KR101933481B1 - Oil-soluble ferrocene derivatives and method for preparing the same - Google Patents
Oil-soluble ferrocene derivatives and method for preparing the same Download PDFInfo
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- KR101933481B1 KR101933481B1 KR1020150161363A KR20150161363A KR101933481B1 KR 101933481 B1 KR101933481 B1 KR 101933481B1 KR 1020150161363 A KR1020150161363 A KR 1020150161363A KR 20150161363 A KR20150161363 A KR 20150161363A KR 101933481 B1 KR101933481 B1 KR 101933481B1
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- South Korea
- Prior art keywords
- ferrocene
- oil
- present
- ferrocene derivative
- fuel
- Prior art date
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 31
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 26
- 239000002816 fuel additive Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000004927 clay Substances 0.000 claims description 16
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 14
- 229960002089 ferrous chloride Drugs 0.000 claims description 13
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 125000004450 alkenylene group Chemical group 0.000 claims description 9
- 125000004419 alkynylene group Chemical group 0.000 claims description 9
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 6
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- 229910052742 iron Inorganic materials 0.000 claims 2
- 239000000446 fuel Substances 0.000 abstract description 42
- 238000002485 combustion reaction Methods 0.000 abstract description 12
- -1 oxa Chemical group 0.000 description 18
- 239000000654 additive Substances 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 125000002971 oxazolyl group Chemical group 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 125000005561 phenanthryl group Chemical group 0.000 description 4
- 125000001725 pyrenyl group Chemical group 0.000 description 4
- 125000001113 thiadiazolyl group Chemical group 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000000335 thiazolyl group Chemical group 0.000 description 3
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 2
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- HLYOOCIMLHNMOG-UHFFFAOYSA-N cyclohexyl nitrate Chemical compound [O-][N+](=O)OC1CCCCC1 HLYOOCIMLHNMOG-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene 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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
-
- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The present invention relates to an oil-soluble ferrocene derivative having improved solubility, and further relates to a process for producing the oil-soluble ferrocene derivative and a use thereof. More specifically, the oil-soluble ferrocene derivative according to the present invention is excellent in miscibility and solubility with various fuels, and can improve the combustion efficiency and ignitability of the fuel.
Description
The present invention relates to an oil-soluble ferrocene derivative having improved solubility, and further relates to a process for producing the oil-soluble ferrocene derivative and a use thereof.
Ferrocene and its derivatives have conventionally been used as additives for various liquid fuels to promote combustion in the engine as well as open flame combustion. For example, Japanese Patent Publication No. 5001376 discloses a process for producing a liquid hydrocarbons in the presence of a fuel additive composition comprising an aromatic solvent, an aliphatic solvent, and / or a petroleum solvent, which is a liquid organic carrier which dissolves ferrocene and a derivative thereof, US 4389220 discloses a method of conditioning a diesel engine in which 20 to 30 ppm of ferrocene is added to the fuel to remove the carbonaceous deposits in the combustion chamber and the fuel consumption per distance traveled Is reduced by about 5%.
Japanese Patent No. 3599337 discloses an additive for a fuel oil for an internal combustion engine made of a heavy residual oil, wherein 1 to 100 ppm of ferrocene and its derivatives are directly added to the fuel without addition of other additives, The ferrocene and ferrocene derivatives used in the present invention have a problem that their solubility in aromatic solvents, aliphatic solvents and petroleum solvents is very low.
Generally, ferrocene is in a solid state, and its low solubility requires much effort to dissolve it. When the solid ferrocene is used as an additive for fuel, if the complete dissolution is not preceded, the fuel flow may be reduced to cause a problem in the operability of the fuel, and the desired combustion efficiency can not be improved.
As a result of continuous research to improve the problems of the prior art, the inventors of the present invention have developed an oil-soluble ferrocene derivative which can easily and stably dissolve or miscible the fuel, and can realize improved fuel combustion efficiency and ignition ability. The present invention has been accomplished to provide a fuel additive composition comprising an economical synthesis method thereof and an oil-soluble ferrocene derivative according to the present invention.
It is an object of the present invention to provide an oil-soluble ferrocene derivative having improved solubility, and further to provide a process for producing ferrocene, which is a raw material economically from crude dicyclopentadiene (crude DCPD) And a fuel additive composition containing the oil-soluble ferrocene derivative.
The present invention includes an oil-soluble ferrocene derivative represented by the following general formula (1).
[Chemical Formula 1]
[In the above formula (1)
Wherein L is a single bond, (C1-C30) alkylene, (C2-C30) alkenylene or (C3-C30) alkynylene;
Wherein R < 1 > is (C6-C30) aryl or (C3-C30) heteroaryl;
Each of R 2 to R 4 is independently hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl or (C 3 -C 30) alkynyl;
Wherein a is an integer of 1 to 3,
And b is an integer of 0 to 3.]
The L in the oil-soluble ferrocene derivative represented by Formula 1 according to an embodiment of the present invention may be a single bond, (C 1 -C 10) alkylene, (C 2 -C 10) alkenylene or (C 3 -C 10) alkynylene .
According to an embodiment of the present invention, R 1 of Formula 1 may be selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, Thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxa, thiazolyl, thiadiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxazolyl, Wherein R 1 is selected from the group consisting of pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, , Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolyl Ginyl, quinoxalinyl, carbazolyl, phenanthridinyl and benzodioxolyl, and the like. And preferably phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, And more preferably, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, and the like, but is not limited thereto.
The oil-soluble ferrocene derivative according to an embodiment of the present invention may be selected from the following structures.
The fuel additive composition according to an embodiment of the present invention may include from 0.01 to 5% by weight of iron (Fe) based on the total weight.
The present invention relates to a process for the production of an oil-soluble ferrocene derivative represented by the following general formula (1) by refluxing a compound represented by the following general formula (2) and ferrocene under a heterogeneous catalyst; ≪ RTI ID = 0.0 > ferrocene < / RTI >
(2)
[Chemical Formula 1]
[In the above formulas (1) and (2)
Wherein L is a single bond, (C1-C30) alkylene, (C2-C30) alkenylene or (C3-C30) alkynylene;
Wherein R < 1 > is (C6-C30) aryl or (C3-C30) heteroaryl;
Each of R 2 to R 4 is independently hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl or (C 3 -C 30) alkynyl;
Wherein a is an integer of 1 to 3,
And b is an integer of 0 to 3.]
The heterogeneous catalyst according to an embodiment of the present invention may be one or more selected from active clay (acidic clay), zeolite, activated carbon, diatomaceous earth, bentonite, alumina, silicalite, fly ash, It is preferable in terms of suppressing the self polymerization of the unsaturated bond and minimizing the side reaction.
The heterogeneous catalyst according to an embodiment of the present invention may be added in an amount of 35 to 100 parts by weight, preferably 35 to 80 parts by weight, more preferably 40 to 60 parts by weight, based on 100 parts by weight of ferrocene But it is not limited thereto.
The ferrocene according to an embodiment of the present invention may be produced by pyrolyzing dicyclopentadiene (DCPD) and distilling it to separate cyclopentadiene (CPD) into a mixture of anhydrous ferrous chloride (FeCl 2 ) and diethylamine , And the produced ferrocene can be purified by further extracting and adding an organic solvent. In this case, the organic solvent used in the extraction is not limited as long as the organic solvent in which the ferrocene capable of selectively extracting the ferrocene is dissolved in a high solubility is selected from benzene, acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, ethyl Ethyl acetate, dichloromethane, and the like.
In the process for producing an oil-soluble ferrocene derivative according to an embodiment of the present invention, the oil-soluble ferrocene derivative represented by Formula 1 may contain 5 to 25% by weight of iron (Fe) based on the total weight, May contain 5 to 18% by weight of iron (Fe), but is not limited thereto.
The oil-soluble ferrocene derivatives according to the present invention have excellent compatibility and solubility for various fuels as well as high thermal stability over a wide temperature range.
The oil-soluble ferrocene derivative according to the present invention is a process for producing an oil-soluble ferrocene derivative that can be synthesized from crude dicyclopentadiene (crude DCPD) obtained from a naphtha cracker by-product, And it has a desirable effect in terms of recycling waste.
Hereinafter, the oil-soluble ferrocene derivative according to the present invention, and further, the method for producing the oil-soluble ferrocene derivative and the use thereof will be described in detail. Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.
The object of the present invention is to improve the low solubility of known ferrocene and ferrocene derivatives as described above. The oil-soluble ferrocene derivatives according to the present invention have excellent compatibility and solubility with various fuels and have improved solubility It is possible to provide an additive for fuel containing a high level of iron (Fe). In addition, the oil-soluble ferrocene derivative according to the present invention can remarkably improve the combustion efficiency of the fuel due to the combustion effect of Fe.
At this time, the above-mentioned "fuel" includes light oil such as gasoline, heavy oil A, kerosene, light oil (diesel); Heavy oil; Heavy residues; lubricant; Waste oil; And a mixed oil thereof; And may include an emulsion fuel containing the fuel material.
That is, by using the oil-soluble ferrocene derivative according to the present invention, it is possible to improve the economy of the fuel, the power and the running performance, and the operation stability of the engine can be improved by using the fuel additive composition containing the same.
The oil-soluble ferrocene derivative according to the present invention may be represented by the following general formula (1).
[Chemical Formula 1]
[In the above formula (1)
Wherein L is a single bond, (C1-C30) alkylene, (C2-C30) alkenylene or (C3-C30) alkynylene;
Wherein R < 1 > is (C6-C30) aryl or (C3-C30) heteroaryl;
Each of R 2 to R 4 is independently hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl or (C 3 -C 30) alkynyl;
Wherein a is an integer of 1 to 3,
And b is an integer of 0 to 3.]
The oil-soluble ferrocene derivative according to the present invention is preferably such that L is a single bond, (C 1 -C 10) alkylene, (C 2 -C 10) alkenylene or (C 3 -C 10) alkynylene, % Or more, or as an oil-soluble ferrocene derivative in a liquid phase, is excellent in compatibility with the above-mentioned fuel.
In addition, the oil-soluble ferrocene derivative according to the present invention has excellent solubility and miscibility with fuel by having the specific substituent as described above, so that a high concentration of the ferrocene derivative can be added to the fuel, It is good to be able to optimize the sex.
That is, the oil-soluble ferrocene derivative according to the present invention, which can provide the additive composition for a high-level iron (Fe) containing fuel, can exhibit an excellent effect of providing fuel with a high fuel consumption.
The oil-soluble ferrocene derivatives according to the present invention are those wherein L is a single bond, (C 1 -C 10) alkylene, (C 2 -C 10) alkenylene or (C 3 -C 10) alkynylene and R 1 is Lt; / RTI > or-C20) heteroaryl. With such a substituent, the oil-soluble ferrocene derivative according to the present invention does not decrease in viscosity even at low temperatures and has improved solubility in fuel, and the fuel additive composition including the above-described oil-soluble ferrocene derivative provides excellent combustion efficiency .
In the oil-soluble ferrocene derivative according to an embodiment of the present invention, the sum of a and b representing the number of substituents may be an integer of 1 to 6, the solubility of the fuel may be appropriately controlled according to the number of substituents, Preferably, the total sum thereof is 1 to 4, more preferably 2 to 4.
According to an embodiment of the present invention, R 1 of the useful ferrocene derivative represented by Formula 1 may be phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, tri Wherein the substituents are selected from the group consisting of phenyl, tolyl, pyrrolyl, pyrenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluoranthenyl, furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, Wherein the heterocyclic ring is selected from the group consisting of oxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, Benzofuranyl, furanyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, , Quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenan Thienyl and benzodioxolyl, preferably phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, Naphthyl, biphenyl, terphenyl, anthryl, indenyl, and the like, but the present invention is not limited thereto.
The oil-soluble ferrocene derivative represented by Formula 1 according to an embodiment of the present invention may have the following structure, but is not limited thereto.
The fuel additive composition according to an embodiment of the present invention may contain 0.01 to 5% by weight of iron (Fe) based on the total weight, and the above-described oil-soluble ferrocene derivative according to the present invention has solubility and miscibility And thus it is possible to provide a high level of iron (Fe) to the fuel even in a small amount of use.
The oil-soluble ferrocene derivative according to one embodiment of the present invention is stable at a wide temperature range and also has excellent fluidity at a low temperature, and in the case of a fuel additive containing the same, it can have phase stability over a wide temperature range. At this time, the above-mentioned temperature range may be a temperature range of -40 to 90 占 폚. Having the phase stability within the above temperature range may mean that the oil-soluble ferrocene derivative according to the present invention is not precipitated or phase-separated. At this time, the liquid oil-soluble ferrocene derivative and the fuel additive composition containing the liquid according to the present invention have a viscosity ranging from 100 to 300 cps (centi-poise) in the temperature range described above, .
The present invention relates to a process for the production of an oil-soluble ferrocene derivative represented by the following general formula (1) by refluxing a compound represented by the following general formula (2) and ferrocene under a heterogeneous catalyst; To a process for producing an oil-soluble ferrocene derivative.
(2)
[Chemical Formula 1]
[In the above formulas (1) and (2)
Wherein L is a single bond, (C1-C30) alkylene, (C2-C30) alkenylene or (C3-C30) alkynylene;
Wherein R < 1 > is (C6-C30) aryl or (C3-C30) heteroaryl;
Each of R 2 to R 4 is independently hydrogen, (C 1 -C 30) alkyl, (C 2 -C 30) alkenyl or (C 3 -C 30) alkynyl;
Wherein a is an integer of 1 to 3,
And b is an integer of 0 to 3.]
The production process according to the present invention is preferable in that the reaction is carried out under solvent-free conditions in order to obtain a high-purity oil-soluble ferrocene derivative in a high yield, but if necessary, furthermore, a solvent such as benzene, acetone, tetrahydrofuran , Dimethylformamide, dimethylsulfoxide, ethyl acetate, dichloromethane and the like.
In the production process according to the present invention, the ferrocene is not only a purified ferrocene compound but also ferrocene synthesized from crude dicyclopentadiene (crude DCPD) obtained from a naphtha cracker by- it is of course possible to use ferrocene. That is, the process for producing an oil-soluble ferrocene derivative according to the present invention is advantageous from the viewpoint of recycling of wastes, and has an advantage that it is possible to synthesize an oil-soluble ferrocene derivative with low cost.
In the process for producing an oil-soluble ferrocene derivative according to an embodiment of the present invention, the ferrocene is obtained by pyrolyzing dicyclopentadiene (DCPD) and distilling it to separate cyclopentadiene (CPD) from anhydrous ferrous chloride 2 ) < / RTI > and diethylamine; . ≪ / RTI > By synthesizing ferrocene using the above-described production method, it is possible to provide ferrocene at a low cost, and it is possible to easily synthesize an oil-soluble ferrocene derivative without further purification.
Also, the ferrocene derivative represented by the formula (1) can be synthesized in one-pot by a reflux reaction with the compound represented by the formula (2) in the presence of a heterogeneous catalyst without further purification of the ferrocene.
That is, the process for producing an oil-soluble ferrocene derivative according to the present invention has an advantageous effect in terms of recycling waste, and is an economical method for synthesizing the oil-soluble ferrocene derivative represented by Formula 1 at a high yield with a low cost and simple method .
In the above-mentioned method of synthesizing ferrocene, the above-mentioned diethylamine is one of the base catalysts and exhibits excellent reactivity in comparison with a base catalyst having a pKa value of a similar level to obtain a higher yield from the purified cyclopentadiene (CPD) And ferrocene can be synthesized.
The cyclopentadiene (CPD) according to one embodiment of the present invention may be added in an amount of 1 to 10 molar equivalents, preferably 1 to 8 molar equivalents, based on 1 molar equivalent of anhydrous ferrous chloride (FeCl 2 ) Preferably 1.5 to 4 molar equivalents. At this time, the yield of ferrocene can be controlled according to the addition amount of the ferrous chloride (FeCl 2 ), and when added in the above range, it is possible to provide an economical synthesis method showing a total reaction yield of 75% or more.
In the process for producing an oil-soluble ferrocene derivative according to the present invention, the heterogeneous catalyst may be at least one selected from the group consisting of activated clay (acidic clay), zeolite, activated carbon, diatomaceous earth, bentonite, alumina, silicalite, (Acidic white clay), zeolite, activated carbon, diatomaceous earth or a mixture thereof, and more preferably an activated clay (acid clay) in terms of high yield of the oil-soluble ferrocene derivative under solventless conditions, , Zeolite, or mixtures thereof. Particularly, it is most preferable to contain an active clay (acidic clay) in order to suppress the self-polymerization of the unsaturated bond and to minimize the side reaction.
At this time, the heterogeneous catalyst according to an embodiment of the present invention may be added in an amount of 1 to 100 parts by weight based on 100 parts by weight of ferrocene, preferably 40 to 80 parts by weight, More preferably 40 to 60 parts by weight.
The present invention provides a fuel additive composition containing an oil-soluble ferrocene derivative represented by the above formula (1). The ferrocene derivative according to the present invention is excellent in compatibility and solubility with various fuels as described above, and can provide a fuel additive containing a high level of iron (Fe).
The fuel additive composition according to an embodiment of the present invention may be used in a fuel cell, such as a bio-fuel oil (biodiesel) or the above-mentioned middle distillate fuel and bio-fuel oil, in addition to the use in a middle distillate fuel of fossil, And additives of a fuel mixture of fuel oil (biodiesel).
The fuel additive composition according to an embodiment of the present invention may contain 0.01 to 5% by weight of iron (Fe) based on the total weight of the composition, and preferably 0.05 to 3 wt% %, More preferably 0.1 to 2 wt%.
The fuel additive composition according to an embodiment of the present invention may be added to the fuel in an amount of preferably 10 to 5000 ppm by weight, preferably 20 to 3000 ppm by weight, more preferably 100 to 1000 ppm by weight But is not limited thereto.
In addition, the oil-soluble ferrocene derivative according to an embodiment of the present invention is stable at a wide temperature range and also has good fluidity at a low temperature, and the additive for fuel including the additive not only has thermal stability, It is possible to improve the combustion efficiency desired over a wide temperature range.
It is to be understood that the fuel additive composition according to the present invention may further include conventional additives for further improving fuel efficiency or suppressing engine wear. Nonlimiting examples of such additives include but are not limited to detergent additives, carrier oils, low temperature flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants, , An antistatic agent, a metallocene, a metal deactivator, a dye and a solvent, and can provide the desired effect in any combination and ratio.
In the above-described fuel additive composition, the lubricity improving agent is one for improving the lubricity and friction of the fuel, and generally may be at least one selected from fatty acids, tall oil fatty acids and fatty acid esters, and the tall oil fatty acid is derived from fir or pine Specific examples of the above-mentioned lubricity improver include C14 to C20 fatty acids, C14 to C20 fatty acid esters, and C14 to C20 unsaturated monocarboxylic acid esters. But it is not limited to these.
In one embodiment of the present invention, the corrosion inhibitor may be a succinic acid ester, a fatty acid derivative of C14 to C20, an alcoholamine of C1 to C5, and the like. Examples of the de-emulsifying agent include tert-butylphenol ethoxylate or tert- But are not limited to, condensation products such as epoxylates, fatty acids, alkylphenols, ethylene oxide (EO), and propylene oxide (PO). Also, the above-mentioned diheter may be an alkoxylated phenol-formaldehyde condensate and the like. Specific examples thereof may include one or more selected from NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite), which are polyether-modified And specific examples thereof include, but are not limited to, one or more selected from TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
In the fuel additive composition according to an embodiment of the present invention, the cetane number improver may include at least one member selected from 2-ethylhexyl nitrate, cyclohexylnitrate, peroxide and di-tert-butyl peroxide Specific examples of the antioxidant include 2,6-di-tert-butyrenol, 6-di-tert-butyl-3-methylphenol and N, N'- Diamine, and the like, but is not limited thereto.
In the fuel additive composition according to an embodiment of the present invention, a specific example of the metal deactivator may be a salicylic acid derivative and N, N'-disalicylidene-1,2-propanediamine. Specific examples of the non-polar organic solvent for dissolving or diluting the ferrocene derivative according to the present invention for excellent handling include toluene, xylene, white spirit, products of the Royal Dutch / Shell Group (SHELLSOL) and EXXSOL (ExxonMobil) And a polar organic solvent. Specific examples thereof include C1-C4 alcohols and the like, but the present invention is not limited thereto.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Various modifications and variations are possible in light of the above teachings.
(Example 1)
Step 1.
4.0 g of anhydrous ferrous chloride (FeCl 2 ) was added to a 100 mL round-bottomed flask, and after replacing with nitrogen, 13.05 mL of diethylamine (4.0 molar equivalent based on ferrous chloride) was added and stirred. When anhydrous ferrous chloride was sufficiently dissolved in diethylamine (pKa = 11.02), 7.86 mL of CPD (2.5 molar equivalent based on ferrous chloride) cracked from DCPD was added and stirred for 6 hours at room temperature (23 DEG C) The reaction was carried out by additionally adding 6.5 mL of diethylamine (2.0 molar equivalents based on the ferrous chloride) due to the reduction of the solvent. After completion of the reaction for 6 hours, 1.5 L of hexane was added, and impurities other than the synthesized ferrocene dissolved in hexane were filtered out and hexane was removed by vacuum distillation to obtain an orange crystalline ferrocene (5.39 g, yield = 91.82%).
1 H-NMR (300 MHz, CDCl 3, ppm): δ 4.160 (s, 10H)
Step 2.
A reflux condenser and a mechanical stirrer were placed in a 100 mL round bottom plaque, and 8.40 g (3.0 molar equivalents based on the ferrocene) of styrene was added, and 5 g of the ferrocene prepared by the above production method without further purification, 2.5 g of DC-260H acid clay (Donghae Chemical Industry Co., Ltd.) catalyst (50 wt% based on ferrocene) was added, and the mixture was gradually heated to 145 캜 and reacted for 2 hours. After the completion of the reaction, the heat source was removed, and the mixture was immediately filtered in a hot state to remove the acidic white clay catalyst. Thus, an oil-soluble ferrocene derivative (5.79 g, yield = 78.24%) in the form of a liquid phase styrene group having a viscosity was obtained.
ICP (Fe content: 11.36%)
The oil-soluble ferrocene derivative synthesized in Example 1 is a liquid compound and has excellent compatibility with the various fuels described above. Therefore, a ferrocene derivative containing a high content of iron (Fe) can be easily used as a fuel additive composition You can. In particular, it was confirmed that the fuel had a solubility of 5% or more in fuel such as gasoline, heavy oil, kerosene, diesel oil and lubricating oil.
(Example 2)
In the same manner as in Example 1 except that 5.97 mL of CPD (1.9 molar equivalents with respect to ferrous chloride) was used in the synthesis of the ferrocene of Example 1 (Step 1), an oil-soluble ferrocene derivative (4.13 g, Yield = 86.40%).
(Example 3)
An oil-soluble ferrocene derivative (5.37 g, yield = 91.48%) was obtained in the same manner as in Example 1, except that 7.96 mL of CPD (3.0 molar equivalents relative to ferrous chloride) was used in the synthesis of the ferrocene of Example 1 (Step 1) ).
(Example 4)
The same procedure as in Example 1 was repeated except that 14.14 mL of CPD (4.5 molar equivalents relative to ferrous chloride) was used in the synthesis of the ferrocene of Example 1 (Step 1), and an oil-soluble ferrocene derivative (3.31 g, Yield = 69.25%).
(Comparative Example 1)
The same procedure as in Example 1 was repeated except that dipropylamine (pKa = 11.00) was used instead of diethylamine (pKa = 11.02) in the synthesis of the ferrocene of Example 1 (Step 1) (2.94 g, yield = 53.16%).
(Comparative Example 2)
The procedure of Example 1 was repeated except that dibutylamine (pKa = 11.25) was used in place of diethylamine (pKa = 11.02) in the ferrocene synthesis (Step 1) (2.96 g, yield = 53.53%).
(Comparative Example 3)
In the same manner as in Example 1, except that 30 wt% of DC-260H acidic white clay catalyst (1.5 g) was used in the synthesis of the oil-soluble ferrocene derivative of Example 1 (Step 2) (12.09 g (including polystyrene)) was obtained.
1 H-NMR (300 MHz, CDCl 3, ppm): Ferrocene; [delta] 4.160 (s, 10H), Polystyrene; ? 7.09-6.37 (m, aromatic protons),? 1.84-1.87 (b, 2H),? 1.596-1.240 (m, 1H)
Viscosity: 1100 cps (25 캜)
(Comparative Example 4)
In the same manner as in Example 1, except that 15 wt% of DC-260H acidic white clay catalyst (0.75 g) was added to the ferrocene reactant in the synthesis of the oil-soluble ferrocene derivative of Example 1, (11.42 g (including polystyrene)) was obtained.
1 H-NMR (300 MHz, CDCl 3, ppm): Ferrocene; [delta] 4.160 (s, 10H), Polystyrene; [delta] 7.162-6.391 (m, aromatic protons), [delta] 1.84-1.87 (b, 2H), [delta] 1.596-1.192
Viscosity: 2000 cps (25 캜)
As the amount of acidic white clay catalyst used in the synthesis of the oil-soluble ferrocene derivatives according to the present invention was reduced (Example 1: 50w% / Comparative Example 3: 30w% / Comparative Example 4: 15w%), reactivity of the reactants decreased, The amount adhered to the ferrocene was reduced, and in the high-temperature reaction, it was confirmed that styrene itself polymerized and polystyrene was formed. In addition, the amount of unreacted ferrocene was increased as the amount of catalyst decreased. In addition, it was confirmed that the oil-soluble ferrocene derivatives synthesized in Comparative Examples 3 and 4 had high viscosity and extremely low miscibility with fuel.
That is, when the amount of the catalyst is out of the range of the amount of the catalyst according to the present invention, the polymer is self-polymerized rather than introducing a substituent into the ferrocene to improve the viscosity of the product and difficult to obtain the desired useful ferrocene derivative. Solubility in various fuels is low and it is difficult to realize the desired effect in the present invention.
Therefore, by using the ferrocene produced by the production process according to the present invention, it is possible to synthesize a high-quality oil-soluble ferrocene derivative at a high yield, as well as to synthesize a crude dicyclopentadiene obtained from a naphtha cracker by- ; crude DCPD) can be recycled into an easy process, thus providing a more economical oil-soluble ferrocene derivative.
Claims (9)
[Chemical Formula 1]
[In the above formula (1)
Wherein L is a single bond, (C1-C10) alkylene, (C2-C10) alkenylene or (C3-C10) alkynylene ;
R1 is phenyl;
Each R2 and R3 is independently hydrogen or (C1-C30) alkyl ;
R4 is hydrogen;
Wherein a is an integer of 1 to 3,
B is an integer of 0 to 3,
a + b is 2 to 4; ]
Wherein the fuel additive composition comprises from 0.01 to 5% by weight of iron based on the total weight of the fuel additive composition.
(2)
[Chemical Formula 1]
[In the above formulas (1) and (2)
Wherein L is a single bond, (C1-C10) alkylene, (C2-C10) alkenylene or (C3-C10) alkynylene ;
R1 is phenyl;
Each R2 and R3 is independently hydrogen or (C1-C30) alkyl ;
R4 is hydrogen;
Wherein a is an integer of 1 to 3,
B is an integer of 0 to 3,
a + b is 2 to 4; ]
Wherein the heterogeneous catalyst is a mixture of activated clay (acidic clay), zeolite, activated carbon, diatomaceous earth, bentonite, alumina, silicalite, fly ash or mixtures thereof.
Wherein the ferrocene is produced by pyrolyzing dicyclopentadiene and distilling it to react the separated cyclopentadiene with a mixture of anhydrous ferrous chloride and diethylamine; ≪ / RTI > wherein the ferrocene derivative is prepared by a process comprising the steps of:
Wherein the ferrocene derivative represented by Formula 1 comprises 5 to 25% by weight of iron based on the total weight of the ferrocene derivative.
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