CN116731269A - Hydrogenated asymmetric long-chain branched polystyrene-conjugated diene copolymer, and preparation method and application thereof - Google Patents
Hydrogenated asymmetric long-chain branched polystyrene-conjugated diene copolymer, and preparation method and application thereof Download PDFInfo
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- CN116731269A CN116731269A CN202210203696.2A CN202210203696A CN116731269A CN 116731269 A CN116731269 A CN 116731269A CN 202210203696 A CN202210203696 A CN 202210203696A CN 116731269 A CN116731269 A CN 116731269A
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- conjugated diene
- chain branched
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- branched polystyrene
- diene copolymer
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 62
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 62
- 229920001577 copolymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 102
- 150000001993 dienes Chemical group 0.000 claims abstract description 55
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920005604 random copolymer Polymers 0.000 claims abstract description 16
- 239000010687 lubricating oil Substances 0.000 claims abstract description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- -1 tertiary amine compounds Chemical class 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000002199 base oil Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 238000011925 1,2-addition Methods 0.000 claims description 4
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 230000008719 thickening Effects 0.000 abstract description 12
- 238000010008 shearing Methods 0.000 abstract description 8
- 230000009974 thixotropic effect Effects 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 94
- 239000003921 oil Substances 0.000 description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 230000008878 coupling Effects 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000003440 styrenes Chemical class 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000006399 behavior Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920000359 diblock copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 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 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006030 multiblock copolymer Polymers 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920005683 SIBR Polymers 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 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
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- C10M143/12—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
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention discloses a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer, and a preparation method and application thereof. Hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer comprising an asymmetric long chain branched polystyrene-conjugated diene copolymer (S-D/Y) n ) Obtained by hydrogenating conjugated diene units thereof, wherein S is a styrene homo-block, D/Y n The conjugated diene and divinylbenzene random copolymer block has n as branching degree, and is used as Viscosity Index Improver (VII) for lubricating oil, and has good solubility, reversible thixotropic property, high low-temperature thickening capacity and high shearing capacityStability Index (SSI)<22, the comprehensive performance is excellent.
Description
Technical Field
The invention relates to a hydrogenated styrene-conjugated diene copolymer, in particular to a hydrogenated asymmetric long-chain branched polystyrene-conjugated diene copolymer, a preparation method thereof and application thereof as a lubricating oil viscosity index improver, and belongs to the technical field of synthesis of lubricating oil viscosity index improvers.
Background
The viscosity index improver (called as viscosity index agent VII for short) of lubricating oil usually contains high molecular compounds such as polymethacrylate, ethylene propylene copolymer, polyisobutylene and the like, and is generally rubber-like or solid at room temperature, the molecular weight of the high molecular polymers is from tens of thousands to hundreds of thousands, and the high molecular polymers with mass fraction of 0.5-1.5% are usually added into neutral oil, so that the polymers form a coil structure in the oil, and the volume of the polymers is much larger than that of base oil with smaller molecular weight, so that the viscosity of the oil is far greater than that of solvent, which is why the thickening can be achieved. 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, namely good low-temperature starting performance and high-temperature lubricating capability, and can be used all the year round. Compared with single-stage oil with the same viscosity grade, the consumption of the lubricating oil can be reduced by 30 percent, and the consumption of the fuel oil can be reduced by 3 to 5 percent. 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 method adopts the mixed solvent of nonpolar alkane and toluene to effectively increase the reaction probability of active PS-Li end groups and isoprene, so as to reduce or eliminate the content of small molecular polystyrene in the hydrogenated styrene/isoprene block copolymer, and improve the dropping point of the two-block or multi-block hydrogenated styrene/isoprene block copolymer when the hydrogenated styrene/isoprene block copolymer is applied to optical fibers and optical cable filling ointment. In China patent (CN 104342231B), a viscosity index improver of lubricating oil is disclosed, and the viscosity index improver is obtained by hydrogenating and modifying polyisoprene-B-polybutadiene-B-polystyrene triblock copolymer, and the preparation method is that after regulator is added into a polymerization reactor with the temperature of 60-70 ℃ and the pressure of 0.1-0.5 MPa, isoprene, butadiene and styrene monomers are sequentially added for polymerization reaction; and after the polymerization reaction is finished, carrying out hydrogenation reaction on the obtained triblock copolymer to obtain the triblock copolymer. The polymer molecular chain is long-chain linear molecule, the entanglement degree between molecules is low, the thixotropic behavior is not ideal, but the thickening effect is achieved when mineral oil is added.
Chinese patent (CN 102731739 a) describes star polymers of lubricating oil viscosity index improvers, having asymmetric arms, composed of two different types of polymer arms, the first type of arms being hydrogenated polyisoprene homopolymers, the second type of arms being copolymers of hydrogenated polyisoprene-hydrogenated polybutadiene-polystyrene block structures, in which the polystyrene segments are close to the core of the star polymer, the hydrogenated polybutadiene segments being in the middle of the arms, the hydrogenated isoprene segments being on the outside of the arms, the star polymer structure containing 2 to 15% polybutadiene blocks, the polyisoprene blocks and the polybutadiene blocks being hydrogenated, and methods for preparing the same. The star polymer of the invention not only shows excellent tackifying effect and shear stability,and has lower pumping viscosity and low temperature start viscosity in formulating thickened engine oils 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 research results show that: the nickel naphthenate/triisobutyl aluminum catalytic system has higher catalytic activity and selectivity, the reaction temperature is 60 ℃, the hydrogen pressure is 4MPa, the catalyst dosage is 2mg/g of dry gel, the Al/Ni is 7, the reaction time is 3h, the hydrogenation degree of SIBR reaches 98%, and the hydrogenation reaction rate of each microstructure in the SIBR is from large to small and is B1,2 is more than B1,4 is more than I3,4. 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. In ("preparation and characterization of Star-shaped hydrogenated random copolymer HSIBR", chemical industry and engineering, 2012, 04), star-shaped styrene-isoprene-butadiene ternary random copolymer (SIBR) is prepared by anionic polymerization using Divinylbenzene (DVB) as a coupling agent and cyclohexane as a solvent, and by reacting nickel naphthenate and triisobutylaluminum as catalysts at 60℃and 4.0MPa hydrogen pressure for 4 hours, a hydrogenated Star-shaped styrene-isoprene-butadiene ternary random copolymer (HSIBR) having a hydrogenation degree of 100% is prepared. The effects of DVB/Li usage, single arm relative molecular mass on polymer Coupling Efficiency (CE) and hydrogenation reaction were examined. And self-made HSIBR is used as a lubricating oil viscosity index improver to test the performance of the lubricating oil viscosity index improver. The result shows that the highest SIBR coupling efficiency obtained by taking DVB as a coupling agent reaches 86.8%, and the synthesized HSIBR is taken as a lubricating oil viscosity index improver. Also in ("viscosity index improvementMolecular structure of the agent HSD ", polymer materials science and engineering, 2012, 11) the viscosity index improver hydrogenated styrene/conjugated diene (butadiene, isoprene) copolymer (HSD) was tested by FT-IR, 1H-NMR and DSC, and the study showed that HSD was a highly hydrogenated high butadiene content styrene-butadiene block copolymer with a mass fraction of styrene of 18.50%, a mass fraction of butadiene of 81.50% and a butadiene hydrogenation of 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, the arm number is 7.10, and the coupling efficiency is 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 addition, ("study of synthesis of branched copolymers based on anionic polymerization and their assembly behavior", jugglutination, university of double denier, 2013 (08)) it is proposed herein that branched block copolymers are a class of multiblock hyperbranched structures connected by polymer chains between branching points. The multicomponent block makes the performance of the whole polymer tend to be diversified, so that the polymer has wide application prospect in the aspects of biology, medicine, materials and the like. Anionic polymerization, as a truly living polymerization, has unique advantages in the synthesis of block copolymers of defined composition and polymers of precisely controlled structure. Thus, synthetic means based on anionic technology are clearly an efficient method for preparing branched block copolymers.
The polymers obtained by coupling the active styrene/conjugated diene copolymer with divinylbenzene DVB in the literature are all of 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. However, hydrogenated polymers of asymmetrically branched polystyrene-conjugated dienes having a low content of linear oligomers and a narrow molecular mass distribution as viscosity index modifiers have not been reported.
Disclosure of Invention
Aiming at the defects that the coupling efficiency is low, the thickening capacity is low due to high content of linear oligomer, and the coupled polymer contains partial super-macromolecules and gel, and the viscosity-temperature performance and the shear stability are poor as the viscosity index modifier in the prior art when the active styrene/conjugated diene copolymer is coupled by divinylbenzene DVB. The first object of the present invention is to provide a hydrogenated polystyrene-conjugated diene polymer (ABHSD) which has a large thickening ability, good viscosity-temperature properties and shear stability, a low oligomer content, no gel, a narrow molecular mass distribution and an asymmetric long chain branching.
It is a second object of the present invention to provide a process for preparing said ABHSD which is simple to operate and low cost.
A third object of the present invention is to provide the use of ABHSD as a viscosity index improver for lubricating oils, which exhibits a Shear Stability Index (SSI) of less than 22, thickening ability, when added to a base oil>8.4mm 2 And/s, the viscosity-temperature curve shows advantages of smoothness along with temperature change, and the like.
In order to achieve the above technical object, the present invention provides a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer obtained by hydrogenating conjugated diene units thereof from an asymmetric long chain branched polystyrene-conjugated diene copolymer; the asymmetric long chain branched polystyrene-conjugated diene copolymer has the following expression: S-D/Y n The method comprises the steps of carrying out a first treatment on the surface of the Wherein S is a styrene homo-block, D/Y n Is a random copolymer block of conjugated diene and divinylbenzene, n is the branching degree of the random copolymer block;s has a number average molecular weight of 4X 10 4 ～6×10 4 ；D/Y n Number average molecular weight of 20X 10 4 ～26×10 4 The method comprises the steps of carrying out a first treatment on the surface of the n is 2 to 6. The invention controls the number average molecular weight of the polystyrene block preferably in the range of Mn=40000-60000, and aims to control the ABHSD to have proper stiffness and high enough melt strength to ensure that the hydrogenated polymer has good powdering stability in finished products prepared in units of extrusion, drying, grinding and the like, and can not be adhered to form a block when stored at medium and low temperatures.
As a preferred embodiment, the asymmetric long chain branched polystyrene-conjugated diene copolymer has a degree of hydrogenation of conjugated diene units of >98%.
As a preferable scheme, the mass ratio of the styrene unit to the conjugated diene unit in the asymmetric long-chain branched polystyrene-conjugated diene copolymer is (15-25)/(85-75); the mass of divinylbenzene units in the random copolymer block of the conjugated diene and the divinylbenzene is 0.05 to 0.10% of the mass of conjugated diene units. The incorporation of minute amounts of divinylbenzene units into the random copolymer blocks of conjugated dienes and divinylbenzene has a relatively large impact on ABHSD performance. Although DVB is higher than the polymerization rate of conjugated diene, when a trace amount of DVB is copolymerized with a high concentration of conjugated diene monomer, the collision probability of the conjugated diene monomer and active lithium is far greater than that of the trace amount of DVB in such a polymerization environment due to the high concentration of the conjugated diene monomer and the active lithium, so that random asymmetric branched copolymerization is shown when the two monomers are copolymerized. In the polymerization of the poly conjugated diene units in the ABHSD copolymer molecule of the invention, DVB containing a small amount of difunctional is selected, and the aim is to carry out random and asymmetric branching on the poly conjugated diene units, thereby reducing the homopolymerization of DVB and reducing the occurrence of ultra-large molecules and coagulated insoluble matters. The branched molecular chain of the ABHSD copolymer with the structure extends outwards and orients under the action of shearing traction, and the branched molecular chain is added into an oil product, so that the viscosity of the oil product at high temperature can be improved, and the shearing resistance of a polymer can be improved and the breakage of the molecular chain can be reduced. In addition, when the shearing traction external force disappears and the temperature is reduced, the branched molecular long chain can shrink, curl and tangle, the thickening capacity of the oil product is reduced, and the engine starting is facilitated, namely, the engine has good low-temperature performance. The above viscosity-temperature properties exhibited by ABHSD copolymers are an essential behavior of VII.
As a preferred embodiment, the conjugated diene unit in the random copolymer block of the conjugated diene and divinylbenzene is at least one of isoprene, piperylene and butadiene.
As a preferable embodiment, the mass fraction of the 1, 2-addition unit or/and 3, 4-addition unit of the conjugated diene unit in the random copolymer block of the conjugated diene and divinylbenzene is 30 to 50%. In order to prevent the conjugated diene units in the ABHSD from containing longer polyethylene units after hydrogenation, which leads to the polymer having a tendency to crystallize and present a polyolefin resin and not soluble in the base oil, the conjugated diene units have enough 1.2-units or 3.4-units, and in addition, the inclusion of partial side-chain structural units in the polymer is beneficial to the viscosity-temperature effect of the hydrogenated ABHSD in the oil.
As a preferred embodiment, the asymmetric long chain branched polystyrene-conjugated diene copolymer has a number average molecular weight Mn=24×10 4 ～32×10 4 Molecular mass distribution index M w /M n =1.05 to 1.17. Weight average molecular weight mw= 250000 ～ 300000 of the asymmetric long chain branched polystyrene-conjugated diene copolymer, oligomer weight fraction in the polymer<0.6％。
The invention provides an ABHSD polymer with a chemical expression: S-D/Y n 。
Wherein S is a block formed by homopolymerization of styrene, the polymerization degree is an integer between 400 and 600, and the number average molecular weight Mn=4×10 4 ～6×10 4 ；D/Y n The method is characterized in that the method is an asymmetric long chain unit formed by random copolymerization of conjugated diene and divinylbenzene, wherein D is a conjugated diene polymerization unit, Y is a divinylbenzene linking unit, n is uneven distribution or the number of asymmetric branched chains (nodes) formed by the divinylbenzene in a random copolymerization chain segment, n is a positive integer between 2 and 6, and the derived physical meaning is branching degree or branching factor; D/Y n Number average molecular weight of (2)Quantity mn=20×10 4 ～26×10 4 ；S-D/Y n Number average molecular mass Mn of 24X 10 4 ～32×10 4 。
The present invention provides ABHSD polymer molecular conformations as follows:
wherein S is a polystyrene block, and the middle asymmetric long chain unit (D/Y n ) Is a random copolymer of a conjugated diene and divinylbenzene, Y being the branching junction in an asymmetric long chain segment.
The invention also provides a preparation method of the hydrogenated asymmetric long-chain branched polystyrene-conjugated diene copolymer, which comprises the steps of adding a styrene monomer into an anion polymerization system containing a structure regulator to carry out homopolymerization reaction, and then adding a divinylbenzene and conjugated diene mixed monomer to carry out copolymerization reaction to obtain an asymmetric long-chain branched polystyrene-conjugated diene copolymer glue solution; adding nickel/aluminum catalyst into the asymmetric long chain branched polystyrene-conjugated diene copolymer glue solution, and introducing hydrogen to perform hydrogenation reaction to obtain the final product.
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; the dosage of the structure regulator relative to conjugated diene monomer is 0.06-0.10 g/100g. In order to ensure that the polydiene block of the ABHSD has enough 1.2-chain units or 3.4-chain units, proper structure regulator is added during polymerization of the conjugated diene, and the preferable structure regulator is tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether and tertiary amine compounds, wherein the preferable structure regulator is at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether and the like, the dosage is 0.06-0.10 g/100g of diene monomer, and the mass fraction of the 1, 2-addition or/and 3.4-addition unit of the controlled conjugated diene block is 30-50%.
As a preferable scheme, the temperature of the homopolymerization reaction is 50-70 ℃ and the time is 20-25 min.
As a preferable scheme, the temperature is controlled within the range of 50-70 ℃ in the copolymerization reaction process, and the mixed monomer of divinylbenzene and conjugated diene is controlled to be uniformly added into a reaction system within 15-20 min, and the mixture of divinylbenzene and conjugated diene is further reacted for 15-25 min after the addition of the mixed monomer of divinylbenzene and conjugated diene is completed. The feeding time of the mixed monomer of divinylbenzene and conjugated diene is controlled to be 15-20 min, the aim is to synchronously and randomly branch DVB along with the molecular chain growth of diene monomer, and further react for 15-25 min, so as to improve the monomer conversion rate.
As a preferred embodiment, the nickel/aluminum catalyst is a complex of nickel isooctanoate-diisobutylaluminum hydride and/or triisobutylaluminum hydride, and the nickel/aluminum catalyst has a molar ratio Ni/Al of 3 to 6.
As a preferable mode, the amount of the nickel/aluminum catalyst is 0.5 to 0.9mmol/100g relative to the amount of the asymmetric long chain branched polystyrene-conjugated diene copolymer gum solution, wherein the nickel/aluminum catalyst is measured by mass of nickel, and the asymmetric long chain branched polystyrene-conjugated diene copolymer gum solution is measured by mass of dry matter.
As a preferred embodiment, the hydrogenation reaction conditions are: the temperature is 70-80 ℃, the hydrogen pressure is 1.2-1.5 MPa, and the reaction time is 1.5-3.0 h.
As a preferred scheme, the solvent adopted by the anionic polymerization system is cyclohexane or n-hexane and a mixture thereof, wherein the mass concentration of the monomer is 10-15%; the initiator used was n-butyllithium.
As a preferred embodiment, the conjugated diene monomer may be at least one of isoprene, piperylene and butadiene, and mixtures thereof, wherein isoprene is most preferred, and isoprene itself contains a short chain branched structure, which is beneficial for improving the visco-thermal effect of ABHSD.
The preparation method of the ABHSD provided by the invention comprises the following two steps:
first step, S-D/Y n Preparation of the polymer:in a cyclohexane-hexane solvent system containing a structure regulator, firstly, initiating styrene monomer by n-butyllithium to carry out anionic polymerization reaction at 50-70 ℃ for 20-25 min, then continuously and uniformly adding mixed monomer formed by conjugated diene dissolved with DVB into the active solution of the first section of formed polystyrene lithium for random copolymerization for 15-20 min, and continuing to react for 15-25 min after diene monomer is added to obtain S-D/Y n The molecular weight, molecular weight distribution index and microstructure of the polymer in the polymer dope can be measured at this time.
Second, preparation of ABHSD:
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, stopping the hydrogenation reaction when the hydrogenation degree of the conjugated diene section in the polymer molecule reaches the set requirement, washing the hydride with water solution of citric acid, centrifuging to remove residual catalyst dissolved in the water phase, and condensing, extruding and drying the hydrogenated solution by water vapor to obtain the ABHSD, wherein the Mooney viscosity of the ABHSD polymer is ML (1+4) 100 ℃ to be 55-65.
The invention also provides application of the hydrogenated asymmetric long-chain branched polystyrene-conjugated diene copolymer as a viscosity index improver of lubricating oil.
As a preferred scheme, the ABHSD belongs to a diblock copolymer, does not have the behaviors of a thermoplastic elastomer and vulcanized rubber, and the polymer has no modulus and strength at low temperature and cannot be used as vulcanized rubber, and is most suitable for being used as VII, and the mass percentage content of the hydrogenated asymmetric long-chain branched polystyrene-conjugated diene copolymer base oil is 0.8-1.5%; most preferably 0.95 to 1.15%.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the prior DVB coupled core multi-arm short linear polystyrene/conjugated diene Hydride (HSD) used as a viscosity index modifier, the modified polyvinyl chloride has no reversible thixotropic property, low thickening capacity, poor high-temperature performance, and super-macromolecules and coagulum containedThe glue is easy to block the oil pump and the piston (ring), and has poor viscosity-temperature performance and shearing stability. The ABHSD polymer is gel-free, has narrow molecular mass distribution, is easily dissolved in base oil, has strong thickening capability, has random asymmetric branched long chains and side chains in a molecular structure, gives the polymer a shearing and drafting acting force to the polymer in the oil, can extend and orient curled molecular chains outwards, increases the viscosity of the oil at a high temperature, and causes shrinkage, curling and entanglement of the branched molecular long chains at a low temperature (when an engine stops running or starts), so that the viscosity of the oil is reduced, and the polymer is beneficial to the starting of the engine, namely has a viscous temperature effect and reversible thixotropic property. The ABHSD has a Shear Stability Index (SSI) of less than 22 and a thickening power when added to a base oil at 1.0 wt% as compared to other commercially available polymers>8.4mm 2 And/s, the viscosity-temperature curve shows advantages of smoothness along with temperature change, and the like. Based on the above behavior, the ABHSD polymers of the present invention are particularly suitable as VII.
The ABHSD polymer preparation technology provided by the invention is simple, can be completed by utilizing the existing mature technology, and is easy to control and industrialize.
Drawings
FIG. 1 is a GPC chart of an asymmetric long chain branched polystyrene-conjugated diene copolymer prepared in example 1.
FIG. 2 is a drawing of an asymmetric long chain branched polystyrene-conjugated diene copolymer H prepared in example 1 1 -NMR spectrum.
FIG. 3 is a drawing of H of a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer prepared in example 1 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 viscosity ML (ML 100 ℃ C. 1+4) of the polymer is measured by a Mooney viscometer;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
Adding 3000mL of cyclohexane, 0.5mL of ETE and 67mL of styrene into a clean 5-liter polymerization kettle, heating to 50-60 ℃, adding 3.0mL of n-butyllithium (NBL) with the concentration of 0.40mol/L to initiate the styrene, and polymerizing for 24min to obtain polystyrene active lithium (S m-Li) + ). Continuously and uniformly adding mixed monomer consisting of 353mL of isoprene and 2.6mL of DVB cyclohexane solution with the concentration of 0.70mol/L into polystyrene active lithium solution for 18min to perform random copolymerization with the formed active lithium polystyrene solution, and continuously reacting for 20min after diene monomer is added to obtain S-D/Y n A polymer stock solution. Sampling the polymer mn=26.83×10 4 The molecular mass distribution index was 1.16, the mass fraction of the oligomer in the polymer was 0.56%, and the 3, 4-addition unit content was 39.5%.
Introducing the polymer stock solution into a 5L hydrogenation kettle, adding 0.2mol/L cyclohexane solution [ wherein n (nickel isooctanoate)/n (triisobutylaluminum) =4.3 ] 9mL of the cyclohexane solution, stirring for 2.5 hours under the conditions of the temperature of 70-80 ℃ and the hydrogen pressure of 1.2-1.4 MPa, measuring the hydrogenation degree of a polydiene unit to be 98.4%, discharging the hydrogenation liquid, adding 120g of 10 weight percent citric acid aqueous solution into the hydrogenation liquid, stirring for 30min, centrifuging to separate a water phase, condensing and drying the oil phase by water vapor to obtain an ABHSD polymer (marked as ABHSD-1#), and obtaining the ABHSD-1# polymer ML100 ℃ 1+4 as 62.6. GPC analysis of the raw Polymer is shown in FIG. 1, H 1 -NMR spectra are shown in figure 2; h of ABHSD-1# 1 The NMR spectrum is shown in FIG. 3.
Example 2
The relevant process and conditions in example 1 were kept unchanged except that the amount of styrene added was changed to 48mL, NBL was 2.6mL, ETE was 0.7mL, and DVB cyclohexane solution was 2.8mL.
As a result, the polymer mn= 29.64 ×10 was measured 4 A molecular mass distribution index of 1.17, a mass fraction of oligomer in the polymer of 0.53%,3, 4-addition unitsThe content is 45.7%; the degree of hydrogenation of the hydrogenated ABHSD polymer (designated ABHSD-2#) was 98.6% and ML 100deg.C 1+4 was 64.7.
Example 3
The relevant process and conditions in example 1 were kept unchanged except that the amount of styrene added was 88mL, NBL was 3.4mL, ETE was 0.4mL, and DVB cyclohexane solution was 2.4mL.
As a result, the polymer mn=25.34×10 was measured 4 The molecular mass distribution index is 1.14, the mass fraction of the oligomer in the polymer is 0.32%, and the content of 3, 4-addition units is 34.6%; the degree of hydrogenation of the hydrogenated ABHSD polymer (designated ABHSD-3#) was 98.7% and ML 100deg.C 1+4 was 56.7.
Example 4
The relevant process and conditions in example 1 were kept unchanged except that 250mL of isoprene, 130mL of butadiene, 3.3mL of NBL, 0.8mL of ETE and 3.4mL of DVB cyclohexane solution were added.
As a result, the polymer mn= 28.65 ×10 was measured 4 The molecular mass distribution index is 1.16, the mass fraction of the oligomer in the polymer is 0.48%, the 3, 4-addition sum unit content of the isoprene segment is 48.7%, and the 1, 2-addition unit content of the butadiene segment is 46.8%; the degree of hydrogenation of the hydrogenated ABHSD polymer (designated ABHSD-4#) was 98.8% and ML 100deg.C 1+4 #.
Example 5
The relevant process and conditions in example 1 were kept unchanged except that 14mL of the added hydrogenation catalyst was changed.
As a result, the hydrogenated ABHSD polymer (designated as ABHSD-5#) was measured to have a hydrogenation degree of 99.3%, the mass fraction of the oligomer in the polymer was 0.47%, and ML 100deg.C 1+4 was 62.9.
Comparative example 1
The relevant process and conditions in example 1 were kept unchanged except that 5mL of the added hydrogenation catalyst was changed. As a result, the degree of hydrogenation of the hydrogenated ABHSD (designated as ABHSD-6#) polymer was 87.6%, the mass fraction of oligomers in the polymer was 0.38%, and ML 100deg.C 1+4 was 62.9.
Comparative example 2
The relevant process and conditions in example 2 were kept unchanged except that the amount of styrene added was changed to 42mL, NBL was 2.4mL, and DVB cyclohexane solution was 2.7mL.
As a result, the polymer mn=26.23×10 was measured 4 The molecular mass distribution index is 1.15, and the content of 3, 4-addition units is 44.6%; the hydrogenation degree of the hydrogenated ABHSD polymer is 98.1 percent, the ML100 ℃ is 62.6 in 1+4, and the mass fraction of the oligomer in the polymer is 0.43 percent; the ABHSD polymer has cold flow phenomenon and caking, and is not easy to be made into powder.
Comparative example 3
The relevant process and conditions in example 3 were kept unchanged except that the amount of styrene added was changed to 94mL.
As a result, the polymer mn=25.72×10 was measured 4 The molecular mass distribution index is 1.15, and the content of 3, 4-addition units is 33.9%; the hydrogenation degree of the hydrogenated ABHSD polymer is 98.5 percent, the ML100 ℃ is 1+4 is 59.4, and the mass fraction of the oligomer in the polymer is 0.45 percent; after adding 1.0% by weight of the ABHSD polymer to the base oil (150N) and stirring at 50-80℃for 60min, the polymer remains partly in the swollen state.
Comparative example 4
The relevant process and conditions in example 1 were kept unchanged except that the mixed monomers consisting of isoprene and DVB were added to the polymerizer at once for copolymerization.
As a result, the polymer mn=22.32×10 was measured 4 The molecular mass distribution index is 1.12,3,4, the content of the addition unit is 38.6%, the hydrogenation degree of the polyisodiene unit is 98.6%, the mass fraction of the oligomer in the polymer is 0.56%, the mass fraction of the polymer ML100 ℃ 1+4 is 59.4, and the hydrogenated polymer is marked as ABHSD-7#.
Comparative example 5
The relevant process and conditions in example 1 were kept unchanged except that 3.0mL of DVB was added for coupling for 25min after the second isoprene polymerization stage was completed.
As a result, the polymer mn= 23.68 ×10 was measured 4 The molecular mass distribution index was 1.18, the mass fraction of oligomer in the polymer was 6.87%, and the 3.4-addition unit content was 38.6%The hydrogenation degree of the polyisodiene unit is 98.6%, the polymer ML100 ℃ 1+4 is 59.4, and the hydrogenated polymer is marked as ABHSD-8#.
Application example 1
The ABHSD prepared in the invention and SV-260 of Shell company were added respectively in an amount of 1.0 wt% to 150N base oil in which an appropriate amount of antioxidant 1076 was dissolved, and the results of VII analysis and study were carried out after stirring at 60 to 80℃for 40 minutes.
TABLE 1 behavior of Polymer VII
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 1, the ABHSD prepared by the design defined in the present invention as VII shows good solubility and viscosity-temperature properties in oil products; meanwhile, the SSI value is smaller than 22, and good shear stability is shown.
Claims (15)
1. A hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer characterized by: the hydrogenated conjugated diene is obtained by hydrogenating an asymmetric long chain branched polystyrene-conjugated diene copolymer;
the asymmetric long chain branched polystyrene-conjugated diene copolymer has the following expression: S-D/Y n The method comprises the steps of carrying out a first treatment on the surface of the Wherein S is a styrene homo-block, D/Y n Is a random copolymer block of conjugated diene and divinylbenzene, n is the branching degree of the random copolymer block;
s has a number average molecular weight of 4X 10 4 ～6×10 4 ；
D/Y n Number average molecular weight of 20X 10 4 ～26×10 4 ；
n is 2 to 6.
2. The hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 1, characterized in that: the degree of hydrogenation of conjugated diene units in the asymmetric long chain branched polystyrene-conjugated diene copolymer is >98%.
3. The hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 1, characterized in that: the mass ratio of the styrene unit to the conjugated diene unit in the asymmetric long-chain branched polystyrene-conjugated diene copolymer is (15-25)/(85-75); the mass of divinylbenzene units in the random copolymer block of the conjugated diene and the divinylbenzene is 0.05 to 0.10% of the mass of conjugated diene units.
4. The hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 1, characterized in that: the conjugated diene unit in the conjugated diene-divinylbenzene random copolymer block is at least one of isoprene, piperylene and butadiene.
5. The hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 1, characterized in that: the mass fraction of the 1, 2-addition units or/and 3, 4-addition units of the conjugated diene units in the conjugated diene-divinylbenzene random copolymer block is 30-50%.
6. The hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 1, characterized in that: the asymmetric long chain branched polystyrene-conjugated diene copolymer has a number average molecular weight mn=24×10 4 ～32×10 4 Molecular mass distribution index M w /M n ＝1.05～1.17。
7. The process for producing a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to any one of claims 1 to 6, characterized in that: in an anion polymerization system containing a structure regulator, firstly adding a styrene monomer for homopolymerization reaction, and then adding a divinylbenzene and conjugated diene mixed monomer for copolymerization reaction to obtain an asymmetric long-chain branched polystyrene-conjugated diene copolymer glue solution; adding nickel/aluminum catalyst into the asymmetric long chain branched polystyrene-conjugated diene copolymer glue solution, and introducing hydrogen to perform hydrogenation reaction to obtain the final product.
8. The process for producing a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 7, 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.
9. The process for producing a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 7, wherein:
the temperature of the homopolymerization reaction is 50-70 ℃ and the time is 20-25 min;
the temperature is controlled within the range of 50-70 ℃ in the copolymerization reaction process, and the mixed monomer of divinylbenzene and conjugated diene is controlled to be uniformly added into a reaction system within 15-20 min, and the mixture of divinylbenzene and conjugated diene is further reacted for 15-25 min after the addition of the mixed monomer of divinylbenzene and conjugated diene is completed.
10. The process for producing a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 7, wherein: the nickel/aluminum catalyst is a complex of nickel isooctanoate-diisobutylaluminum hydride and/or triisobutylaluminum hydride, and the Ni/Al molar ratio of the nickel/aluminum catalyst is=3-6.
11. The process for preparing a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 7 or 10, characterized in that: the dosage of the nickel/aluminum catalyst is 0.5-0.9 mmol/100g relative to the dosage of the asymmetric long-chain branched polystyrene-conjugated diene copolymer glue solution, wherein the nickel/aluminum catalyst is measured by nickel mass, and the asymmetric long-chain branched polystyrene-conjugated diene copolymer glue solution is measured by dry basis mass.
12. The process for producing a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 7, wherein: the hydrogenation reaction conditions are as follows: the temperature is 70-80 ℃, the hydrogen pressure is 1.2-1.5 MPa, and the reaction time is 1.5-3.0 h.
13. Use of a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to any one of claims 1 to 6, characterized in that: as viscosity index improver for lubricating oil.
14. Use of a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 13, characterized in that: the mass percentage content of the hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer base oil added is 0.8-1.5%.
15. Use of a hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer according to claim 14, characterized in that: the mass percentage content of the hydrogenated asymmetric long chain branched polystyrene-conjugated diene copolymer base oil added is 0.95-1.15%.
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