion resistance agent (0.05%) , And it was found that the abrasion loss diameter was reduced more than that in Comparative Example 1 which was used twice as much as 0.10% (see Experimental Example 1 and Table 1).
또한, 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 윤활유 조성물에 있어서 화학식 1로 표시되는 화합물의 구조에 따른 내마모성능을 확인하기 위하여, 화학식 1로 표시되는 화합물의 알킬렌 링커의 길이(A) 및 R1의 종류를 달리하여 내마모성능을 평가한 결과, In order to confirm the abrasion resistance performance of the compound represented by the formula (1) in the lubricating oil composition containing the compound represented by the formula (1) according to the present invention, the length of the alkylene linker of the compound represented by the formula ) And R 1 were different, and as a result,
본 발명에 따른 화학식 1로 표시되는 화합물은 디카르복실산의 알킬렌 링커의 길이가 증가할수록 마모성능이 증가하는 것을 알 수 있었으며(실험예 2-1 및 표 2 참조), 디알킬 포스페이트의 알킬기(본 발명에 따른 화학식 1의 R1)의 길이가 증가할수록 마모성능이 증가하는 것을 알 수 있었다(실험예 2-2 및 표 3 참조).It was found that the compound represented by the formula (1) according to the present invention had an increased wear performance as the length of the alkylene linker of the dicarboxylic acid was increased (see Experimental Example 2-1 and Table 2) (R 1 in the formula ( 1 ) according to the present invention), the abrasion performance was increased (see Experimental Examples 2-2 and 3).
따라서, 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 윤활유 조성물은 내마모성능이 종래 윤활유 조성물보다 우수할 뿐만 아니라, 종래 윤활유 조성물보다 적은 함량으로 사용하여도 보다 우수한 효과를 나타내고, 중금속을 사용하지 않아 친환경적이므로, 엔진유, 변속기용 윤활유, 기어-기름, 터빈유, 작동유, 냉동기유, 압축기유, 진공펌프유, 베어링유, 미끄럼면유, 작암유, 금속 절삭유, 소성가공유, 열처리유, 윤활유 또는 가공유의 첨가제로 유용하게 사용될 수 있다.Therefore, the lubricating oil composition containing the compound represented by the formula (1) according to the present invention is superior in wear resistance performance to the conventional lubricating oil composition, and exhibits superior effects even when used in a content lower than that of the conventional lubricating oil composition. It is eco-friendly, so it can be used for engine oil, transmission lubricant, gear oil, turbine oil, hydraulic oil, refrigerator oil, compressor oil, vacuum pump oil, bearing oil, sliding oil, lubricating oil, metal cutting oil, It can be usefully used as an oil additive.
이하, 본 발명의 실시예 및 실험예에 대해 상세히 설명한다.Hereinafter, examples and experimental examples of the present invention will be described in detail.
단, 하기 실시예 및 실험예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예 및 실험예에 한정되는 것은 아니다.However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.
<< 실시예Example 1> 1> 디이소옥틸Diisooctyl 디티오포스페이트Dithiophosphate 언데칸디오에이트Undecandioate 에스테르 (8-DP-10A-MOM)의 제조 Preparation of ester (8-DP-10A-MOM)
단계 1: Step 1: 비스Bis [[ 하이드록시Hydroxy 메타아크릴로릴옥시Methacrylolyloxy 프로필] profile] 언데칸디오에이트의Undecandioate 제조(A=C9) Preparation (A = C9)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 언데칸디오익 산 (151.4 g, 0.7 mol), 글라이시딜 메타아크릴레이트 (215.4 g, 1.5 mol), 트리페닐 포스파인 (3.7 g, 14 mmol), 메톡시 하이드로퀴논 (0.1 g, 1.1 mmol)을 반응기에 넣은 후 90 ℃로 3시간 동안 교반하였다. 반응액을 상온으로 냉각시킨 후 에틸아세테이트에 희석한 후 물로 2회 씻어준 뒤에 감압 증류하여 용매를 제거하여 검은색의 액체 (341.2 g, 99%) 를 얻었다.(151.4 g, 0.7 mol), glycidyl methacrylate (215.4 g, 1.5 mol), and triphenylphosphine (3.7 g, 0.03 mol) were placed in a three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath. , 14 mmol) and methoxyhydroquinone (0.1 g, 1.1 mmol) were placed in a reactor, followed by stirring at 90 ° C for 3 hours. The reaction solution was cooled to room temperature, diluted with ethyl acetate, washed twice with water, and then distilled under reduced pressure to remove the solvent to obtain a black liquid (341.2 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (t, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28 (m, 10H) 1 H NMR (300 MHz, CDCl 3): δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (m, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28
단계 2: Step 2: 디이소옥틸Diisooctyl 디티오포스페이트의Dithiophosphate 제조(R Manufacturing 1One == Ci8Ci8 ))
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 포스포러스 펜타설파이트 (112.2 g, 0.5 mol), 이소옥틸 알코올 (263.1 g, 2 mol)을 넣고 100 ℃에서 20 시간 동안 교반하여 초록색의 액체 (349.5g, 99%) 를 얻었다.After adding a thermometer, a condenser, a stirrer and an oil bath to a three-necked reactor, phosphorus pentasulfite (112.2 g, 0.5 mol) and isooctyl alcohol (263.1 g, 2 mol) were added and stirred at 100 ° C for 20 hours, Of a liquid (349.5 g, 99%).
단계 3: Step 3: 디이소옥틸Diisooctyl 디티오포스페이트Dithiophosphate 언데칸디오에이트Undecandioate 에스테르의 제조(R Preparation of ester (R 1One =Ci8, A=C9)= C18, A = C9)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 후, 단계 1의 비스[하이드록시 메타아크릴로릴옥시 프로필] 언데칸디오에이트 (5.1 g, 10 mmol), 단계 2의 디이소옥틸 디티오포스페이트 (7.5 g, 21 mmol), 트리에틸아민 (0.004 g, 0.04 mmol) 을 넣고 80 ℃에서 24 시간 교반 후 갈색의 액체를 얻었고, 반응용액의 일부 (5.0 g, 4 mmol) 를 취하여 4구 반응기로 옮겼다. 그 후, 온도계, 컨덴서, 적가 깔때기를 설치하고 메톡시메틸 클로라이드 2 M 톨루엔 용액 (8 ml, 16 mmol) 을 천천히 적가하여 준다. 적가 후 24 시간 동안 교반한 뒤에 반응용액을 에틸아세테이트에 희석한 후 물로 2회 씻어주고, 감압 증류를 하여 용매를 제거하여 연한 갈색의 용액 (5.2 g, 99%) 을 얻었다.After a thermometer, a condenser, a stirrer and an oil bath were installed in a three-necked reactor, bis (hydroxymethacrylolyloxypropyl) undecan diioate (5.1 g, 10 mmol) of step 1, diisooctyldithi A portion of the reaction solution (5.0 g, 4 mmol) was added to the solution and the resulting mixture was stirred at 80 ° C. for 24 hours to obtain a brown liquid. Lt; / RTI > Thereafter, a thermometer, a condenser and a dropping funnel are installed, and a methoxymethyl chloride 2 M toluene solution (8 ml, 16 mmol) is slowly added dropwise. After stirring for 24 hours, the reaction solution was diluted with ethyl acetate and washed twice with water. The solvent was distilled off under reduced pressure to obtain a pale brown solution (5.2 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 5.18-5.32 (m, 4H) 3.87-4.39 (m, 14H), 3.57-3.75 (m, 6H), 3.22-3.35 (m, 2H), 2.76-3.15 (m, 2H), 2.27-2.37 (m, 4H), 1.55-1.61 (m, 8H), 1.28-1.41 (m, 44H), 0.86-0.93 (m, 24H) 1 H NMR (300 MHz, CDCl 3 ):? 5.18-5.32 (m, 4H), 3.87-4.39 (m, 14H), 3.57-3.75 (m, 6H), 3.22-3.35 (m, 2H), 2.27-2.37 (m, 4H), 1.55-1.61 (m, 8H), 1.28-1.41 (m, 44H), 0.86-0.93
<< 실시예Example 2> 2> 디부틸Dibutyl 디티오포스페이트Dithiophosphate 언데칸디오에이트Undecandioate 에스테르(4-DP-10A-MOM)의 제조 Preparation of ester (4-DP-10A-MOM)
단계 1: Step 1: 비스Bis [[ 하이드록시Hydroxy 메타아크릴로릴옥시Methacrylolyloxy 프로필] profile] 언데칸디오에이트의Undecandioate 제조(A=C9) Preparation (A = C9)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 언데칸디오익 산 (151.4 g, 0.7 mol), 글라이시딜 메타아크릴레이트 (215.4 g, 1.5 mol), 트리페닐 포스파인 (3.7 g, 14 mmol), 메톡시 하이드로퀴논 (0.1 g, 1.1 mmol)을 반응기에 넣은 후 90 ℃로 3시간 동안 교반하였다. 반응액을 상온으로 냉각시킨 후 에틸아세테이트에 희석한 후 물로 2회 씻어준 뒤에 감압 증류하여 용매를 제거하여 검은색의 액체 (341.2 g, 99%) 를 얻었다.(151.4 g, 0.7 mol), glycidyl methacrylate (215.4 g, 1.5 mol), and triphenylphosphine (3.7 g, 0.7 mol) were placed in a three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath. , 14 mmol) and methoxyhydroquinone (0.1 g, 1.1 mmol) were placed in a reactor, followed by stirring at 90 ° C for 3 hours. The reaction solution was cooled to room temperature, diluted with ethyl acetate, washed twice with water, and then distilled under reduced pressure to remove the solvent to obtain a black liquid (341.2 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (t, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28 (m, 10H) 1 H NMR (300 MHz, CDCl 3): δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (m, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28
단계 2: Step 2: 디부틸Dibutyl 디티오포스페이트의Dithiophosphate 제조(R Manufacturing 1One =C4)= C4)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 포스포러스 펜타설파이트 (112.2 g, 0.5 mol), 부틸 알코올 (149.7 g, 2 mol)을 넣고 100 ℃에서 20 시간 동안 교반하여 초록색의 액체 (241.9g, 99%) 를 얻었다.After adding a phosphorus pentasulfite (112.2 g, 0.5 mol) and butyl alcohol (149.7 g, 2 mol) to a three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath, the mixture was stirred at 100 ° C for 20 hours, A liquid (241.9 g, 99%) was obtained.
단계 3: Step 3: 디부틸Dibutyl 디티오포스페이트Dithiophosphate 언데칸디오에이트Undecandioate 에스테르의 제조(R Preparation of ester (R 1One =C4, A=C9)= C4, A = C9)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 단계 1의 비스[하이드록시 메타아크릴로릴옥시 프로필) 언데칸디오에이트 (5.1 g, 10 mmol), 단계 2의 디부틸 디티오포스페이트 (5.1 g, 21 mmol), 트리에틸아민 (0.004 g, 0.04 mmol) 을 넣고 80 ℃에서 24 시간 교반 후 갈색의 액체를 얻었고, 반응용액의 일부 (4.1 g, 4 mmol) 를 취하여 4구 반응기로 옮겼다. 그 후, 온도계, 컨덴서, 적가 깔때기를 설치하고 메톡시메틸 클로라이드 2 M 톨루엔 용액 (8 ml, 16 mmol) 을 천천히 적가하여 준다. 적가 후 24 시간 동안 교반한 뒤에 반응용액을 에틸아세테이트에 희석한 후 물로 2회 씻어주고, 감압 증류를 하여 용매를 제거하여 연한 갈색의 용액 (4.3 g, 99%) 을 얻었다.A three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath was charged with bis (hydroxymethacrylyloxypropyl) undecanedioate (5.1 g, 10 mmol) of Step 1, dibutyldithiophosphate (5.1 g, 21 mmol) and triethylamine (0.004 g, 0.04 mmol) were added and the mixture was stirred at 80 ° C for 24 hours to obtain a brown liquid. A part of the reaction solution (4.1 g, 4 mmol) I moved. Thereafter, a thermometer, a condenser and a dropping funnel are installed, and a methoxymethyl chloride 2 M toluene solution (8 ml, 16 mmol) is slowly added dropwise. After stirring for 24 hours, the reaction solution was diluted with ethyl acetate and washed twice with water. The solvent was distilled off under reduced pressure to obtain a pale brown solution (4.3 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 5.18-5.32 (m, 4H) 3.95-4.44 (m, 14H), 3.63-3.76 (m, 6H), 2.85-3.22 (m, 8H), 2.27-2.37 (m, 2H), 1.58-1.73 (m, 12H), 1.26-1.45 (m, 26H), 0.91-0.97 (m, 12H) 1 H NMR (300 MHz, CDCl 3 ):? 5.18-5.32 (m, 4H) 3.95-4.44 (m, 14H), 3.63-3.76 (m, 6H), 2.85-3.22 (m, 2H), 1.58-1.73 (m, 12H), 1.26-1.45 (m, 26H), 0.91-0.97
<< 실시예Example 3> 3> 디도데실Didodecyl 디티오포스페이트Dithiophosphate 언데칸디오에이트Undecandioate 에스테르 (12-DP-10A-MOM)의 제조 Preparation of ester (12-DP-10A-MOM)
단계 1: Step 1: 비스Bis [[ 하이드록시Hydroxy 메타아크릴로릴옥시Methacrylolyloxy 프로필] profile] 언데칸디오에이트의Undecandioate 제조(A=C9) Preparation (A = C9)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 언데칸디오익 산 (151.4 g, 0.7 mol), 글라이시딜 메타아크릴레이트 (215.4 g, 1.5 mol), 트리페닐 포스파인 (3.7 g, 14 mmol), 메톡시 하이드로퀴논 (0.1 g, 1.1 mmol)을 반응기에 넣은 후 90 ℃로 3시간 동안 교반하였다. 반응액을 상온으로 냉각시킨 후 에틸아세테이트에 희석 한 후 물로 2회 씻어준 뒤에 감압 증류하여 용매를 제거하여 검은색의 액체 (341.2 g, 99%) 를 얻었다.(151.4 g, 0.7 mol), glycidyl methacrylate (215.4 g, 1.5 mol), and triphenylphosphine (3.7 g, 0.7 mol) were placed in a three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath. , 14 mmol) and methoxyhydroquinone (0.1 g, 1.1 mmol) were placed in a reactor, followed by stirring at 90 ° C for 3 hours. The reaction solution was cooled to room temperature, diluted with ethyl acetate, washed twice with water, and then distilled under reduced pressure to remove the solvent to obtain a black liquid (341.2 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (t, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28 (m, 10H) 1 H NMR (300 MHz, CDCl 3): δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (m, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28
단계 2: Step 2: 디도데실Didodecyl 디티오포스페이트의Dithiophosphate 제조(R Manufacturing 1One =C12)= C12)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 포스포러스 펜타설파이트 (112.2 g, 0.5 mol), 도데실 알코올 (376.4 g, 2 mol)을 넣고 100 ℃에서 20 시간 동안 교반하여 초록색의 액체 (470.3g, 99%) 를 얻었다.After adding a phosphorus pentasulfite (112.2 g, 0.5 mol) and dodecyl alcohol (376.4 g, 2 mol) to a three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath, Of a liquid (470.3 g, 99%).
단계 3: Step 3: 디도데실Didodecyl 디티오포스페이트Dithiophosphate 언데칸디오에이트Undecandioate 에스테르의 제조(R Preparation of ester (R 1One =C12, A=C9)= C12, A = C9)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 비스[하이드록시 메타아크릴로릴옥시 프로필] 언데칸디오에이트 (15.0 g, 30 mmol), 디도데실 디티오포스페이트 (29.6 g, 62 mmol), 트리에틸아민 (0.007 g, 0.07 mmol) 을 넣고 80 ℃에서 24 시간 교반 후 갈색의 액체를 얻었고, 반응용액의 일부 (5.7 g, 4 mmol) 를 취하여 4구 반응기로 옮겼다. 그 후, 온도계, 컨덴서, 적가 깔때기를 설치하고 메톡시메틸 클로라이드 2 M 톨루엔 용액 (8 ml, 16 mmol) 을 천천히 적가하여 준다. 적가 후 24 시간 동안 교반한 뒤에 반응용액을 에틸아세테이트에 희석한 후 물로 2회 씻어주고, 감압 증류를 하여 용매를 제거하여 연한 갈색의 용액 (5.9 g, 99%) 을 얻었다.After adding a thermometer, a condenser, a stirrer and an oil bath to a three-necked reactor, bis (hydroxymethacrylolyloxypropyl) undecanedioate (15.0 g, 30 mmol) and didodecyldithiophosphate (29.6 g, 62 mmol ) And triethylamine (0.007 g, 0.07 mmol) were added thereto, and the mixture was stirred at 80 ° C for 24 hours to obtain a brown liquid. A part of the reaction solution (5.7 g, 4 mmol) was taken and transferred to a four-necked reactor. Thereafter, a thermometer, a condenser and a dropping funnel are installed, and a methoxymethyl chloride 2 M toluene solution (8 ml, 16 mmol) is slowly added dropwise. After stirring for 24 hours, the reaction solution was diluted with ethyl acetate and washed twice with water. The solvent was distilled off under reduced pressure to obtain a pale brown solution (5.9 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 5.18-5.32 (m, 4H) 3.93-4.44 (m, 14H), 3.63-3.76 (m, 6H), 2.87-3.27 (m, 8H), 2.26-2.37 (m, 2H), 1.11-1.76 (m, 76H), 0.91-0.97 (m, 12H) 1 H NMR (300 MHz, CDCl 3 ):? 5.18-5.32 (m, 4H) 3.93-4.44 (m, 14H), 3.63-3.76 (m, 6H), 2.87-3.27 (m, 2H), 1.11-1.76 (m, 76H), 0.91-0.97 (m, 12H)
<< 실시예Example 4> 4> 디이소옥틸Diisooctyl 디티오포스페이트Dithiophosphate 헥산디오에이트Hexanedioate 에스테르 (8-DP-6A-MOM)의 제조 Preparation of ester (8-DP-6A-MOM)
단계 1: (1) Step 1: (1) 비스Bis [[ 하이드록시Hydroxy 메타아크릴로릴옥시Methacrylolyloxy 프로필] profile] 헥산디오에이트의Hexanedioate 제조(A=C4) Production (A = C4)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 헨산디오익 산 (102.3 g, 0.7 mol), 글라이시딜 메타아크릴레이트 (215.4 g, 1.5 mol), 트리페닐 포스파인 (3.7 g, 14 mmol), 메톡시 하이드로퀴논 (0.1 g, 1.1 mmol)을 반응기에 넣은 후 90 ℃로 3시간 동안 교반하였다. 반응액을 상온으로 냉각시킨 후 에틸아세테이트에 희석 한 후 물로 2회 씻어준 뒤에 감압 증류하여 용매를 제거하여 검은색의 액체 (296.4 g, 99%) 를 얻었다.After adding a thermometer, a condenser, a stirrer and an oil bath to a three-necked reactor, a solution of phenol dioic acid (102.3 g, 0.7 mol), glycidyl methacrylate (215.4 g, 1.5 mol), triphenylphosphine 14 mmol) and methoxyhydroquinone (0.1 g, 1.1 mmol) were placed in a reactor, followed by stirring at 90 ° C for 3 hours. The reaction solution was cooled to room temperature, diluted with ethyl acetate, washed twice with water and then distilled under reduced pressure to remove the solvent to obtain a black liquid (296.4 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (t, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.28-1.32 (m, 2H) 1 H NMR (300 MHz, CDCl 3): δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (m, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.28-1.32
단계 2: Step 2: 디이소옥틸Diisooctyl 디티오포스페이트의Dithiophosphate 제조(R Manufacturing 1One == Ci8Ci8 ))
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 포스포러스 펜타설파이트 (112.2 g, 0.5 mol), 이소옥틸 알코올 (263.1 g, 2 mol)을 넣고 100 에서 20 시간 동안 교반하여 초록색의 액체 (349.5g, 99%) 를 얻었다.After adding a thermometer, a condenser, a stirrer and an oil bath to a three-necked reactor, phosphorus pentasulfite (112.2 g, 0.5 mol) and isooctyl alcohol (263.1 g, 2 mol) were added and stirred at 100 for 20 hours to obtain a green A liquid (349.5 g, 99%) was obtained.
단계 3: Step 3: 디이소옥틸Diisooctyl 디티오포스페이트Dithiophosphate 헥산디오에이트Hexanedioate 에스테르의 제조(R Preparation of ester (R 1One =Ci8, A=C4)= C18, A = C4)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 비스[하이드록시 메타아크릴로릴옥시 프로필] 헥산디오에이트 (15.1 g, 35 mmol), 디이소옥틸 디티오포스페이트 (26.2 g, 72 mmol), 트리에틸아민 (0.007 g, 0.07 mmol) 을 넣고 80 ℃에서 24 시간 교반 후 갈색의 액체를 얻었고, 반응용액의 일부 (4.5 g, 4 mmol) 를 취하여 4구 반응기로 옮겼다. 그 후, 온도계, 컨덴서, 적가 깔때기를 설치하고 메톡시메틸 클로라이드 2 M 톨루엔 용액 (8 ml, 16 mmol) 을 천천히 적가하여 준다. 적가 후 24 시간 동안 교반한 뒤에 반응용액을 에틸아세테이트에 희석한 후 물로 2회 씻어주고, 감압 증류를 하여 용매를 제거하여 연한 갈색의 용액 (4.6 g, 97%) 을 얻었다.A thermometer, a condenser, a stirrer and an oil bath were placed in a three-necked reactor, and bis (hydroxy methacryloyloxypropyl) hexanedioate (15.1 g, 35 mmol) and diisooctyldithiophosphate (26.2 g, 72 mmol ), And triethylamine (0.007 g, 0.07 mmol) were added thereto. The mixture was stirred at 80 ° C for 24 hours to obtain a brown liquid, and a part of the reaction solution (4.5 g, 4 mmol) was transferred to a four-necked reactor. Thereafter, a thermometer, a condenser and a dropping funnel are installed, and a methoxymethyl chloride 2 M toluene solution (8 ml, 16 mmol) is slowly added dropwise. After stirring for 24 hours, the reaction solution was diluted with ethyl acetate and washed twice with water. The solvent was distilled off under reduced pressure to obtain a pale brown solution (4.6 g, 97%).
1H NMR (300 MHz, CDCl3) : δ 5.18-5.32 (m, 4H) 3.87-4.39 (m, 14H), 3.57-3.75 (m, 6H), 3.22-3.35 (m, 2H), 2.76-3.15 (m, 2H), 2.27-2.37 (m, 4H), 1.55-1.61 (m, 8H), 1.28-1.41 (m, 34H), 0.86-0.93 (m, 24H) 1 H NMR (300 MHz, CDCl 3 ):? 5.18-5.32 (m, 4H), 3.87-4.39 (m, 14H), 3.57-3.75 (m, 6H), 3.22-3.35 (m, 2H), 2.27-2.37 (m, 4H), 1.55-1.61 (m, 8H), 1.28-1.41 (m, 34H), 0.86-0.93
<< 실시예Example 5> 5> 디이소옥틸Diisooctyl 디티오포스페이트Dithiophosphate 도데실디오에이트Dodecyl diate 에스테르 (8-DP-12A-MOM) Ester (8-DP-12A-MOM)
단계 1: Step 1: 비스Bis [[ 하이드록시Hydroxy 메타아크릴로릴옥시Methacrylolyloxy 프로필] profile] 도데실디오에이트의Of dodecyl diate 제조(A=C10) Preparation (A = C10)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 도데실디오익 산 (156.8 g, 0.7 mol), 글라이시딜 메타아크릴레이트 (215.4 g, 1.5 mol), 트리페닐 포스파인 (3.7 g, 14 mmol), 메톡시 하이드로퀴논 (0.1 g, 1.1 mmol)을 반응기에 넣은 후 90 ℃로 3시간 동안 교반하였다. 반응액을 상온으로 냉각시킨 후 에틸아세테이트에 희석 한 후 물로 2회 씻어준 뒤에 감압 증류하여 용매를 제거하여 검은색의 액체 (351.5 g, 98%) 를 얻었다.(156.8 g, 0.7 mol), glycidyl methacrylate (215.4 g, 1.5 mol), and triphenylphosphine (3.7 g, 0.7 mol) were placed in a three-necked reactor equipped with a thermometer, condenser, , 14 mmol) and methoxyhydroquinone (0.1 g, 1.1 mmol) were placed in a reactor, followed by stirring at 90 ° C for 3 hours. The reaction solution was cooled to room temperature, diluted with ethyl acetate, washed twice with water and then distilled under reduced pressure to remove the solvent to obtain a black liquid (351.5 g, 98%).
1H NMR (300 MHz, CDCl3) : δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (t, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28 (m, 12H) 1 H NMR (300 MHz, CDCl 3): δ 6.11-6.17 (m, 2H) 5.59-5.62 (m, 2H), 3.98-4.51 (m, 8H), 3.75-3.78 (m, 2H), 2.32-2.37 (m, 4H), 1.93-1.97 (m, 6H), 1.58-1.62 (m, 4H), 1.23-1.28
단계 2: Step 2: 디이소옥틸Diisooctyl 디티오포스페이트의Dithiophosphate 제조(R Manufacturing 1One == Ci8Ci8 ))
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 포스포러스 펜타설파이트 (112.2 g, 0.5 mol), 이소옥틸 알코올 (263.1 g, 2 mol)을 넣고 100 에서 20 시간 동안 교반하여 초록색의 액체 (349.5g, 99%) 를 얻었다.After adding a thermometer, a condenser, a stirrer and an oil bath to a three-necked reactor, phosphorus pentasulfite (112.2 g, 0.5 mol) and isooctyl alcohol (263.1 g, 2 mol) were added and stirred at 100 for 20 hours to obtain a green A liquid (349.5 g, 99%) was obtained.
단계 2: Step 2: 디이소옥틸Diisooctyl 디티오포스페이트Dithiophosphate 도데실디오에이트Dodecyl diate 에스테르의 제조(R Preparation of ester (R 1One =Ci8, A=C10)= C18, A = C10)
3구 반응기에 온도계, 컨덴서, 교반기, 오일배스를 설치한 다음 비스[하이드록시 메타아크릴로릴옥시 프로필] 도데실디오에이트 (18.0 g, 35 mmol), 디이소옥틸 디티오포스페이트 (26.2 g, 72 mmol), 트리에틸아민 (0.007 g, 0.07 mmol) 을 넣고 80 ℃에서 24 시간 교반 후 갈색의 액체를 얻었고, 반응용액의 일부 (4.8 g, 4 mmol) 를 취하여 4구 반응기로 옮겼다. 그 후, 온도계, 컨덴서, 적가 깔때기를 설치하고 메톡시메틸 클로라이드 2 M 톨루엔 용액 (8 ml, 16 mmol) 을 천천히 적가하여 준다. 적가 후 24 시간 동안 교반한 뒤에 반응용액을 에틸아세테이트에 희석한 후 물로 2회 씻어주고, 감압 증류를 하여 용매를 제거하여 연한 갈색의 용액 (5.1 g, 99%) 을 얻었다.(18.0 g, 35 mmol), diisooctyldithiophosphate (26.2 g, 72 mmol) was added to a three-necked reactor equipped with a thermometer, a condenser, a stirrer and an oil bath, and then bis (hydroxy methacryloyloxypropyl) dodecyl di mmol) and triethylamine (0.007 g, 0.07 mmol) were added. The mixture was stirred at 80 ° C for 24 hours to obtain a brown liquid, and a portion (4.8 g, 4 mmol) of the reaction solution was transferred to a four-necked reactor. Thereafter, a thermometer, a condenser and a dropping funnel are installed, and a methoxymethyl chloride 2 M toluene solution (8 ml, 16 mmol) is slowly added dropwise. After stirring for 24 hours, the reaction solution was diluted with ethyl acetate and washed twice with water. The solvent was distilled off under reduced pressure to obtain a pale brown solution (5.1 g, 99%).
1H NMR (300 MHz, CDCl3) : δ 5.18-5.32 (m, 4H) 3.87-4.39 (m, 14H), 3.57-3.75 (m, 6H), 3.22-3.35 (m, 2H), 2.76-3.15 (m, 2H), 2.27-2.37 (m, 4H), 1.55-1.61 (m, 8H), 1.28-1.41 (m, 46H), 0.86-0.93 (m, 24H) 1 H NMR (300 MHz, CDCl 3 ):? 5.18-5.32 (m, 4H), 3.87-4.39 (m, 14H), 3.57-3.75 (m, 6H), 3.22-3.35 (m, 2H), 2.27-2.37 (m, 4H), 1.55-1.61 (m, 8H), 1.28-1.41 (m, 46H), 0.86-0.93
<< 비교예Comparative Example 1> 1> 징크디디피Jink didifie
상업용 내마모제인 징크디디피(ZDDPpulsTM사의 ZDDP plus)를 비교예로 사용하였다.A commercial abrasion resistance agent, Zinc Disodium (ZDDP plus from ZDDPpuls TM ), was used as a comparative example.
<실험예 1> 본 발명의 화합물 함량에 따른 윤활유 조성물의 내마모능 평가 EXPERIMENTAL EXAMPLE 1 Evaluation of abrasion resistance of a lubricant composition according to the compound content of the present invention
본 발명에 따른 실시예 화합물 함량에 따른 윤활유 조성물의 내마모성능을 보기 위하여 하기와 같은 실험을 수행하였다. 그 결과는 하기 표 1에 나타내었다.The following experiment was carried out in order to examine the abrasion resistance performance of the lubricant composition according to the compound contents of the examples according to the present invention. The results are shown in Table 1 below.
구체적으로, 실시예 1 에서 얻은 화합물 및 비교예 1을 광물유(150N BO)에 0.002~1% 첨가하여 4-볼 내마모 시험기(영국 Stannhope-seta사)를 이용하여, ASTM D4172법으로 마모시험을 평가하였다.Specifically, 0.001% to 1% of the compound obtained in Example 1 and Comparative Example 1 were added to mineral oil (150N BO), and the abrasion test was carried out using a 4-ball abrasion tester (Stannhope-seta, England) according to ASTM D4172 Respectively.
회전속도는 1200 ± 10 rpm, 테스트 온도는 75 ± 1.7 ℃, 하중은 40 kg 이며, 테스트 시간은 60 ± 1 분으로 하였다. 4-볼 내마모 시험이 완료된 후 3 개의 쇠 볼의 마모흔 직경을 측정하여 나타내었다.The rotation speed was 1200 ± 10 rpm, the test temperature was 75 ± 1.7 ° C, the load was 40 kg, and the test time was 60 ± 1 min. After the wear test of 4 balls was completed, the wear diameter of the three steel balls was measured and shown.
상기 표 1에 나타난 바와 같이, 본 발명에 따른 실시예 1의 함량 비율이 커질수록 마모흔 직경이 감소하고, 0.05 % 이상으로 사용하였을 때는 그 감소폭이 줄어드는 것을 알 수 있었다. As shown in Table 1, it can be seen that as the content ratio of Example 1 according to the present invention increases, the abrasion loss diameter decreases, and when the use amount is more than 0.05%, the decrease width decreases.
또한, 0.05 %로 동일한 함량을 사용하였을 때, 통상적으로 사용되는 상업용 내마모제인 징크디피피(비교예 1)와 비교하여 마모흔의 직경이 0.2 mm 이상 현저하게 감소한 것을 확인하였으며, 비교예 1을 0.10 %로 두배로 사용하였을 경우보다도 마모흔 직경이 감소한 것을 알 수 있었다.In addition, when the same content was used as 0.05%, it was confirmed that the diameter of the abrasion marks was remarkably decreased by 0.2 mm or more as compared with the zinc abrasive (Comparative Example 1), which is a commercially available abrasion resistance agent for commercial use, %, The abrasion radius was decreased.
따라서, 본 발명에 따른 상기 화학식 1로 표시되는 화합물을 포함하는 윤활유 조성물은 종래 사용되던 윤활유 조성물보다 내마모성능이 우수하며, 더 적은 양을 사용하여도 보다 우수한 효과를 나타내므로 윤활유 조성물로 유용하게 사용할 수 있다.Therefore, the lubricating oil composition containing the compound represented by the formula (1) according to the present invention has better abrasion resistance than the conventional lubricating oil composition and shows a superior effect even when used in a smaller amount, so that it can be effectively used as a lubricating oil composition have.
<실험예 2> 본 발명의 화합물 구조에 따른 윤활유 조성물의 내마모능 평가 < Experimental Example 2> Evaluation of abrasion resistance of lubricating oil composition according to the compound structure of the present invention
[화학식 1][Chemical Formula 1]
1) 상기 화학식 1에서 1) 디카르복실릭의Dicarboxylic 알킬렌 링커 길이(n의 수)에 따른 Depending on the alkylene linker length (number of n) 내마모능Abrasion resistance 평가 evaluation
본 발명에 따른 본 발명의 화학식 1로 표시되는 화합물의 디카르복실릭의 알킬렌 링커 길이에 따른 윤활유 조성물의 내마모능을 평가하기 위하여, 알킬렌 링커 길이를 제외하고 다른 치환기는 동일한 본 발명에 따른 실시예 1, 4 및 5에서 얻은 화합물을 광물유(150N BO)에 각각 0.05% 함량으로 첨가하여 4-볼 내마모 실험을 통해 내마모성능을 측정하여 그 결과를 하기 표 2에 나타내었다.In order to evaluate the abrasion resistance of the lubricating oil composition according to the length of the dicarboxylic alkylene linker of the compound represented by the formula (1) according to the present invention, other substituents other than the alkylene linker length are used in the same invention The compounds obtained in Examples 1, 4 and 5 were added to mineral oil (150N BO) in an amount of 0.05%, respectively, and the abrasion resistance performance was measured through the 4-ball wear test. The results are shown in Table 2 below.
상기 표 2에 나타난 바와 같이, As shown in Table 2,
본 발명에 따른 화학식 1로 표시되는 화합물은 디카르복실산의 알킬렌 링커의 길이가 증가할수록 내마모성능이 증가하는 것을 알 수 있었다.It was found that the abrasion resistance of the compound represented by the formula (1) according to the present invention increases as the length of the alkylene linker of the dicarboxylic acid increases.
2) 상기 화학식 1에서 2) 디알킬Dialkyl 포스페이트의Phosphate 알킬기(R Alkyl group (R 1One ) 종류에 따른 ) Depending on the type 내마모능Abrasion resistance 평가 evaluation
본 발명에 따른 본 발명의 화학식 1로 표시되는 화합물의 디알킬 포스페이트의 알킬기 종류에 따른 윤활유 조성물의 내마모능을 평가하기 위하여, 디알킬 포스페이트의 알킬기를 제외하고 다른 치환기는 동일한 실시예 1 내지 3에서 얻은 화합물을 광물유(150N BO)에 각각 0.05% 함량으로 첨가하여 4-볼 내마모 실험을 통해 내마모성능을 측정하여 그 결과를 하기 표 3에 나타내었다.In order to evaluate the abrasion resistance of the lubricating oil composition according to the kind of the alkyl group of the dialkyl phosphate of the compound represented by the formula (1) according to the present invention, other substituents except the alkyl group of the dialkyl phosphate are the same as those of the examples 1 to 3 Were added to mineral oil (150N BO) in an amount of 0.05%, respectively, and the abrasion resistance performance was measured through the 4-ball wear test. The results are shown in Table 3 below.
상기 표 3에 나타난 바와 같이, As shown in Table 3,
본 발명에 따른 화학식 1로 표시되는 화합물은 디알킬 포스페이트의 알킬기의 길이가 증가할수록 내마모성능이 증가하는 것을 알 수 있었다.The compound represented by the formula (1) according to the present invention has increased abrasion resistance as the alkyl group length of the dialkyl phosphate increases.
상기 실험 결과를 통하여, 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 윤활유 조성물은 내마모성능이 종래 윤활유 조성물보다 우수할 뿐만 아니라, 종래 윤활유 조성물보다 적은 함량으로 사용하여도 보다 우수한 효과를 나타내며, 디카르복실산 알킬렌 링커의 길이가 길수록, 디알킬 포스페이트의 알킬기의 길이가 증가할수록 내마모성능이 우수함을 알 수 있었다. The lubricating oil composition containing the compound represented by the formula (1) according to the present invention has superior abrasion resistance performance compared with the conventional lubricating oil composition, and exhibits superior effects even when used in a content lower than that of the conventional lubricating oil composition. It was found that the longer the length of the alkylene oxide linker and the length of the alkyl group of the dialkyl phosphate were, the better the abrasion resistance.
따라서, 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 윤활유 조성물은 내마모성능이 종래 윤활유 조성물보다 우수할 뿐만 아니라, 종래 윤활유 조성물보다 적은 함량으로 사용하여도 보다 우수한 효과를 나타내고, 중금속을 사용하지 않아 친환경적이므로, 엔진유, 변속기용 윤활유, 기어-기름, 터빈유, 작동유, 냉동기유, 압축기유, 진공펌프유, 베어링유, 미끄럼면유, 작암유, 금속 절삭유, 소성가공유, 열처리유, 윤활유 또는 가공유의 첨가제로 유용하게 사용될 수 있다.Therefore, the lubricating oil composition containing the compound represented by the formula (1) according to the present invention is superior in wear resistance performance to the conventional lubricating oil composition, and exhibits superior effects even when used in a content lower than that of the conventional lubricating oil composition. It is eco-friendly, so it can be used for engine oil, transmission lubricant, gear oil, turbine oil, hydraulic oil, refrigerator oil, compressor oil, vacuum pump oil, bearing oil, sliding oil, lubricating oil, metal cutting oil, It can be usefully used as an oil additive.
Claims (10)
비스[3-(3'-(디알킬옥시포스포로티오닐)티오-2'-프로판오일옥시)-2-메톡시메틸옥시프로필] 알칸디오에트;인 화합물이되,
상기 화합물명에서, 디알킬의 알킬은 직쇄 또는 측쇄의 C3-20 알킬이고,
알칸디오에트는 직쇄 또는 측쇄의 C1-18 알칸디오에트인 것을 특징으로 하는 화합물.
Bis [3- (3 '- (dialkyloxyphosphorothioyl) thio-2'-methylpropanoyloxy) -2-methoxymethyloxypropyl] alkanedioate; or
Bis [3- (3 '- (dialkyloxyphosphorothioyl) thio-2'-propanoyloxy) -2-methoxymethyloxypropyl] alkanedioate;
In the above compound names, the alkyl of the dialkyl is straight or branched C 3-20 alkyl,
Wherein the alkanedioate is a straight or branched C 1-18 alkanedioate.
화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계를 포함하는 제1항에 기재된 화합물의 제조방법:
[반응식 1]
(상기 반응식 1에서,
R1, R2, R3 및 A는 제1항에 기재된 어느 하나의 화합물에 의해서 정해진다).
As shown in Scheme 1 below,
A process for producing a compound according to claim 1, comprising the step of reacting a compound represented by formula (2) with a compound represented by formula (3) to obtain a compound represented by formula (1)
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
R 1 , R 2 , R 3 and A are defined by any one of the compounds according to claim 1).
화학식 1a으로 표시되는 화합물과 화학식 6으로 표시되는 화합물을 반응시켜 화학식 1로 표시되는 화합물을 얻는 단계를 포함하는 제1항에 기재된 화합물의 제조방법:
[반응식 2]
(상기 반응식 2에서,
R1, R2, R3 및 A는 제1항에 기재된 어느 하나의 화합물에 의해서 정해지고; 및
X는 할로겐이다).
As shown in Scheme 2 below,
A process for producing a compound according to claim 1, comprising the step of reacting a compound represented by formula (1a) with a compound represented by formula (6) to obtain a compound represented by formula (1)
[Reaction Scheme 2]
(In the above Reaction Scheme 2,
R 1 , R 2 , R 3 and A are defined by any one of the compounds according to claim 1; And
And X is halogen.
반응식 1의 화학식 2로 표시되는 화합물은 하기 반응식 3에 나타낸 바와 같이,
화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물을 반응시켜 화학식 2a로 표시되는 화합물을 얻는 단계(단계 a); 및
상기 단계 a에서 얻은 화학식 2a로 표시되는 화합물과 화학식 6으로 표시되는 화합물을 반응시켜 화학식 2로 표시되는 화합물을 얻는 단계(단계 b)를 포함하는 포함하는 제조방법에 의해 제조되는 것을 특징으로 하는 제조방법:
[반응식 3]
(상기 반응식 3에서,
R2, R3 및 A는 제1항에 기재된 어느 하나의 화합물에 의해서 정해지고; 및
X는 할로겐이다).
5. The method of claim 4,
The compound represented by the formula (2) in the reaction formula (1)
Reacting a compound represented by the formula (4) with a compound represented by the formula (5) to obtain a compound represented by the formula (2a) (step a); And
Comprising the step of reacting the compound represented by the formula (2a) and the compound represented by the formula (6) obtained in the step (a) to obtain the compound represented by the formula (2) (step b) Way:
[Reaction Scheme 3]
(In the above scheme 3,
R 2 , R 3 and A are defined by any one of the compounds according to claim 1; And
And X is halogen.
상기 반응식 1의 화학식 3으로 표시되는 화합물은 하기 반응식 4에 나타낸 바와 같이,
화학식 7로 표시되는 포스포러스(V) 설파이드 화합물과 화학식 8로 표시되는 알콜 화합물을 반응시켜 화학식 3으로 표시되는 화합물을 얻는 단계를 포함하는 제조방법에 의해 제조되는 것을 특징으로 하는 제조방법:
[반응식 4]
(상기 반응식 4에서,
R1은 제1항에 기재된 어느 하나의 화합물에 의해서 정해진다).
5. The method of claim 4,
The compound represented by the general formula (3)
Reacting a phosphorus (V) sulfide compound represented by the formula (7) with an alcohol compound represented by the formula (8) to obtain a compound represented by the formula (3)
[Reaction Scheme 4]
(In the above Scheme 4,
R < 1 > is defined by any one of the compounds according to claim 1).
An anti-wear agent comprising the compound of claim 1.
상기 기유 100 질량부에 대하여, 제1항의 화합물을 0.0001 내지 10 질량부로 포함하는 윤활유 조성물.
Base oil; And
Wherein the lubricating oil composition contains 0.0001 to 10 parts by mass of the compound of claim 1 based on 100 parts by mass of the base oil.
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| US20020151444A1 (en) * | 1992-06-02 | 2002-10-17 | Horst Zinke | Bisdithiophosphoric acid derivatives as lubricant additives |
| CN103951698A (en) | 2014-05-09 | 2014-07-30 | 中国化工橡胶株洲研究设计院 | O,O'-diene dithiophosphate and preparation method thereof |
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| US20020151444A1 (en) * | 1992-06-02 | 2002-10-17 | Horst Zinke | Bisdithiophosphoric acid derivatives as lubricant additives |
| CN103951698A (en) | 2014-05-09 | 2014-07-30 | 中国化工橡胶株洲研究设计院 | O,O'-diene dithiophosphate and preparation method thereof |
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