CN117487101A - Multi-arm radial hydrogenated conjugated diene-styrene block copolymer, preparation method thereof and application thereof in lubricating oil - Google Patents
Multi-arm radial hydrogenated conjugated diene-styrene block copolymer, preparation method thereof and application thereof in lubricating oil Download PDFInfo
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- CN117487101A CN117487101A CN202210882222.5A CN202210882222A CN117487101A CN 117487101 A CN117487101 A CN 117487101A CN 202210882222 A CN202210882222 A CN 202210882222A CN 117487101 A CN117487101 A CN 117487101A
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- conjugated diene
- block copolymer
- styrene block
- styrene
- hydrogenated conjugated
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- 229920006132 styrene block copolymer Polymers 0.000 title claims abstract description 27
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims description 39
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 25
- 238000005859 coupling reaction Methods 0.000 claims description 24
- 150000001993 dienes Chemical group 0.000 claims description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229920000359 diblock copolymer Polymers 0.000 claims description 12
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 9
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 9
- -1 tertiary amine compounds Chemical class 0.000 claims description 9
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011925 1,2-addition Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 89
- 239000002199 base oil Substances 0.000 abstract description 12
- 230000008719 thickening Effects 0.000 abstract description 11
- 230000009974 thixotropic effect Effects 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 32
- 239000003921 oil Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 16
- 238000010168 coupling process Methods 0.000 description 16
- 230000008878 coupling Effects 0.000 description 14
- 229920001195 polyisoprene Polymers 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920001400 block copolymer Polymers 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 7
- 239000008186 active pharmaceutical agent Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 229920005683 SIBR Polymers 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920006030 multiblock copolymer Polymers 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101710095395 Histidine decarboxylase proenzyme Proteins 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- CJGBPPZRFOVLNI-UHFFFAOYSA-N cyclohexane;oxolane Chemical compound C1CCOC1.C1CCCCC1 CJGBPPZRFOVLNI-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- OELFLUMRDSZNSF-BRWVUGGUSA-N nateglinide Chemical compound C1C[C@@H](C(C)C)CC[C@@H]1C(=O)N[C@@H](C(O)=O)CC1=CC=CC=C1 OELFLUMRDSZNSF-BRWVUGGUSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a multi-arm radial hydrogenated conjugated diene-styrene block copolymer, a preparation method thereof and application thereof in lubricating oil. The structural expression of the multi-arm radial hydrogenated conjugated diene-styrene block copolymer is as follows: (HDS) n -P; wherein HDS is hydrogenated conjugated diene-b-styrene copolymer arms; n is the number of arms; p is a coupling agent residue; the polymer is used as viscosity index of lubricating oilAn improver (VII) which exhibits excellent solubility, reversible thixotropic properties and high and low temperature thickening ability, and Shear Stability Index (SSI) in base oils<21, the comprehensive behavior is excellent.
Description
Technical Field
The invention relates to a hydrogenated conjugated diene-styrene copolymer, in particular to a multi-arm radial hydrogenated conjugated diene-styrene block copolymer, a preparation method thereof and application of the copolymer as a viscosity index improver of lubricating oil, and belongs to the technical field of synthesis of the viscosity index improver of the lubricating oil.
Background
The viscosity index improver (called as viscosity index agent VII for short) of lubricating oil usually comprises high molecular compounds such as polymethacrylate, ethylene-propylene copolymer, polyisobutylene and the like, wherein the mass fraction of the high molecular compounds is 0.5-1.5% in neutral base oil, and the high molecular compounds form a coil structure in the oil product, and the volume of the high molecular compounds is much larger than that of the base oil with smaller molecular weight, so that the viscosity of the oil product is much larger than that of the oil product. The polymer can be compacted into a compact molecular conformation of coil under the static state at low temperature, the viscosity increasing capability is small, and the influence on the viscosity of oil products is small; under the friction, shearing, traction and stretching actions of the reciprocating motion of an engine oil pump and a piston, the compound oil generates heat, molecular coils of polymer molecules are directionally stretched in a high-temperature environment, the hydrodynamic volume is increased, the viscosity of the oil is increased, the flow blocking action on the oil is increased, the viscosity of the oil is obviously increased, and when the engine stops working, the compound oil is cooled to room temperature, the viscosity of the compound oil is recovered to a original state, and the compound oil is called reversible thixotropic property in the process. The thickened internal combustion engine oil, hydraulic oil, gear oil and the like prepared by VII have good viscosity-temperature performance, smooth viscosity-temperature curve, good low-temperature starting performance and high-temperature lubricating capability, and are universal in four seasons. In recent years, with the advent of hydrogenated styrene conjugated diene copolymers represented by the SV series of Shell, the prepared lubricating oil has low-temperature startability and good viscosity at high temperatures, i.e., good viscometric properties. However, the molecular structure of the polymer is not disclosed, and the polymer belongs to the special technology.
In the prior art, chinese patent (CN 107793542 a) describes a method for synthesizing hydrogenated styrene/isoprene block copolymer, which is to synthesize a diblock copolymer or multiblock copolymer comprising styrene block and isoprene block in an anionic polymerization system using nonpolar alkane and toluene as polymerization solvents, and hydrogenate the diblock copolymer or multiblock copolymer to obtain hydrogenated styrene/isoprene block copolymer; the hydrogenated styrene/isoprene block copolymer is applied to optical fiber and optical cable filling ointment. In China patent (CN 104342231B), a lubricant viscosity index improver and a preparation method thereof are disclosed, wherein the lubricant viscosity index improver is obtained by hydrogenating and modifying polyisoprene-B-polybutadiene-B-polystyrene triblock copolymer, the molecular chain of the polymer is long-chain linear molecule, the entanglement degree among molecules is low, and the thixotropic behavior is avoided.
Chinese patent (CN 102731739A) describes star polymers of lubricating oil viscosity index improvers, their preparation and use, of the formula (EP 1) M-X- (S-EB-EP 2) n2, wherein EP1 is a first type of arms of the star polymer, a polyisoprene block having a number average molecular weight of 10000 to 150000 before hydrogenation, X is the core of a divinylbenzene coupling agent, S-EB-EP2 is a second type of arms of the star polymer, wherein S is adjacent to the core X of the divinylbenzene coupling agent of the star polymer, EB is in the middle of the arms, EP2 is outside the arms, S is a polystyrene block having a number average molecular weight of 2000 to 15000, EB is a polybutadiene block having a number average molecular weight of 1500 to 12000 and at least 85% or more of 1, 4-polymerized polybutadiene block, EP2 is a polyisoprene block having a number average molecular weight of 10000 to 20000 before hydrogenation, n 1 For the number of arms of EP1, n2 is the number of arms of S-EB-EP2, nl+n2 is the asymmetric number of arms of the block copolymer in the star polymer obtained when 2 or more moles of divinylbenzene coupling agent are coupled per mole of living block copolymer, wherein the star polymer structure contains 2 to 15wt% of polybutadiene blocks, and the polyisoprene blocks and polybutadiene blocks in the star polymer structure are at least partially hydrogenated. The star polymer not only exhibits excellent tackifying effect and shear stability, but also is useful in formulating thickened engine oilsHas a low pumping viscosity and low temperature start-up viscosity and does not form crystals or gels in the engine oil.
In ("research of hydrogenated SIBR for viscosity index improver", university of company, high molecular material, 2009), a series of SIBRs with controllable molecular weight and narrow molecular weight distribution are synthesized in cyclohexane solvent by adopting a molecular design method and an anionic polymerization technology, wherein n-butyllithium is used as an initiator, tetrahydrofuran is used as a structure regulator, and styrene, isoprene and butadiene are used as monomers; the 1,2 structure of polybutadiene chain segment and 3,4 structure content of polyisoprene chain segment in SIBR are regulated by adopting a tetrahydrofuran monobasic regulating system, and hydrogenation reaction research is carried out on synthesized SIBR sample by adopting nickel naphthenate/triisobutylaluminum as a homogeneous catalytic system. The hydrogenated SIBR can be used for a viscosity index improver, and the main properties of the viscosity index improver include thickening ability, shear stability, high-temperature high-shear property, low-temperature property and the like. FT-IR, 1H-NMR and DSC tests were also conducted on the viscosity index improver hydrogenated styrene/conjugated diene (butadiene, isoprene) copolymer (HSD) in the section "molecular structure of viscosity index improver HSD", polymer materials science and engineering, 2012, and showed that HSD was a highly hydrogenated styrene-butadiene block copolymer having a high butadiene content, the mass fraction of styrene was 18.50%, the mass fraction of butadiene was 81.50%, and the butadiene hydrogenation degree was 98.20%. HSD12F number average molecular weight of 4.59X10 by gel chromatography GPC 5 g/mol, single arm number average molecular weight of 6.47×10 4 g/mol, shows that HSD is a star-shaped styrene-butadiene block copolymer with an arm number of 7.10 and a coupling efficiency of 86.44%. That is, the polymer is linear living polymer before coupling and then coupling is performed by DVB, however, DVB is added into the living lithium polymer in the coupling method, and the DVB is quickly copolymerized with DVB monomer after being combined with the living lithium chain due to the higher activity of divinylbenzene, so that a large amount of gel is generated, and other living molecular chains are not coupled.
In the process of preparing eight-arm star block copolymer by living anion polymerization and hydrogenation reaction thereofIn the "high molecular theory, 09 in 2020"), the synthesis of lithium (PS-PI-Li) active chain by active anion polymerization method was studied, and then the coupling reaction with octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) was carried out to obtain octa-arm star-shaped block copolymer (PS-PI) 8 POSS; finally, pair (PS-PI) 8 The PI chain segment in POSS is subjected to hydrogenation addition reaction to prepare another novel eight-arm star-shaped block copolymer (PS-PI) containing saturated hydrocarbon chain segments 8 POSS, tested with thermogravimetric analysis (TGA) (PS-PI) 8 Thermal stability of POSS before and after hydrogenation addition reaction. However, the polystyrene (PS-) chain of the polymer is at the outermost side of the "-PI-" chain taking P0SS as a core, and can be characterized as star SIS or the hydrogenated polymer is multi-arm star SEPS, and the polymer has high modulus and high elasticity and shows the behavior of a thermoplastic elastomer, and meanwhile, the behavior description applied to the aspect of a viscosity index improver of lubricating oil is not related.
The number average molecular mass Mn= (32-36) x 10 of the SV-260 currently available on the market 4 Is obtained by coupling hydrogenation of conjugated diene-styrene polymer, and the number average molecular mass Mn= (5.5-6.5) x 10 of the polymer before coupling 4 Hydrogenated polymers are not strong and are not elastic and are used primarily as viscosity index improvers for lubricating oils, and their preparation is proprietary to Kraton.
In summary, the polymers obtained by coupling the active styrene/conjugated diene copolymer with divinylbenzene DVB are all multi-arm molecular structures of core radiation-short branched chains, the coupling efficiency of the polymers is only 86%, the lower linear polymers with the mass fraction of 14% still remain, and the oligomers are not resistant to shearing in oil products; meanwhile, DVB is extremely easy to self-polymerize or cyclize to form hyperbranched polymer, super-macromolecules or gel are generated, the polymer containing the gel and the linear polymer is not suitable to be used as a lubricating oil viscosity index improver, the gel is easy to cause easy blockage of fluid, and the linear polymer with low molecules is easy to have defects of molecular chain breakage, poor viscosity temperature performance and the like when being sheared. Thermoplastic elastomers coupled with octaethylene-POSS are also unsuitable as viscosity index modifiers.
Disclosure of Invention
Aiming at the defects of low coupling efficiency, low thickening capacity caused by high content of linear oligomer, poor viscosity-temperature performance and shear stability and the like of the coupled polymer which is shown as a viscosity index modifier in the coupling process of the active styrene/conjugated diene copolymer in the prior art, and the eight-arm star-shaped block copolymer (PS-PI) obtained by coupling reaction of a (polystyrene-b-isoprene) lithium active chain and octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) 8 POSS has the technical problems of high modulus, high elasticity, behavior of a thermoplastic elastomer, inapplicability to being used as a viscosity index improver of lubricating oil and the like.
A first object of the present invention is to provide a multi-arm radial hydrogenated conjugated diene-styrene block copolymer [ (HDS) n -P]，(HDS) n P has a special molecular structure, so that the oil exhibits good viscosity-temperature performance, the arm molecular chains can be outwards stretched and oriented under the shearing traction effect in the base oil, so that the viscosity of the oil is improved when the shearing friction heat generation generates high temperature, the breaking probability of spherical star-shaped short molecular chains is reduced, and when the shearing traction external force disappears and the temperature is reduced, the branched arm molecular chains shrink, curl and tangle, so that the thickening capacity of the oil is reduced, and the starting of an engine is beneficial.
A second object of the present invention is to provide a process for preparing (HDS) which is simple to operate and low in cost n -P method.
A third object of the present invention is to provide a method of (HDS) n Use of P as viscosity index improver for lubricating oils, (HDS) n P has the actions of large thickening capacity, good viscosity-temperature performance, good shear stability and the like under the state of adding a small amount of P into base oil, and has the Shear Stability Index (SSI) lower than 20 and the thickening capacity>8.8mm 2 And/s, the viscosity-temperature curve shows the characteristics of smoothness and the like along with the temperature change.
In order to achieve the above technical object, the present invention provides a multi-arm radial hydrogenated conjugated diene-styrene block copolymer having the following structural expression: (HDS) n -P; wherein HDS isHydrogenated conjugated diene-b-styrene copolymer arms; n is the number of polymer arms; p is a coupling agent residue.
The invention (HDS) n P has a radial molecular structure which enables the arm molecular chains to extend and orient outwards in the base oil under the action of shear traction, the viscosity of the oil is increased when the heat generated by shear friction is high, the probability of breakage of the short molecular chains of spherical star-shaped polymers is reduced, in addition, when the external force of shear traction disappears and the temperature is reduced, the branched arm molecular chains shrink, curl and tangle, resulting in the reduction of the thickening capacity of the oil, which has beneficial engine starting, i.e. the hydride has good low-temperature performance, (HDS) n The abovementioned viscometric properties exhibited by P are the essential behaviour of VII.
As a preferred embodiment, n is 5 to 7 (integer).
As a preferred embodiment, the said (HDS) n P has a number average molecular mass of M n ＝22×10 4 ～42×10 4 Molecular mass distribution index M w /M n =1.02 to 1.08. Number average molecular weight M of the HDS n ＝4.5×10 4 ～ 6×10 4 . It is known that after a certain mileage of engine operation, the viscosity of the lubricating oil decreases and the oil needs to be replaced again, which is due to the breakage of the thickened polymer molecular chains in the oil. The present invention controls the number average molecular weight mn=45000-60000 of HDS, and aims to prevent the long molecular chain from molecular chain scission under shearing action in the base oil, resulting in the reduction of thickening ability. (HDS) n The P also contains small amounts of oligomers, generally the mass fractions of oligomers<3.0％。
As a preferred embodiment, the said (HDS) n The mass percentage content of the styrene unit in the P is 10-20%. (HDS) n The quality of the styrene units in P is controlled within a preferred range, the number average molecular weight of the polystyrene blocks is preferably within a range of Mn=6000 to 12000, the polystyrene blocks giving the whole (HDS) n P suitable modulus, prevention (HDS) n P is self-adhesive, so that the finished product prepared in the extrusion, drying, grinding and other units has good formationThe powder has stability and can not be adhered to form a block when stored at medium and low temperature.
As a preferred embodiment, the hydrogenated conjugated diene-b-styrene copolymer arms are obtained by hydrogenating conjugated diene-b-styrene diblock copolymers; the conjugated diene unit in the conjugated diene-b-styrene diblock copolymer is at least one of butadiene, isoprene and piperylene. The most preferred conjugated diene unit is isoprene. When isoprene is adopted as conjugated diene in the conjugated diene-b-styrene diblock copolymer, the content of the introduced short branched side group is relatively high, which is beneficial to improving the dissolution and the extension of the hydrogenated conjugated diene-b-styrene copolymer arm in a solution system.
As a preferable embodiment, the mass ratio of the 1, 2-addition unit or/and the 3, 4-addition unit of the conjugated diene unit in the conjugated diene-b-styrene diblock copolymer is 30 to 50%. In order to prevent (HDS) n P has a tendency to crystallize, which renders it insoluble in the base oil, and when sufficient 1.2-or 3.4-mer is incorporated in the conjugated diene segment, its crystallization properties are advantageously reduced, while the polymer contains some side-chain structural units which are also advantageous after Hydrogenation (HDS) n P exhibits a visco-thermal effect in the oil.
As a preferred embodiment, the conjugated diene units in the conjugated diene-b-styrene diblock copolymer have a degree of hydrogenation of >98%. While the styrene units are hardly hydrogenated.
The invention provides (HDS) n P is a polymer (DS) of molecular structure n -P hydrogenation. (DS) n -P is a core radial polymer formed by coupling octavinyl POSS or octaphenyl silsesquioxane with conjugated diene-b-styrene diblock copolymer as branching arms, having the molecular structure of formula 1:
wherein D is a conjugated diene block, S is a styrene block, and P is a coupler residue core; n is the degree of coupling of DS.
The invention also provides a preparation method of the multi-arm radial hydrogenated conjugated diene-styrene segmented copolymer, which comprises the steps of adding an initiator and conjugated diene monomer into an anion polymerization solution system containing a structure regulator to initiate a first-stage polymerization reaction, adding styrene monomer to perform a second-stage polymerization reaction, adding a coupling agent to perform a coupling reaction, and obtaining a coupling reaction product through hydrogenation reaction.
As a preferable scheme, the structure regulator is at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether and tertiary amine compounds. To ensure (DS) n The poly-conjugated diene block of P has a sufficient number of 1.2-or 3.4-units, and it is necessary to add a suitable structure regulator during the polymerization of the conjugated diene, most preferably at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether, etc. As a preferred embodiment, the structure modifier is used in an amount of 0.06 to 0.10g/100g relative to the conjugated diene monomer. The preferable structure regulator and the mass fraction of the 1, 2-addition or/and 3, 4-addition units in the poly conjugated diene block with controllable dosage are 30-50%.
As a preferable scheme, the anionic polymerization solution system comprises a mixed solvent composed of cyclohexane, tetrahydrofuran and/or toluene; wherein the mass ratio of the cyclohexane to the tetrahydrofuran and/or the toluene is 1-3/1. The octavinylsilsesquioxane and octaphenylsilsesquioxane have poor solubility, so that coupling efficiency is generally poor when the octavinylsilsesquioxane and octaphenylsilsesquioxane are used as coupling agents, and coupling efficiency of octavinylposs and octaphenylsilsesquioxane can be greatly improved by using cyclohexane together with an appropriate amount of tetrahydrofuran or toluene as a solvent. The amount of the mixed solvent is used to ensure that the mass percentage concentration of the polymerized monomer is 8-12%.
As a preferred scheme, the temperature of the first-stage polymerization reaction is 50-70 ℃ and the time is 20-25 min.
As a preferable scheme, the temperature of the two-stage polymerization reaction is 50-70 ℃ and the time is 20-25 min.
As a preferable scheme, the temperature of the coupling reaction is 50-70 ℃ and the time is 20-25 min;
as a preferred embodiment, the coupling agent is octavinyl POSS and/or octaphenyl silsesquioxane; the coupling agent is mainly a soluble compound capable of coupling with lithium at the end of the living polymer and having 5 to 7 active functional groups, and the coupling agent and butyllithium (NBL) are used in an amount of NBL/coupling agent= (5 to 8)/1 (molar ratio), the amount of NBL being consumed by reaction with moisture in the polymerization environment.
As a preferred scheme, the hydrogenation reaction adopts a catalytic system composed of nickel isooctanoate and diisobutyl aluminum hydride and/or triisobutyl aluminum, wherein the molar ratio of Ni/Al in the catalytic system is=3-6; the dosage of the catalytic system relative to the coupling reaction product is 0.5-0.9 mmol/100g. Preferred hydrogenation catalysts are capable of selectively hydrogenating alkenyl groups in the polymer without hydrogenating the benzene ring.
As a preferred embodiment, the hydrogenation reaction conditions are: the temperature is 80-85 ℃, the hydrogen pressure is 1.2-1.5 MPa, and the reaction time is 2.0-3.0 h.
The invention (DS) n P (HDS) n -P preparation method comprising the following specific steps:
first step, (DS) n -preparation of P polymer: in a cyclohexane-tetrahydrofuran solvent system containing a structure regulator, firstly, carrying out anionic polymerization reaction on conjugated diene monomer by initiating with n-butyllithium at 50-70 ℃ for 20-25 min, then adding styrene monomer for second-stage copolymerization for 20-25 min, and finally, coupling active lithium polymer with a coupling agent to form multi-arm radial (DS) n -P-glue, in which case the molecular mass, distribution index and microstructure of the polymer in the polymerized glue can be determined.
Second step, (HDS) n -preparation of P:
adding quantitative nickel isooctanoate-diisobutyl aluminum hydride or triisobutyl aluminum complex (commonly called Ni/Al catalyst) into the polymerized glue solution to carry out hydrogenation reaction, and stopping hydrogenation reaction when the hydrogenation degree of diene segments in polymer molecules reaches the set requirement, thereby obtaining hydrogenWashing the obtained compound with citric acid water solution, centrifuging to remove residual catalyst dissolved in water phase, and collecting hydrogenated liquid by vapor condensation, extrusion, and drying (HDS) n P, if necessary, grinding the hydrides into powder, in order to be readily soluble in the base oil.
The invention also provides application of the multi-arm radial hydrogenated conjugated diene-styrene block copolymer as a lubricating oil viscosity index improver.
As a preferable embodiment, the multi-arm radial hydrogenated conjugated diene-styrene block copolymer is added to the lubricating oil in an amount of 0.95 to 1.15wt%.
The invention (HDS) n P has no thermoplastic elastomer behaviour and no modulus and strength at low temperatures and is suitable only for VII.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the prior polystyrene/conjugated diene Hydride (HSD) serving as a viscosity index modifier, the modified polystyrene/conjugated diene hydride has the defects of no reversible thixotropic property, low thickening capacity, poor high-temperature performance, easy blockage of oil pumps and pistons (rings) by contained super-macromolecules and gel, poor viscosity-temperature performance and shear stability and the like. The present invention provides for the first time a multi-arm radial hydrogenated conjugated diene-styrene block copolymer [ (HDS) of non-molecular linear long chain and non-thermoplastic elastomer behavior n -P]The molecules of the polymer take on spherical multi-arm radial structures, the polymer has narrow molecular mass distribution, no gel and easy dissolution in base oil, and the curled coupled multi-arm molecular chains can be outwards stretched and oriented under the shearing and stretching acting force of the polymer in the oil product, so that the viscosity of the oil product at high temperature is increased; under the condition of low temperature or engine stop operation or starting, the coupled multi-arm molecular chain is contracted, curled and entangled, the viscosity of the oil product is reduced, and the engine is beneficial to starting, namely, the engine has viscosity-temperature effect and reversible thixotropic property. Compared to other polymers commercially available, (HDS) n P has a Shear Stability Index (SSI) of less than 21 and a thickening power when added to a base oil in an amount of 0.95 to 1.15% by weight>9.0mm 2 And/s, the viscosity-temperature curve shows advantages of smoothness along with temperature change, and the like.
Based on the above performance, the present invention (HDS) n P is particularly suitable as VII.
The invention (HDS) n The preparation technology of the P is simple, can be finished by utilizing the existing mature technology, and is easy to control and industrialize.
Drawings
FIG. 1 shows a raw polymer (I-S) prepared in example 5 n -GPC profile of P.
FIG. 2 shows the raw polymer (I-S) prepared in example 5 n H of P 1 -NMR spectrum.
FIG. 3 is a H of a hydrogenated EPS-P-5# polymer prepared in example 5 1 -NMR。
Detailed Description
The following examples are intended to illustrate the invention in further detail and are not to be construed as limiting the scope or practice of the claimed invention.
The number average molecular mass and the molecular weight distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; by H 1 -quantitative determination of the microstructure of the polymer by NMR spectroscopy; the thickening ability of the polymer was tested by SH/T0566-93 method; the Shear Stability Index (SSI) of VII was tested using the SH/T0103-2007 method; the fluidity of the thickened oil product is 25 ℃ by adopting a coating-4 # cup method.
Example 1
1500mL of cyclohexane, 1200mL of Tetrahydrofuran (THF), 0.3mL of ditetrahydrofuran propane and 320mL of isoprene are firstly added into a clean 5-liter polymerization kettle, 0.40mol/L of n-butyllithium (NBL) and 8.5mL of initiation are added when the temperature is raised to 55 ℃ for initiation and polymerization for 25min, and polyisoprene active lithium (I) is obtained a -Li + ). Adding 36mL of styrene into the glue solution at one time, and polymerizing at 70 ℃ for 25min to obtain I a -S b -Li + Next, 4.0mL of a THF solution of 0.10mol/L octaethylene-silsesquioxane was added to the polymerization gum solution and coupled at 65℃for 25 minutes to obtain (I) a S b ) n P glue, molecular mass and microstructure of the polymer obtained by sampling are shown in Table 1.
Introducing polymer virgin rubber liquid into a 5L hydrogenation kettleAnd adding a hexane solution catalyst containing 0.22mol/L nickel [ wherein n (nickel isooctanoate)/n (triisobutylaluminum) =4.5]8.4mL, stirring at 80deg.C under hydrogen pressure of 1.40MPa for 140min to obtain polyisoprene unit hydrogenation degree 98.23%, adding 10% (weight) citric acid aqueous solution 110mL into the discharged glue solution, stirring for 30min, separating water phase at 2800 rpm in high-speed centrifuge, condensing oil phase with water vapor, and drying to obtain (EP S) n Hydrogenated polymer P (designated EPS-P-1#).
Example 2
The relevant process and conditions in example 1 were kept unchanged except that 1700mL of cyclohexane, 1000mL of toluene, 0.3mL of ditetrahydrofurfuryl propane, 8.0mL of NBL, 40mL of styrene, and 3.8mL of a tetrahydrofuran solution of octaethylene-silsesquioxane were added; 9.0mL of the glue solution hydrogenation catalyst.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 98.56%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-2#.
Example 3
The relevant process and conditions in example 1 were kept unchanged except that 2000mL of cyclohexane, 800mL of toluene, 0.5mL of tetrahydrofurfuryl alcohol ethyl ether, 9.0mL of NBL, 36mL of styrene, and 4.2mL of a toluene solution of 0.12mol/L of octaphenyl silsesquioxane were added; 9.5mL of glue solution hydrogenation catalyst.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 98.87%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-3#.
Example 4
The relevant process and conditions in example 1 were kept unchanged except that 2200mL of cyclohexane, 600mL of toluene, 0.6mL of tetrahydrofurfuryl alcohol ethyl ether, 7.5 mL of NBL, 34mL of styrene, and 3.6mL of a toluene solution of 0.12mol/L of octaphenyl silsesquioxane were added; 10.0mL of the glue solution hydrogenation catalyst.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 99.32%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-4#.
Example 5
The relevant process and conditions in example 4 were kept unchanged except that 1500mL of cyclohexane, 1500mL of toluene, 0.7mL of tetrahydrofurfuryl alcohol ethyl ether, 7.0 mL of NBL, 37mL of styrene, and 4.5mL of a 0.12mol/L toluene solution of octaphenyl silsesquioxane were added; 8.0mL of the glue solution hydrogenation catalyst.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 98.56%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-5#.
EPS-P-5# protopolymer (I-S) n GPC analysis of P is shown in FIG. 1, protopolymer H 1 -NMR spectra are shown in figure 2; EPS-P-5# polymer is shown in FIG. 3.
Example 6
The relevant process and conditions in example 4 were kept unchanged except that 1800mL of cyclohexane, 900mL of toluene, 8.2mL of NBL, and 4.7mL of a toluene solution of 0.12mol/L of octaphenyl silsesquioxane as a mixed monomer consisting of 140mL of butadiene and 240. 240 mL of isoprene in the first stage polymerization were added.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 99.32%, and the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated as EBPS-P-6#.
Comparative example 1
The relevant process and conditions in example 2 were kept unchanged except that 2400mL of cyclohexane, 400mL of toluene, and 9.5mL of NBL were added.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 98.45%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-T 1 。
Comparative example 2
The relevant process and conditions in example 2 were kept unchanged except that 2400mL of cyclohexane, 400mL of toluene, and 6.8mL of NBL were added.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 98.45%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-T 2 。
Comparative example 3
The relevant process and conditions in example 4 were kept unchanged except that 6.0mL of hydrogenation catalyst was added.
As a result, the degree of hydrogenation of polyisoprene units in the hydrogenated polymer was 87.69%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-T 3 。
Comparative example 4
The relevant process and conditions in example 6 were kept unchanged except that in the first polymerization stage, the diene was 380mL of a mixed monomer composed of butadiene and 40mL of isoprene, and that 4.7mL of a toluene solution of 0.12mol/L octaphenyl silsesquioxane was used.
As a result, the degree of hydrogenation of conjugated diene units in the hydrogenated polymer was 99.41%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated as EBPS-P-T 4 。
Comparative example 5
The relevant process and conditions in example 2 were kept unchanged except that 9.0mL of NBL was added.
As a result, the degree of hydrogenation of conjugated diene units in the hydrogenated polymer was 98.48%, the molecular mass and microstructure of the raw polymer are shown in Table 1, and the hydrogenated polymer was designated EPS-P-T 5 。
Table 1 molecular mass and microstructure of the hydrogenated Polymer base Polymer in the examples
Note that: the content of the 4-unit and the vinyl unit is the mass fraction in the isoprene section and in the polybutadiene section respectively; e is a polyethylene chain segment formed by completely hydrogenating 1, 4-addition units of isoprene and butadiene, P is a polyisopropylene side chain formed by hydrogenating an isoprene addition unit to form polypropylene and/or a 3, 4-addition unit, and B is a polybutene side chain formed by hydrogenating a butadiene 1, 2-addition unit.
Application example 1
The (HDS) prepared in the examples of the present invention was added separately to 150BS base oil in which an appropriate amount of antioxidant 1076 was dissolved n 1.0% by weight of each of the styrene-diene copolymer hydride (SV-260) and ethylene propylene diene monomer (EPDM 4045) produced by Shell and P were stirred at 70 to 80℃for 30 minutes, and then subjected to VII analysis, the results of which are shown in Table 2.
TABLE 2 analysis of Polymer VII behavior
Note that: "SSI" is the shear stability index of polymer VII, the greater the number, the poorer the shear stability.
As can be seen from Table 2, the design of the present invention was prepared (HDS) n P as VII shows good solubility and viscosity-temperature properties in the oil; meanwhile, the SSI value is smaller than 21, and the excellent and good shear stability is shown.
Claims (16)
1. A multi-arm radial hydrogenated conjugated diene-styrene block copolymer characterized by:
has the following structural expression: (HDS) n -P；
Wherein,
HDS is the hydrogenated conjugated diene-b-styrene copolymer arm;
n is the number of arms;
p is a coupling agent residue.
2. The multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 1, wherein: n is 5 to 7.
3. The multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 1, wherein: said (HDS) n P has a number average molecular mass of M n ＝22×10 4 ～42×10 4 Molecular mass distribution index M w /M n =1.02 to 1.08; number average molecular weight M of the HDS n ＝4.5×10 4 ～6×10 4 。
4. A multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 1 or 3, characterized in that: said (HDS) n The mass percentage content of the styrene unit in the P is 10-20%.
5. The multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 1, wherein:
the hydrogenated conjugated diene-b-styrene copolymer arm is obtained by hydrogenating a conjugated diene-b-styrene diblock copolymer;
the conjugated diene unit in the conjugated diene-b-styrene diblock copolymer is at least one of butadiene, isoprene and piperylene.
6. The multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 5, wherein: the total mass ratio of the 1, 2-addition units or/and the 3, 4-addition units of the conjugated diene units in the conjugated diene-b-styrene diblock copolymer is 30-50%.
7. The multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 5, wherein: the conjugated diene units in the conjugated diene-b-styrene diblock copolymer have a degree of hydrogenation of >98%.
8. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to any one of claims 1 to 7, characterized in that: in an anionic polymerization solution system containing a structure regulator, an initiator and conjugated diene monomer are firstly added to initiate a first-stage polymerization reaction, then styrene monomer is added to perform a second-stage polymerization reaction, then a coupling agent is added to perform a coupling reaction, and the obtained coupling reaction product is subjected to hydrogenation reaction, thus obtaining the catalyst.
9. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 8, wherein:
the structure regulator is at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether and tertiary amine compounds;
the dosage of the structure regulator relative to conjugated diene monomer is 0.06-0.10 g/100g.
10. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 8, wherein: the anionic polymerization solution system comprises a mixed solvent composed of cyclohexane, tetrahydrofuran and/or toluene; wherein the mass ratio of the cyclohexane to the tetrahydrofuran and/or the toluene is 1-3/1.
11. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 8, wherein:
the temperature of the first-stage polymerization reaction is 50-70 ℃ and the time is 20-25 min;
the temperature of the two-stage polymerization reaction is 50-70 ℃ and the time is 20-25 min;
the temperature of the coupling reaction is 50-70 ℃ and the time is 20-25 min.
12. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 8, wherein:
the coupling agent is octavinyl POSS and/or octaphenyl silsesquioxane;
the mole ratio of the coupling agent to the initiator is 1 (5-8).
13. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 8, wherein: the hydrogenation reaction adopts a catalytic system composed of nickel isooctanoate, diisobutyl aluminum hydride and/or triisobutyl aluminum, wherein the Ni/Al molar ratio in the catalytic system is=3-6; the dosage of the catalytic system relative to the coupling reaction product is 0.5-0.9 mmol/100g.
14. The process for producing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 8 or 13, wherein: the hydrogenation reaction conditions are as follows: the temperature is 80-85 ℃, the hydrogen pressure is 1.2-1.5 MPa, and the reaction time is 2.0-3.0 h.
15. Use of a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to any one of claims 1 to 7, characterized in that: as an improver of the viscosity index of lubricating oil.
16. The process for preparing a multi-arm radial hydrogenated conjugated diene-styrene block copolymer according to claim 15, wherein: the addition amount of the multi-arm radial hydrogenated conjugated diene-styrene block copolymer in the lubricating oil is 0.95-1.15 wt%.
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