CN102653696A - Viscosity index improver and preparation method thereof - Google Patents
Viscosity index improver and preparation method thereof Download PDFInfo
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- CN102653696A CN102653696A CN2011100512400A CN201110051240A CN102653696A CN 102653696 A CN102653696 A CN 102653696A CN 2011100512400 A CN2011100512400 A CN 2011100512400A CN 201110051240 A CN201110051240 A CN 201110051240A CN 102653696 A CN102653696 A CN 102653696A
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- ethylene
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- viscosity index
- propylene copolymer
- index improver
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 229920001577 copolymer Polymers 0.000 claims abstract description 58
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 imidazoline compound Chemical class 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002199 base oil Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- 229920000768 polyamine Polymers 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000004291 polyenes Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 5
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000006017 1-propenyl group Chemical group 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 125000002960 margaryl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920013639 polyalphaolefin Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000002948 undecyl group Chemical group [H]C([*])([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])[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000006039 1-hexenyl group Chemical group 0.000 claims description 2
- 125000006023 1-pentenyl group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000004071 soot Substances 0.000 abstract description 13
- 125000002636 imidazolinyl group Chemical group 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000010705 motor oil Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 18
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 7
- 239000005642 Oleic acid Substances 0.000 description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000010710 diesel engine oil Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- AFSNIGFOSBGQOB-UHFFFAOYSA-N NCCC=1N(CCN1)CC1=CC=CC=C1 Chemical compound NCCC=1N(CCN1)CC1=CC=CC=C1 AFSNIGFOSBGQOB-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NFCPRRWCTNLGSN-UHFFFAOYSA-N 2-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NC1=CC=CC=C1 NFCPRRWCTNLGSN-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a viscosity index improver and a preparation method thereof, wherein the viscosity index improver comprises the following components in percentage by weight: 60 to 94.5 percent of base oil, 5 to 39.5 percent of ethylene-propylene copolymer and 0.5 to 10 percent of imidazoline compound; the preparation method comprises the following steps: grafting maleic anhydride on the ethylene-propylene copolymer by using a solution grafting method, and connecting an imidazoline group on the ethylene-propylene copolymer; imidazoline groups are connected on the ethylene-propylene copolymer through chemical reaction, so that the product has excellent soot dispersing performance and antirust performance, can meet the requirements of the current medium-high grade internal combustion engine oil, has strong operability of the preparation method, and is suitable for industrial large-scale production.
Description
Technical field
The present invention relates to a kind of method that has the multifunctional viscosity index improver of good distribution and rustless property and prepare viscosity index improver.
Background technology
Along with fuel oil late injection technology, the especially development of EGR Technology of turbocharging technology of diesel motor, the soot amount that in combustion processes, produces is increasing.If soot can not get effective dispersion, can cause oil viscosity to increase rapidly, reduce the life cycle of oil product significantly, not only increase use cost, also cause failure of engine components when serious.
In order to address the above problem, adopt viscosity index improver to realize disperseing the sooty purpose usually.Existing viscosity index improver is made up of with the polar group that is grafted on the main chain the high polymer main chain as matrix; Macromolecule matrix comprises ethylene-propylene copolymer, gathers (methyl) propenoate etc.; Like U.S. Pat 4089794 a kind of dispersion type ethylene-propylene copolymer viscosity index improver is disclosed, by obtaining through amination or esterification behind maleic anhydride and the ethylene-propylene copolymer generation solution graft copolymerization again.Used aminate of this patent or carboxylate comprise polyamine, polyvalent alcohol, hydramine or its mixture, and this product is used for lubricating oil, have the performance of controlling soot and greasy filth preferably.But raising along with the diesel engine oil specification; Requirement to the soot dispersing property also increases substantially; The decentralized viscosity index improver of mentioning among the US4089794 can not satisfy actual needs, and the ethylene-propylene copolymer with higher percentage of grafting could satisfy present request for utilization.But after bringing up to the maleic anhydride grafting ratio on the ethylene-propylene copolymer to a certain degree, with polyamine or polyol reaction crosslinking reaction takes place easily again, thereby cause product viscosity too high or lose flowability and can't use.U.S. Pat 6107257 discloses a kind of decentralized viscosity index improver; The compound that contains aromatic amines such as N-phenyl-phenylenediamine in the structure is as polar group; Polar group in order to the soot surface interacts; Nonpolar high polymer main chain then can provide powerful dissipation of ferees, and small soot particles can be suspended in the lubricating oil, is unlikely to assemble each other to form bigger particle.But aromatic amine type compound is virose material, in the process of producing and using, is prone to cause environmental pollution and health risk.
Summary of the invention
The object of the present invention is to provide a kind of method that has the viscosity index improver of excellent soot dispersing property and good rustless property and prepare viscosity index improver, utilize this method can the obtained performance good quality production.
The composition of viscosity index improver provided by the invention and content are by weight percentage:
Base oil 60%～94.5%, ethylene-propylene copolymer 5%～39.5%, imidazolinium compounds 0.5%～10%, wherein the general formula of imidazolinium compounds is:
R representes hydrogen, alkyl, alkenyl or aromatic base; N is 1-10.
Imidazolinium compounds and the oil motor soot molecule that produces that is in operation has stronger interaction.Imidazolinium compounds is connected on the ethylene-propylene copolymer through chemical reaction, and in diesel engine oil, adds this product and can suppress soot particles and reunite each other, avoid diesel engine oil in use viscosity increase rapidly, prolong the work-ing life of diesel engine oil.Simultaneously, good anti-rust properties can be provided, guarantee the normal operation of equipment.The ethylene-propylene copolymer too high levels can cause the too high operational difficulty of product viscosity, cross lowly then not to possess enough dispersing propertys, so its content is 5%～39.5%, is preferably 8%～30%, most preferably is 10%～20%.0.5%～10% imidazolinium compounds content is to guarantee that product disperses and the key of rustless property, is preferably 3%～6%.
Described alkyl is the alkyl with straight or branched of 1-20 carbon atom, comprising: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, sec.-butyl, amyl group, neo-pentyl, hexyl, heptyl, undecyl, tridecyl, pentadecyl, heptadecyl, nonadecyl.The alkyl that preferably has the straight or branched of 7-19 carbon atom especially preferably has the alkyl of 11-17 carbon atom, most preferably undecyl or heptadecyl.
Alkenyl is the alkenyl with straight or branched of 1-20 carbon atom, comprising: vinyl, 1-propenyl, 2-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 1-heptenyl, 7-hexadecylene base, 8-17 thiazolinyls.Be preferably vinyl, 1-propenyl, 7-hexadecylene base, 8-17 thiazolinyls, be preferably 7-hexadecylene base or 8-17 thiazolinyls especially.Most preferably be 8-17 thiazolinyls.
Aromatic base has the structure of being shown below, and wherein R1 representes the alkyl of hydrogen, hydroxyl or amino or 1-10 carbon atom.
The weight-average molecular weight of ethylene-propylene copolymer that the present invention uses between 000, is preferably 12,000～250,000 10,000～1,000, most preferably is 15,000～10,000,000.Ethylene content is 15%～85%, and propylene content is that the 85%～15%, the 3rd monomer comprises ENB, hexadiene etc., and its content is 0～5%.Ethylene content is preferably 35～65%, most preferably is 45%～55%.
The preparation method of viscosity index improver provided by the present invention carries out according to the following steps:
1. utilize solution grafting grafted maleic anhydride on ethylene-propylene copolymer, solution grafting solvent for use content is 60%～95%, and solvent species comprises I or II or III class base oil and polyalphaolefin or other organic solvents.Above-mentioned other organic solvents comprise alkylnaphthalene or chlorobenzene or orthodichlorobenzene or Meta Dichlorobenzene or santochlor or toluene or o-Xylol or p-Xylol or m-xylene etc., and the method with underpressure distillation after graft reaction finishes removes.The content of ethylene-propylene copolymer is 5%～39.5%, is preferably 8%～30%, most preferably is 10%～20%.The used initiator of grafting comprises peroxidized t-butyl perbenzoate or Lucidol or 2,5-dimethyl--2, and 5-bis(t-butylperoxy) hexane or Di Cumyl Peroxide 99 etc., dosage is 0.05%～2%.The dosage of maleic anhydride is 0.2～3%.The grafting temperature is 150 ℃～200 ℃.3～6 hours graft reaction time.After reaction finishes, remove unreacted maleic anhydride, finally obtain the ethylene-propylene copolymer intermediate product of maleic anhydride graft with nitrogen injection or vacuum extraction.
2. imidazoline group is connected on the ethylene-propylene copolymer; Method A is: at first; Adopt the synthetic imidazolinium compounds of organic acid and polyethylene polyamine reaction; The weight ratio of organic acid and polyamines polyene is 1: 1～1.5, is that benchmark adds 10%～40% azeotropic agent and can make reaction carry out more thoroughly with the gross weight of organic acid and polyamines polyene, and azeotropic agent comprises toluene, YLENE.Under 100 ℃ temperature, slowly splash into organic acid in the polyamines polyene; Dropwise the back and add azeotropic agent; After being warmed up to 220 ℃ continuously slowly from 100 ℃, about 4 hours of temperature-rise period, reach 220 ℃ after isothermal reaction 2 hours again; Vacuum is removed raw material and the azeotropic agent that has neither part nor lot in reaction, obtains imidazolinium compounds.The general formula of polyethylene polyamine is: H
2N (CH
2CH
2NH)
N+1H, n are 1,2,3......10, are preferably 1,2,3,4, most preferably are 1 and 2.R representes hydrogen or alkyl or alkenyl or aromatic base.Reaction formula is following:
Then, with the ethylene-propylene copolymer and the imidazolinium compounds reaction of maleic anhydride graft, temperature of reaction is 80 ℃～220 ℃, is preferably 120 ℃～200 ℃, most preferably is 140 ℃～180 ℃, and the reaction times is 4～8 hours, obtains multifunctional viscosity index improver.
Perhaps method B is: directly on the ethylene-propylene copolymer of maleic anhydride graft, introduce imidazoline group, with the ethylene-propylene copolymer and the polyethylene polyamine reaction of maleic anhydride graft, the general formula of polyethylene polyamine is H earlier
2N (CH
2CH
2NH)
N+1H, n are 1,2,3......10, are preferably 1,2,3,4, most preferably are 1 and 2.The dosage of polyamines polyene is 0.5～5%.Temperature of reaction is 80 ℃～220 ℃, is preferably 120 ℃～200 ℃, most preferably is 140 ℃～180 ℃.Reaction times is 4～8 hours, obtains intermediate product.Again above-mentioned reaction product and organic acid are reacted organic acid by adding with 1: 1 mol ratio of polyamines polyene, the organic acid general formula is: R-COOH, R represent hydrogen or alkyl or alkenyl or aromatic base.Temperature of reaction is from 100 ℃～250 ℃, is warmed up to continuously slowly about 220 ℃ from 100 ℃ usually, and temperature-rise period is about 4 hours.After finishing, reaction can obtain multifunctional viscosity index improver.
Characteristics of the present invention are: on ethylene-propylene copolymer, connect imidazoline group through chemical reaction, make product have excellent soot dispersing property and rustless property, can satisfy the needs of present medium-to-high grade diesel engine oil.The preparation method is workable, is fit to large-scale industrialization production.
With the carbon black dispersing method sample that contains multifunctional viscosity index improver is carried out the dispersing property evaluation, method is following: the watch-glass that 1. the carbon black sample will be housed places the baking oven dried overnight, and oven temperature is 120 ℃.Taking-up is placed on naturally cooling in the loft drier, prevents the carbon black suction with water-absorbing materials such as silica gel or calcium chloride; 2. in 5% ratio multi-functional viscosity index improver is added in the HVI H5 base oil, add 7% dispersion agent T-151A simultaneously, 60～80 ℃ of following stirring and dissolving; 3. add carbon black in 2% ratio at the above-mentioned oil product that is modulated into, disperseed 30 minutes rotating speed 10,000rpm with the high speed dispersion clarifixator; 4. treat that the intact back of sample dispersion carries out the viscosity test 60 ℃ under with the viscometer of prior preheating rapidly, and with this viscosity number with add the make comparisons percentage of calculating viscosity increase of carbon black viscosity before, Δ V in result such as the table 1
kShown in the value.The percentage that increases through the sample viscosity that contrasts discovery, contain among the present invention the multifunctional viscosity index improver that is provided is obviously lower, so this multifunctional viscosity index improver provides the soot dispersing property of obvious excellence to the oil product band.
Rustless property is tested with method of polarization curve, specifically is to adopt Gamry-Reference600 electro-chemical test system, and be 7.5cm with effective working area
2The steel plate that is soaked with slushing oil be working electrode, be counter electrode with the carbon dioxide process carbon electrode, SCE is a reference electrode.Adopt the scanning potential method to test the polarization curve of antirust oil film, the scanning current potential is-0.5V～0.5V that the sampling period is 2 seconds.Whole test is carried out under room temperature (25 ℃), with the index of corrosion potential value as judgement sample rustless property.Test sample preparation: the ratio in 5% is added multi-functional viscosity index improver in the HVI H5 base oil to, adds 7% dispersion agent T-151A simultaneously, 60～80 ℃ of following stirring and dissolving.The result of corrosion potential sees table 1, and contrast finds, it is higher that the corrosion potential of the sample of the multifunctional viscosity index improver that contains among the present invention to be provided is compared the sample that adds common viscosity index improver, therefore has better rustless property.
Embodiment:
Embodiment 1:
In four neck flasks with stirring and nitrogen protection, add 100g ethylene-propylene copolymer and 1900g II class base oil, dissolving is about 5 hours under 130 ℃ temperature.Be warming up to 200 ℃, drop into maleic anhydride 10g, after 5 minutes, add peroxidized t-butyl perbenzoate 10g.Whole process is carried out under nitrogen protection, and temperature remains on 200 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-1.
In the device of water trap is housed, 84.6g oleic acid is heated to 100 ℃, be added dropwise to the 39.6g diethylenetriamine again, it is azeotropic agent that the back that finishes adds 21g YLENE.Be warming up to 220 ℃ slowly continuously, whole temperature-rise period is 4 hours, reach 220 ℃ after isothermal reaction 2 hours again, last vacuum is removed raw material and the azeotropic agent that has neither part nor lot in reaction, obtains imidazolinium compounds 2-aminoethyl 17 alkenyl imidazoline 105.3g.
Under nitrogen protection, the ethylene-propylene copolymer Y-1 2000g of maleic anhydride graft is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 104.5g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-01 165 ℃ of reactions.
Embodiment 2:
In four neck flasks with stirring and nitrogen protection, add 2Kg ethylene-propylene copolymer and 18Kg III class base oil, dissolving is about 4 hours under 130 ℃ temperature.Be warming up to 170 ℃, drop into maleic anhydride 150g, after 5 minutes, add peroxidized t-butyl perbenzoate 50g.Whole process is carried out under nitrogen protection, and temperature remains on 170 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-2.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, the ethylene-propylene copolymer Y-2 2000g of maleic anhydride graft is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 52g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-02 140 ℃ of reactions.
Embodiment 3:
In four neck flasks with stirring and nitrogen protection, add 300g ethylene-propylene copolymer and 1700g I class base oil, dissolving is about 5 hours under 130 ℃ temperature.Be warming up to 200 ℃, drop into maleic anhydride 20g, after 5 minutes, add peroxidized t-butyl perbenzoate 10g.Whole process is carried out under nitrogen protection, and temperature remains on 200 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-3.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, the ethylene-propylene copolymer Y-3 2000g of maleic anhydride graft is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 200g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-03 150 ℃ of reactions.
Embodiment 4:
In four neck flasks with stirring and nitrogen protection, add 400g ethylene-propylene copolymer and 1600g polyalphaolefin synthetic oil, dissolving is about 5 hours under 130 ℃ temperature.Be warming up to 180 ℃, drop into maleic anhydride 30g, after 5 minutes, add Di Cumyl Peroxide 99 10g.Whole process is carried out under nitrogen protection, and temperature remains on 180 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-4.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, maleic anhydride graft ethylene-propylene copolymer Y-4 2000g is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 40g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-04 160 ℃ of reactions.
Embodiment 5:
In four neck flasks with stirring and nitrogen protection, add 500g ethylene-propylene copolymer and 1500g III class base oil, dissolving is about 5 hours under 130 ℃ temperature.Be warming up to 180 ℃, drop into maleic anhydride 50g, after 5 minutes, add Di Cumyl Peroxide 99 10g.Whole process is carried out under nitrogen protection, and temperature remains on 180 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-5.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, maleic anhydride graft ethylene-propylene copolymer Y-5 2000g is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 20g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-05 165 ℃ of reactions.
Embodiment 6:
In four neck flasks with stirring and nitrogen protection, add 600g ethylene-propylene copolymer and 1400g III class base oil, dissolving is about 5 hours under 130 ℃ temperature.Be warming up to 180 ℃, drop into maleic anhydride 30g, after 5 minutes, add 2,5-dimethyl--2,5-dual-tert-butyl peroxy hexane 15g.Whole process is carried out under nitrogen protection, and temperature remains on 180 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-6.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, the ethylene-propylene copolymer Y-6 2000g of maleic anhydride graft is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 150g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-06 170 ℃ of reactions.
Embodiment 7:
In four neck flasks with stirring and nitrogen protection, add 700g ethylene-propylene copolymer and 1300g III class base oil, dissolving is about 5 hours under 130 ℃ temperature.Be warming up to 180 ℃, drop into maleic anhydride 30g, after 5 minutes, add 2,5-dimethyl--2,5-dual-tert-butyl peroxy hexane 15g.Whole process is carried out under nitrogen protection, and temperature remains on 180 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-7.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, the ethylene-propylene copolymer Y-7 2000g of maleic anhydride graft is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 170g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-07 175 ℃ of reactions.
Embodiment 8:
In four neck flasks with stirring and nitrogen protection, add 790g ethylene-propylene copolymer and 1210g III class base oil, dissolving is about 6 hours under 130 ℃ temperature.Be warming up to 200 ℃, drop into maleic anhydride 40g, after 5 minutes, add Lucidol tert-butyl ester 15g.Whole process is carried out under nitrogen protection, and temperature remains on 200 ℃, reacts 4 hours, removes the maleic anhydride of not participating in reaction with vacuum, obtains intermediate product Y-8.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection, the ethylene-propylene copolymer Y-8 2000g of maleic anhydride graft is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 50g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-A-08 180 ℃ of reactions.
Embodiment 9:
In four neck flasks with stirring and nitrogen protection, add 100g ethylene-propylene copolymer and 500g o-Xylol, dissolving is about 3 hours under 130 ℃ temperature.Under 130 ℃, drop into maleic anhydride 3g, after 5 minutes, add Lucidol 1g.Whole process is carried out under nitrogen protection, and temperature remains on 130 ℃, reacts 4 hours, and o-Xylol and unreacted maleic anhydride are removed in underpressure distillation, obtain intermediate product Y-9.
Press embodiment 1 said method Synthetic 2-aminoethyl 17 alkenyl imidazolines.
Under nitrogen protection; The ethylene-propylene copolymer Y-9 100g of maleic anhydride graft is dissolved in 500gIII class base oil, is heated to 160 ℃, add 2-aminoethyl 17 alkenyl imidazoline 104.5g; After 6 hours, obtain multifunctional viscosity index improver product MOCP-A-09 165 ℃ of reactions.
Embodiment 10:
In the device of water trap is housed, the 30g LAURIC ACID 99 MIN is heated to 120 ℃, be added dropwise to the 19.8g diethylenetriamine again, it is azeotropic agent that the back that finishes adds 10.5g YLENE.Be warming up to 160 ℃ of reaction dehydrations 2 hours, elevated temperature to 200 ℃ reaction dehydration is 4 hours again, and last vacuum is removed unreacted diethylenetriamine, obtains 2-aminoethyl hendecene base tetrahydroglyoxaline 40g.
Under nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-2 2000g that obtains among the embodiment 2 is heated to 160 ℃, add 2-aminoethyl hendecene base tetrahydroglyoxaline 40g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-B 165 ℃ of reactions.
Embodiment 11:
In the device of water trap is housed, the 18.3g phenylformic acid is heated to 120 ℃, be added dropwise to the 19.8g diethylenetriamine again, it is azeotropic agent that the back that finishes adds 10.5g YLENE.Be warming up to 160 ℃ of reaction dehydrations 2 hours, elevated temperature to 200 ℃ reaction dehydration is 4 hours again, and last vacuum is removed unreacted diethylenetriamine, obtains 2-aminoethyl benzylimidazoline 28.3g.
Under nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-2 2000g that obtains among the embodiment 2 is heated to 160 ℃, add 2-aminoethyl benzylimidazoline 28g, after 6 hours, obtain multifunctional viscosity index improver product MOCP-C 165 ℃ of reactions.
Embodiment 12:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 160 ℃, adds diethylenetriamine 16.5g, react after 4 hours, vacuum is removed the diethylenetriamine of not participating in reaction.Add oleic acid 43.8g again, temperature rises to 200 ℃ of reactions 6 hours, obtains MOCP-D.
Embodiment 13:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 150 ℃, adds diethylenetriamine 16.5g, react after 4 hours, vacuum is removed the diethylenetriamine of not participating in reaction.Add LAURIC ACID 99 MIN 31.1g again, temperature rises to 200 ℃ of reactions 6 hours, obtains MOCP-E.
Embodiment 14:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 140 ℃, adds diethylenetriamine 16.5g, react after 4 hours, vacuum is removed the diethylenetriamine of not participating in reaction.Add phenylformic acid 19g again, temperature rises to 200 ℃ of reactions 7 hours, obtains MOCP-F.
Embodiment 15:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 150 ℃, adds triethylene tetramine 23.4g, react after 4 hours, vacuum is removed the triethylene tetramine of not participating in reaction.Add oleic acid 43.8g again, temperature rises to 200 ℃ of reactions 4 hours, obtains MOCP-G.
Embodiment 16:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 160 ℃, adds TEPA 32.6g, react after 4 hours, vacuum is removed the TEPA of not participating in reaction.Add oleic acid 43.8g again, temperature rises to 200 ℃ of reactions 5 hours, obtains MOCP-H.
Embodiment 17:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 170 ℃, adds five ethene hexamine 52.5g, reacted 4 hours.Add oleic acid 43.8g again, temperature rises to 200 ℃ of reactions 6 hours, obtains MOCP-I
Embodiment 18:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 180 ℃, adds polyethylene polyamine (mixture of N atom number 5～10) 52.5g, reacted 4 hours.Add oleic acid 43.8g again, temperature rises to 200 ℃ of reactions 6 hours, obtains MOCP-J
Embodiment 19:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 160 ℃, adds triethylene tetramine 23.4g, react after 4 hours, vacuum is removed the triethylene tetramine of not participating in reaction.Obtain DOCP-A.
Embodiment 20:
The maleic anhydride graft ethylene-propylene copolymer Y-2 2000g that obtains among the embodiment 2,2-aminoethyl 17 alkenyl imidazoline 52g 60 ℃ of following mechanical stirring 30 minutes, are obtained BOCP-A.
Embodiment 21:
Under the nitrogen protection, the maleic anhydride graft ethylene-propylene copolymer Y-22000g that obtains among the embodiment 2 is heated to 160 ℃, adds diethylenetriamine 16.5g, react after 4 hours, vacuum is removed the diethylenetriamine of not participating in reaction.Add oleic acid 43.8g again,, obtain BOCP-B 60 ℃ of following mechanical stirring 30 minutes.
Only enumerated the performance data of gained sample among part embodiment and the comparative example in the table 1, the gained sample all can provide good soot dispersing property and rustless property among other embodiment.
Table 1 obtains the viscosity rate of increase and the corrosion potential of sample segment from embodiment
| V 100℃，(mm 2/s) | ΔV k，(％) | Corrosion potential, (mv) | |
| MOCP-A-02 | 10.32 | 26 | -526.0 |
| MOCP-A-04 | 13.56 | 18 | -512.0 |
| MOCP-B | 10.28 | 27 | -533.0 |
| MOCP-C | 10.31 | 25 | -535.0 |
| MOCP-D | 10.34 | 25 | -558.0 |
| MOCP-E | 10.31 | 26 | -571.0 |
| MOCP-F | 10.27 | 26 | -566.0 |
| MOCP-G | 10.35 | 24 | -550.0 |
| DOCP-A | 10.34 | 31 | -671.0 |
| BOCP-A | 10.26 | 39 | -680.0 |
| BOCP-B | 10.24 | 38 | -678.0 |
| OCP | 10.26 | 39 | -682.0 |
Claims (8)
1. viscosity index improver is characterized in that: form and content is by weight percentage:
Base oil 60%～94.5%, ethylene-propylene copolymer 5%～39.5%, imidazolinium compounds are 0.5%～10%, wherein the general formula of imidazolinium compounds is:
R representes hydrogen, alkyl, alkenyl or aromatic base; N is 1-10.
2. viscosity index improver according to claim 1 is characterized in that: the ethylene-propylene copolymer weight percent is 10%～30%.
3. viscosity index improver according to claim 1 is characterized in that: the imidazolinium compounds weight percent is 2%～8%.
4. viscosity index improver according to claim 1 is characterized in that: described alkyl is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, sec.-butyl, amyl group, neo-pentyl, hexyl, heptyl, undecyl, tridecyl, pentadecyl, heptadecyl or nonadecyl.
5. viscosity index improver according to claim 1 is characterized in that: alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 1-heptenyl, 7-hexadecylene base or 8-17 thiazolinyls.
6. viscosity index improver according to claim 1 is characterized in that: aromatic base has following structure, and wherein R1 representes the alkyl of hydrogen, hydroxyl, an amino or 1-10 carbon atom.
7. the preparation method of the described viscosity index improver of claim 1 is characterized in that:
(1) utilize solution grafting grafted maleic anhydride on ethylene-propylene copolymer: the gross weight to form solution is a benchmark, and solution grafting solvent for use weight is 60～95%, and solvent is I, II, III class base oil, polyalphaolefin or other organic solvent; Initiator is peroxidized t-butyl perbenzoate, Lucidol, 2; 5-dimethyl--2,5-bis(t-butylperoxy) hexane or Di Cumyl Peroxide 99, weight is 0.05～2%; The weight of maleic anhydride is 0.2～3%; The grafting temperature is 150 ℃～200 ℃, and 3～6 hours graft reaction time is after reaction finishes; Remove unreacted maleic anhydride with nitrogen injection or vacuum extraction, obtain the ethylene-propylene copolymer intermediate product of maleic anhydride graft;
(2) imidazoline group is connected on the ethylene-propylene copolymer:
Method A is: at first, with organic acid and the synthetic imidazolinium compounds of polyethylene polyamine reaction, the weight ratio of organic acid and polyethylene polyamine is 1: 1～1.5; Gross weight with organic acid and polyamines polyene is that benchmark adds 10～40% azeotropic agent, and azeotropic agent is toluene or YLENE, under 100 ℃ temperature, slowly splashes into organic acid in the polyamines polyene; Dropwise the back and add azeotropic agent; Slowly be warmed up to 220 ℃ continuously from 100 ℃, temperature-rise period is 4 hours, reach 220 ℃ after isothermal reaction 2 hours; Vacuum is removed raw material and the azeotropic agent that has neither part nor lot in reaction, obtains imidazolinium compounds;
Then, with the ethylene-propylene copolymer and the imidazolinium compounds reaction of maleic anhydride graft, temperature of reaction is 80 ℃～220 ℃, and the reaction times is 4～8 hours, obtains viscosity index improver;
Or method B is: with the ethylene-propylene copolymer and the polyethylene polyamine reaction of maleic anhydride graft, the weight of polyethylene polyamine is 0.5～5% earlier, and temperature of reaction is 80 ℃～220 ℃, and the reaction times is 4～8 hours, obtains intermediate product; Intermediate product and organic acid are reacted, organic acid and polyethylene polyamine mol ratio are 1: 1 again; The organic acid general formula is: R-COOH, R represent hydrogen, alkyl, alkenyl or aromatic base; Temperature of reaction is from 100 ℃～250 ℃, is warmed up to 220 ℃ slowly continuously from 100 ℃, and temperature-rise period is about 4 hours; Obtain viscosity index improver;
The general formula of described polyethylene polyamine is H
2N (CH
2CH
2NH)
N+1H, n are 1-10.
8. the preparation method of viscosity index improver according to claim 7, it is characterized in that: described other organic solvent is alkylnaphthalene, chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, santochlor, toluene, o-Xylol, p-Xylol or m-xylene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864993A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Dispersion type ethylene-propylene copolymer and preparation method thereof |
| CN110156928A (en) * | 2019-05-29 | 2019-08-23 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method for dispersing wear-resistant type boronation viscosity index improver |
| CN110452755A (en) * | 2018-05-08 | 2019-11-15 | 中国石油天然气股份有限公司 | Viscosity index improver and preparation method thereof |
| CN111040082A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Viscosity index improver and preparation method and application thereof |
| WO2023279554A1 (en) * | 2021-07-08 | 2023-01-12 | 中国石油化工股份有限公司 | Application of naphthenic imidazoline in inhibiting formation of natural gas hydrates and composition containing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2097800A (en) * | 1981-05-06 | 1982-11-10 | Exxon Research Engineering Co | Ethylene copolymer viscosity index improver-dispersant additive useful in oil compositions |
| US6107257A (en) * | 1997-12-09 | 2000-08-22 | Ethyl Corporation | Highly grafted, multi-functional olefin copolymer VI modifiers |
| CN1364820A (en) * | 2001-01-11 | 2002-08-21 | 中国石油天然气股份有限公司大连石化分公司 | Viscosity index improver for disperse anti-oxygen type ethylene-propylene copolymer and its preparaing method |
| CN101117363A (en) * | 2006-08-04 | 2008-02-06 | 中国石油天然气股份有限公司大连润滑油研究开发中心 | Process for producing high-nitrogen dispersion type ethylene-propylene copolymer viscosity index improver |
-
2011
- 2011-03-03 CN CN201110051240.0A patent/CN102653696B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2097800A (en) * | 1981-05-06 | 1982-11-10 | Exxon Research Engineering Co | Ethylene copolymer viscosity index improver-dispersant additive useful in oil compositions |
| US6107257A (en) * | 1997-12-09 | 2000-08-22 | Ethyl Corporation | Highly grafted, multi-functional olefin copolymer VI modifiers |
| CN1364820A (en) * | 2001-01-11 | 2002-08-21 | 中国石油天然气股份有限公司大连石化分公司 | Viscosity index improver for disperse anti-oxygen type ethylene-propylene copolymer and its preparaing method |
| CN101117363A (en) * | 2006-08-04 | 2008-02-06 | 中国石油天然气股份有限公司大连润滑油研究开发中心 | Process for producing high-nitrogen dispersion type ethylene-propylene copolymer viscosity index improver |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864993A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Dispersion type ethylene-propylene copolymer and preparation method thereof |
| CN103864993B (en) * | 2012-12-10 | 2016-08-03 | 中国石油天然气股份有限公司 | Dispersion type ethylene-propylene copolymer and preparation method thereof |
| CN110452755A (en) * | 2018-05-08 | 2019-11-15 | 中国石油天然气股份有限公司 | Viscosity index improver and preparation method thereof |
| CN110452755B (en) * | 2018-05-08 | 2022-02-01 | 中国石油天然气股份有限公司 | Viscosity index improver and preparation method thereof |
| CN111040082A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Viscosity index improver and preparation method and application thereof |
| CN111040082B (en) * | 2018-10-15 | 2022-10-21 | 中国石油化工股份有限公司 | Viscosity index improver and preparation method and application thereof |
| CN110156928A (en) * | 2019-05-29 | 2019-08-23 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method for dispersing wear-resistant type boronation viscosity index improver |
| WO2023279554A1 (en) * | 2021-07-08 | 2023-01-12 | 中国石油化工股份有限公司 | Application of naphthenic imidazoline in inhibiting formation of natural gas hydrates and composition containing same |
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