CN108503741A - 可用作润滑剂添加剂的氢化聚丁二烯 - Google Patents
可用作润滑剂添加剂的氢化聚丁二烯 Download PDFInfo
- Publication number
- CN108503741A CN108503741A CN201810160335.8A CN201810160335A CN108503741A CN 108503741 A CN108503741 A CN 108503741A CN 201810160335 A CN201810160335 A CN 201810160335A CN 108503741 A CN108503741 A CN 108503741A
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- CN
- China
- Prior art keywords
- butadiene polymer
- hydrogenated butadiene
- weight
- polymer
- hydrogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 100
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 title claims description 73
- 239000003879 lubricant additive Substances 0.000 title description 3
- 239000000314 lubricant Substances 0.000 claims abstract description 43
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 34
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000012530 fluid Substances 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- 239000002199 base oil Substances 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 22
- 230000005540 biological transmission Effects 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000009472 formulation Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 8
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000010687 lubricating oil Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 239000010705 motor oil Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- 239000012208 gear oil Substances 0.000 claims description 5
- 239000010720 hydraulic oil Substances 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000001979 organolithium group Chemical group 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005461 lubrication Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 38
- 239000002585 base Substances 0.000 description 27
- 229920013639 polyalphaolefin Polymers 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 238000007792 addition Methods 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- -1 cyclic aliphatic Chemical class 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000010722 industrial gear oil Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 238000011925 1,2-addition Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000013558 reference substance Substances 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010718 automatic transmission oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UUQLCJCZFWUWHH-UHFFFAOYSA-N lithium;1-phenylhexylbenzene Chemical compound [Li+].C=1C=CC=CC=1[C-](CCCCC)C1=CC=CC=C1 UUQLCJCZFWUWHH-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- XWRJSDBMRJIGSK-UHFFFAOYSA-N lithium;phenylmethylbenzene Chemical compound [Li+].C=1C=CC=CC=1[CH-]C1=CC=CC=C1 XWRJSDBMRJIGSK-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C10M143/14—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing non-conjugated diene
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
- C10M107/08—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing butene
-
- 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
- C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及低分子量氢化聚丁二烯和涉及制备这些聚合物的方法。本发明还涉及包含这些聚合物的润滑剂组合物及其用途。
Description
技术领域
本发明涉及低分子量氢化聚丁二烯和涉及制备这些聚合物的方法。本发明还涉及包含这些聚合物的润滑剂组合物,和涉及这些润滑剂组合物用作自动传动流体、手动传动流体、无级变速传动流体、发动机油、齿轮油配制剂、工业齿轮油配制剂、轴流体配制剂、双离合传动流体、专用混合动力传动流体或作为液压油的用途。
背景技术
本发明涉及润滑领域。润滑剂是降低表面之间的摩擦的组合物。除了允许两个表面之间的运动自由度和降低表面的机械磨损外,润滑剂还可抑制表面的腐蚀和/或可抑制由于热或氧化导致的对表面的损坏。润滑剂组合物的实例包括但不限于发动机油、传动流体、齿轮油、工业润滑油、油脂和金属加工油。
典型的润滑剂组合物包括基础流体和任选一种或多种添加剂。常规基础流体是烃,例如矿物油。术语“基础油”或“基础流体”通常可互换使用。此处,将“基础流体”用作通用术语。
根据润滑剂的预期用途,可以将各种添加剂与基础流体组合。润滑剂添加剂的实例包括但不限于粘度指数改进剂、增稠剂、氧化抑制剂、腐蚀抑制剂、分散剂、高压添加剂、消泡剂和金属钝化剂。
典型的非聚合物型基础流体作为润滑剂是较不有效的,这是因为它们的低的粘度和在较高工作温度下进一步降低的粘度。因此,将聚合物型添加剂用于增稠所述基础油和使粘度随温度变化的变化降低。术语“粘度指数(VI)”用于描述这种粘度随温度的变化。所述VI越低,粘度随温度的变化就越大,并且反之亦然。因此,对于润滑剂配制剂,高的VI是希望的。为了改进VI,可将聚合物型添加剂或粘度指数改进剂(VII)添加到润滑剂配制剂中。将聚合物型添加剂添加到润滑剂配制剂中的缺点是,它们随着时间流逝将经历剪切应力和将机械降解。较高分子量聚合物是较好的增稠剂,但将更易遭受导致聚合物降解的剪切应力。为了降低聚合物降解的量,可将聚合物的分子量降低,从而获得更加剪切稳定的聚合物。这些剪切稳定的低分子量聚合物不再是非常有效的增稠剂,并且为了达到希望的粘度必须在所述润滑剂中以较大的浓度使用。这些低分子量聚合物典型地具有低于20,000g/mol的分子量,并且也叫做合成高粘度基础流体。
常用的合成基础流体是聚α烯烃、聚甲基丙烯酸烷基酯和乙烯-丙烯共聚物,它们的关键特征是在粘度方面良好的操作性能,因为这些基础流体在性质上是聚合物型的并提供改进的粘度指数。
美国专利5,945,485和美国专利3,312,621公开了包含1,4-丁二烯和1,2-丁二烯单体单元的氢化嵌段共聚物的用途。所述共聚物是氢化的并包含至少10重量%的至少一种可结晶链段和至少一种低结晶度链段。所述聚合物据说可用作粘度指数改进剂。
EP0318848B1描述了以AB嵌段结构的丁二烯的氢化嵌段共聚物,其具有高于30,000g/mol的数均分子量。这些聚合物会太粘稠以至于不能用作合成基础流体。另外,所述高分子量不会提供由基础流体要求的足够的剪切稳定性。
美国专利3,312,621描述了丁二烯共聚物,其具有75,000至300,000g/mol,优选150,000至250,000g/mol的数均分子量。这些共聚物具有嵌段结构,并具有至少90%的1,4构型并且不是氢化的。
美国专利5,310,814描述了1,2-丁二烯和1,4-丁二烯的非氢化嵌段共聚物作为粘度指数改进剂。没有公开作为合成基础流体的用途,并且推荐的在油中的重量百分比在0.1重量%至3重量%范围内,这是粘度指数改进剂的典型特征。
美国专利3,600,311公开了丁二烯的氢化共聚物,其中所述丁二烯单体的45-95重量%处于1,4构型,和所述丁二烯的10-55重量%处于1,2构型。所述聚合物被说明是用于控制蜡沉积的有用添加剂。
美国专利3,329,613涉及可用作油添加剂的非氢化聚丁二烯聚合物的用途。所公开的聚合物应当基本上处于1,4构型。
现有的产品,例如聚α烯烃(PAO),对于一些应用不具有必要的性能水平。还需要提供在工业齿轮油领域中而不仅仅用于工业润滑剂的替代方案。特别地,希望替换现有高粘度聚α烯烃,因为这些产品是昂贵的,需要大量的聚合物增稠至希望的粘度,并且对于关键的配制剂组分不提供充分的溶解性。因此,本发明的目的是提供高剪切稳定的合成基础流体或润滑油添加剂,其在润滑油组合物中对于油溶解性和组分溶解性以及对于低温性能具有有利影响。另外,与典型使用的聚α烯烃相比使用更低量的聚合物,这些新的聚合物还应当能够将油增稠到希望的粘度。这些高剪切稳定的聚合物还应该具有高的粘度指数,高的闪点和良好的氧化稳定性。
发明内容
在充分的研究后,本发明的发明人已经惊奇地发现,如权利要求1中限定的具有包含在2,000g/mol和10,000g/mol之间的范围内的重均分子量的氢化聚丁二烯,根据它们在润滑组合物中的处理率(treat rate),可用作高剪切稳定的润滑油添加剂或合成基础流体。所述聚合物是由权利要求1中限定的统计分布的衍生自1,2加成和1,4加成的重复单元组成的丁二烯的氢化均聚物。衍生自1,2加成的聚丁二烯重复单元也被称为“1,2-聚丁二烯”或“1,2-丁二烯的单体单元的聚丁二烯”。1,2-聚丁二烯的不饱和双键是末端的乙烯基型不饱和结构。衍生自1,4加成的聚丁二烯重复单元也被称为“1,4-聚丁二烯”或“1,4-丁二烯的单体单元的聚丁二烯”。1,4-聚丁二烯的不饱和双键是内型不饱和结构,其要么以顺式构型要么以反式构型。为了维持良好的油溶性和良好的低温性能,需要1,2对1,4加成的特定重量比例。特别地,本发明的氢化聚丁二烯由基于所述氢化聚丁二烯的总重量计25至45重量%的1,4-丁二烯单体单元和55至75重量%的1,2-丁二烯单体单元组成,以及还具有大于99%的氢化度。
要求保护的氢化聚丁二烯的重均分子量是使用聚丁二烯作为标准物和THF作为洗脱剂通过凝胶渗透色谱法(GPC)测定的。
在本发明的一个优选实施方案中,所述氢化聚丁二烯由基于所述氢化聚丁二烯的总重量计30至45重量%的1,4-丁二烯单体单元和55至70重量%的1,2-丁二烯单体单元组成。
在本发明的一个甚至更优选实施方案中,所述氢化聚丁二烯由基于所述氢化聚丁二烯的总重量计30至40重量%的1,4-丁二烯单体单元和60至70重量%的1,2-丁二烯单体单元组成。
在本发明的另一个优选的实施方案中,所述氢化聚丁二烯具有包括在1.0和1.5之间的范围内的多分散指数(PDI)。根据本发明的一个特别的实施方案,所述氢化聚丁二烯具有包括在1.0和1.2之间的范围内的PDI。
根据本发明的一个特别的实施方案,所述氢化聚丁二烯具有包括在3,000g/mol和9,000g/mol之间的范围内,甚至更优选包括在4,000g/mol和8,000g/mol之间的范围内的重均分子量。
根据另一个方面,本发明还涉及制备本发明的氢化聚丁二烯的方法,所述方法包括如下步骤:
(i)在第一步骤中通过1,3-丁二烯的阴离子聚合制备聚丁二烯,和
(ii)在第二步骤中通过催化氢化将步骤(i)的聚丁二烯氢化。
根据所述方法的一个优选实施方案,步骤(i)的阴离子聚合是在至少一种选自脂族、脂环族或芳族烃溶剂的溶剂中,使用有机金属试剂作为引发剂和在没有任何氧和质子试剂的存在下进行的。
在有机金属试剂中,有机钠、有机锂或有机钾是优选的。
本发明还涉及润滑油组合物,其包含基础油和至少一种本发明的氢化聚丁二烯。
在本发明的优选实施方案中,所述润滑油组合物包含基于所述润滑组合物的总重量计50至99.9重量%的至少一种基础油和0.01至50重量%的至少一种根据本发明的氢化聚丁二烯。取决于所述润滑油组合物的应用,适应性改变所述氢化聚丁二烯在所述油配制剂中的处理率。根据本发明,取决于在所述润滑油组合物中的处理率,所述氢化聚丁二烯可被认为是润滑油添加剂(对于低处理率)或被认为是合成基础流体(对于高处理率)。
本发明还涉及根据本发明的氢化聚丁二烯作为润滑油添加剂或基础流体,尤其在自动传动流体、手动传动流体、无级变速传动流体、发动机油、齿轮油配制剂、工业齿轮油配制剂、轴流体配制剂、双离合器传动流体、专用混合动力传动流体中或在液压油中的用途。
发明详述
根据本发明的氢化聚丁二烯
本发明的发明人已经发现,为了实现希望的性能,本发明的氢化聚丁二烯聚合物的重均分子量必须包括在2,000和10,000g/mol之间的范围内。
在一个优选实施方案中,所述氢化聚丁二烯的多分散指数PDI包括在1.0和1.5之间的范围内。根据本发明的一个特别的实施方案,所述氢化聚丁二烯具有包括在1.0和1.2之间的范围内的PDI。
根据本发明,所要求保护的氢化聚丁二烯具有大于99%的氢化度。所述氢化度被定义为相对于非氢化聚合物,通过加氢实现的碳碳键的摩尔饱和程度。通常,经由核磁共振(NMR)波谱或通过测定碘值探测氢化度。根据本发明的氢化聚丁二烯的氢化度是使用对苯二甲酸二甲酯作为标准物,通过在氘代氯仿溶液中的定量质子核磁共振(质子1H NMR)进行测量的。使用溶剂信号校准化学位移。为了测定所述氢化度,将所述标准物的相应信号积分与烯属质子的信号积分建立关联。对于每个样品,为了定义0%的氢化度,必须使用非氢化参比样品重复所述测量和测定。
如上解释的,在两步法中制备本发明的氢化聚丁二烯,第一步对应于所述聚丁二烯聚合物的制备和第二步是聚丁二烯聚合物的氢化。
第一方法步骤:聚丁二烯制备
根据所述方法的第一步骤,本发明的聚丁二烯聚合物是经由1,3-丁二烯单体的活性阴离子聚合制备的。
这种类型的反应是已经成熟的并且详细描述在H.L.Hsieh,R.P.Quirk,AnionicPolymerization,Principles and Practical Applications,1996,Marcel Dekker,Inc.New York中。
根据本发明,对于1,3-丁二烯的活性阴离子聚合,间歇或半间歇类型的方法是优选的。丁二烯。也可考虑在连续方法中的活性聚合。
通常在脂族、环脂族或芳族烃溶剂中实施所述聚合。脂族烃溶剂的实例是己烷或庚烷。脂环族烃溶剂的实例是环己烷或甲基环己烷。芳族烃溶剂的实例是苯或甲苯。还可将诸如叔胺和/或醚和/或环状醚的极性杂脂族溶剂用作溶剂或共溶剂。叔胺的实例是四亚甲基二胺或N,N,N’,N”,N”-五甲基二亚乙基二胺。醚或环状醚的实例是乙醚和四氢呋喃。通常使用脂族、环脂族或芳族烃溶剂和极性杂脂族溶剂的溶剂混合物。
通常的引发剂是有机金属试剂,其中金属来自碱金属或来自碱土金属。典型的实例是作为引发剂的单或双官能的有机钠、有机锂或有机钾,例如正丁基锂、仲丁基锂、叔丁基锂、1,1-二苯基己基锂、二苯基甲基锂、1,1,4,4,-四苯基-1,4-二锂丁烷、锂萘和它们的钠和钾同系物。根据本发明,有机锂引发剂是优选的,并且正丁基锂引发剂是特别优选的。
在排除氧和质子试剂的情况下,阴离子聚合的活性特征对所得的分子量和多分散指数PDI提供了优异的控制。
通常,使用用于中和大分子阴离子的质子试剂终止所述聚合反应,所述质子试剂例如甲醇、乙醇、2-丙醇或水。
例如描述于WO2014075901中的,典型的反应温度范围在10℃和120℃之间,和典型的反应压力范围在1和100巴之间。
公知的是,经由所述反应混合物的极性和/或经由所述反应温度和/或经由抗衡离子的类型调整1,2-和1,4-加成的重量比例。如上已经指出的,根据本发明,要求所述氢化聚丁二烯由基于所述氢化聚丁二烯的总重量计25至45重量%的1,4-丁二烯单体单元和55至75重量%的1,2-丁二烯单体单元组成。
所述方法的第二步骤:氢化
为了改进抵抗氧化的稳定性,大于99%的聚丁二烯聚合物的高氢化度是理想的。
聚丁二烯和其它不饱和烃聚二烯的催化氢化是成熟的。在如下公开出版物中提供了全面的综述:N.K.Singha,S.Bhattacharjee,S.Sivarim,Hydrogenation of dieneelastomers,their properties and applications:A critical review,RubberChemistry and Technology,1996,第70卷,第309-367页。通常,所述反应要么使用不溶性的负载金属催化剂以非均相形式,要么使用可溶性的有机金属催化剂以均相形式进行。均相催化的氢化的详细描述可例如在US 3,541,064和GB 1,030,306中找到。由于其提供了经济优点,因此使用不溶性的负载的金属作为催化剂的非均相催化广泛用在工业氢化中,并且通常优于均相催化。
通常,为了实现尽可能高的氢化度(即为了产生没有由不饱和C-C键组成的结构)的目标,使用具有高反应性和选择性的方法,在没有副反应(例如降解或通过碳碳偶联的交联)的情况下,进行使用不溶性的负载的金属作为催化剂的聚丁二烯和其它不饱和烃聚二烯的氢化。对于本发明的氢化聚丁二烯,所述的目标也适用。通过除其它参数外还调整催化活性金属的类型、其载体的类型、其在所述载体上的加载量、其浓度、压力、温度和反应时间来满足这些要求属于现有技术(参见WO 2015/040095、US 2,864,809、DE 2,459,115、WO01/42319)。
通常,用于聚丁二烯和其它不饱和烃聚二烯的氢化的催化活性金属包括但不限于Ru、Rh、Pd、Ir、Pt、Mn、Cr、Fe、Co、Ni、U、Cu、Nd、In、Sn、Zn、Ag、Cr和这些金属中的一种或多种的合金。典型的催化剂载体包括但不限于氧化物(Al2O3、TiO2、SiO2或其它氧化物)、碳、硅藻土或其它载体。在间歇或连续操作中,在溶液或本体中,常用的非均相氢化方法,例如填充床或浆液催化剂应用,是适用的。
根据本发明的氢化是使用非均相Al2O3负载的Ru催化剂进行的。
润滑油组合物-基础油
如上指出的,本发明还涉及润滑油组合物,其包含基础油和至少一种本发明的氢化聚丁二烯。
所述基础油对应于适合于它们的应用的/根据预期的用途选择的润滑剂基础油、矿物的、合成的或天然的、动物的或植物的油。
用于配制根据本发明的润滑油组合物的基础油包括例如常规基料,其选自API(美国石油学会)基料类别,其已知被称为第I组、第II组、第III组、第IV组和第V组。所述第I和II组基料是具有小于120的粘度指数(或VI)的矿物油材料(例如石蜡基油和环烷油)。第I组与第II组进一步的区别在于,后者含有大于90%的饱和材料和前者含有小于90%的饱和材料(即大于10%的不饱和材料)。第III组被认为是最高水平的矿物基础油,其具有大于或等于120的VI和大于或等于90%的饱和物水平。优选地,包括在本发明的润滑油组合物中的基础油选自API第II和III组基础油。最优选地,所述润滑剂组合物包含API第III组基础油。第IV组基础油是聚α烯烃(PAO)。第V组基础油是酯和任何其它不包括在第I至IV组基础油中的基础油。这些基础油可以单独使用或者作为混合物使用。
在本发明的优选实施方案中,所述润滑油组合物包含基于所述润滑组合物的总重量计50至99.9重量%的至少一种基础油和0.01至50重量%的至少一种根据本发明的氢化聚丁二烯。
所有如上对于根据本发明的氢化聚丁二烯、基础油、本发明的方法指出的特性和优选项都适合于所述润滑油组合物。
额外的添加剂
根据本发明的润滑油组合物还可以包含任何其它适合用于所述配制剂中的额外的添加剂。这些添加剂包括粘度指数改进剂、倾点降低剂、分散剂、破乳剂、消泡剂、润滑性添加剂、摩擦改进剂、抗氧化剂、洗涤剂、染料、腐蚀抑制剂和/或添味剂。
氢化聚丁二烯的应用
本发明还涉及根据本发明的氢化聚丁二烯根据在所述润滑油组合物中的处理率作为润滑油添加剂或作为合成基础流体的用途。
本发明的氢化聚丁二烯和包含根据本发明的氢化聚丁二烯的润滑油组合物有利地用于驱动体系润滑油(例如手动传动流体、差动齿轮油、自动传动流体和带-无级变速传动流体、轴流体配制剂、双离合传动流体和专用混合动力传动流体)、液压油(例如用于机械装置的液压油、动力方向盘油、减震器油)、发动机油(用于汽油发动机和用于柴油发动机)和工业油配制剂(例如风力涡轮机)。
从根据本发明的氢化聚丁二烯的运动粘度的观点出发,在所述润滑油组合物中的氢化聚丁二烯的重量含量优选包括在基于所述润滑油组合物的总重量计的,关于氢化聚丁二烯的重量方面,1重量%和50重量%之间的范围内。
如果将根据本发明的润滑油组合物用作发动机油,其优选在所述基础油中包含基于所述润滑油组合物的总重量计的2重量%和20重量%之间的本发明的氢化聚丁二烯,这导致在100℃下的运动粘度在4mm2/s至10mm2/s范围内。
如果将本发明的粘度指数改进剂用作机动车齿轮油,其优选在所述基础油中包含基于所述润滑油组合物的总重量计的3重量%至30重量%之间的氢化聚丁二烯,这导致在100℃下的运动粘度在2mm2/s至10mm2/s范围内。
如果将本发明的粘度指数改进剂用作自动传动油,其优选在所述基础油中包含基于所述润滑油组合物的总重量计的3重量%和25重量%之间的氢化聚丁二烯,这导致在100℃下的运动粘度在2mm2/s至6mm2/s范围内。
如果将本发明的粘度指数改进剂用作工业齿轮油,其优选在所述基础油中包含基于所述润滑油组合物的总重量计的15重量%和50重量%之间的氢化聚丁二烯,这导致在100℃下的运动粘度在10mm2/s至40mm2/s范围内。
通过如下非限制性实施例进一步示例性说明本发明。
具体实施方式
实验部分
下文中参照实施例和对比例进一步详细示例性说明本发明,而不意于对本发明的范围进行限制。
样品制备
实施例1是通过两步过程制备的,其包括在第一步骤中的1,3-丁二烯的阴离子聚合和在第二步骤中的催化氢化。1,3-丁二烯的阴离子聚合是通过将如下物质加料到无水和无氧的5升高压釜中进行的:1527g环己烷(在分子筛上纯化的)、48g四氢呋喃(THF)和91g正丁基锂溶液(在环己烷中2.0M)。在T=40℃和p=3.7巴下的剧烈搅拌下,在800g/h的速率下添加1068g丁二烯(在分子筛上纯化的),产生6.3巴的最终压力。即刻将反应混合物冷却到T=20℃,并在p=1巴下添加38g甲醇。在30分钟后,将所述混合物过滤,随后蒸发挥发性溶剂。获得的聚丁二烯具有如下性质:Mw=4.8kg/mol;PDI=1.06;1,2-含量=75重量%;1,4-含量=25重量%。
为了催化氢化,根据Robinson-Mahoney法,将1.5L的50重量%的获得的聚丁二烯在环己烷中的溶液加料到具有催化剂筐的2升高压釜中,并引入8g 3%的Ru/Al2O3壳催化剂。在T=120℃和p=200巴的H2压力下实施氢化24小时。将排出物过滤和将挥发性溶剂蒸发。获得的氢化聚丁二烯的氢化度是100%。
类似于实施例1制备实施例2-13,除了如在表1中所述的在阴离子聚合过程中使用的原材料的量以及在氢化过程中的固体含量。实施例11和12是AB嵌段共聚物样品,其中A/B=50/50(重量/重量)。
使用的试验方法
本发明的氢化聚丁二烯的重均分子量Mw和多分散指数PDI是使用Tosoh EcoSECGPC系统“HLC-8320”,在0.3mL/分钟的流速下,在T=40℃下,采用四氢呋喃(THF)作为洗脱剂,相对于聚丁二烯校正标准物测定的,所述Tosoh EcoSEC GPC系统“HLC-8320”配备有PSSSDV 5μm前置柱和30cm PSS SDV 5μm线性S分离柱,以及RI检测器。
所述对比聚α烯烃(PAO)、聚甲基丙烯酸烷基酯(PAMA)和烯烃共聚物(OCP)样品的重均分子量是通过凝胶渗透色谱法(GPC),使用聚甲基丙烯酸甲酯校正标准物和THF作为洗脱剂测定的。
根据本发明的氢化聚丁二烯的1,2-和1,4-加成重量含量,以及氢化度是借助于1H-NMR光谱法在氘代氯仿中测定的。
根据ASTM D 445测量运动粘度。
自动传动流体、齿轮油、扭矩(torque)和牵引机流体和工业和机动车液压油的低温、低剪切速率粘度对于许多机械装置的恰当操作是相当重要的。为了测量流体的低温粘度性能,可使用Brookfield粘度计。在润滑剂配制剂实施例中报道的Brookfield粘度是根据ASTM D 2983在-30℃的温度下测量的。
石油产品的倾点是其适用于某些应用的适用性的最低温度的指标。流动特性,如倾点,对于正确操作润滑系统、燃料系统和管线作业可能是关键的。所示的实施例的倾点(PP)是根据ASTM D 97测量的。
在根据DIN 51350T6的圆锥滚子轴承试验中,在40℃下在100小时后测量粘度损失。粘度损失是作为1-KV40后/KV40前计算的。
根据ASTM D 92使用Cleveland开杯试验器测量闪点。
经由热重分析法,使用得自TA Instruments的TGA Q5000仪器测量热氧化降解。在空气下,使用室温至505℃的温度范围,在每分钟5℃的速率下完成分析。所述仪器记录了所述样品的初始重量以及相对于温度的重量损失。在所述试验完成时,使用计算机软件获得微商热重分析(DTG)结果。对于每个样品,观察到一个主要的窄的峰,其代表至少98%的重量损失。记录了所述微商峰温度或DTG峰温度,并将其用于比较各种聚合物。
油和对比样品
PAO 8是具有8 cSt的KV100的不同α烯烃的共聚物。用于所述实施例的样品是得自Chevron Phillips的商业产品,PAO 8。
RC 9420是得自Rhein Chemie Additives的商业工业齿轮油添加剂包。
对比例PAO是得自Chevron Phillips的可商购产品。它是高粘度第IV组基础流体(PAO100),其是1-癸烯的均聚物。
对比例PAMA是根据US20130229016A1中的实施例1合成的甲基丙烯酸C12-15酯的共聚物。
对比例OCP是得自Mitsui Chemicals的商业产品HC-600,并对应于烃基合成油,其不具有极性基团并且是乙烯和丙烯的共聚物(烯烃共聚物(OCP))。
在表2和3中示出的结果的解释
表2显示了本体聚合物的一些性质。所述氢化聚丁二烯的本体粘度与聚甲基丙烯酸烷基酯、烯烃共聚物和聚α烯烃在相同的范围内。实际上,本发明的实施例1至6说明了在分子量的小变化的情况下宽范围的粘度,使得本发明的聚合物适合于宽范围的应用和粘度等级。它们的优异的粘度性质符合任何基础流体的操作性能要求。另外,所述氢化聚丁二烯的粘度指数和倾点对于润滑剂应用也是非常好的。
表3显示了用各种聚合物制备的一些工业齿轮油润滑剂配制剂。在低粘度基础流体PAO8中掺混所有的聚合物,达到在40℃下的320 cSt的粘度。在所述配制剂混合物中还以1.8重量%包括RC 9420。
本发明的实施例1至6表明,为了实现320 cSt的KV40,需要与标准基础油相比更小量的聚合物,所述标准基础油例如聚甲基丙烯酸烷基酯(实施例PAMA)和聚α烯烃(实施例PAO)。
因此,所有的实验数据都表明根据本发明的聚合物在保持良好的粘度指数、倾点和Brookfield粘度的同时提供优异的增稠功效。
当将用聚α烯烃(PAO)和实施例3的聚丁二烯制备的配制剂相比较时,这两种配制剂提供了类似的KV40、粘度指数、倾点和剪切稳定性;但所述氢化聚丁二烯配制剂使用少49重量%的聚合物。这种根据本发明的聚合物的显著降低的量提供了经济优点。当将用聚甲基丙烯酸烷基酯(实施例PAMA)和本发明实施例5的氢化聚丁二烯制备的配制剂进行比较时可看见类似的优点。此处,为了实现相同的KV40,需要少51.1重量%的氢化聚丁二烯聚合物,并且用本发明实施例5制备的配制剂提供了改进的在-30℃下Brookfield粘度和粘度指数,而在其它配制剂性质方面没有缺点。使用所述OCP聚合物(实施例OCP)的配制剂还可以与用本发明实施例5制备的配制剂相当。配制剂性质是类似的,但所述氢化聚丁二烯配制剂使用少21.6重量%的聚合物提供了这些性质。
另外,根据本发明的聚合物的低重均分子量和窄的PDI使得所述聚合物能够具有优异的剪切稳定性。在100小时圆锥滚子轴承试验后的粘度损失低于3%,这对于提供这样好的增稠功效的聚合物是令人惊奇地好的。
本发明的发明人已经发现,1,2加成对1,4加成的重量比例影响所述Brookfield-30℃粘度和倾点。特别地,本发明的发明人已经发现,所述氢化聚丁二烯必须由基于所述氢化聚丁二烯的总重量计25至45重量%的1,4-丁二烯单体单元和55至75重量%的1,2-丁二烯单体单元组成。实际上,如果1,2:1,4加成的重量比例过高或过低,则所述Brookfield-30℃粘度和倾点被提高。因此,重要的是保持在如上所述的重量比例内,以保持良好的低温性能。当将本发明实施例3的聚丁二烯与对比例7相比较时,可以看到这种效果。二者具有类似的重均分子量,但对比例7的氢化聚丁二烯具有增加量的1,4加成。所得到的用对比例7制备的配制剂具有在-30℃下Brookfield粘度方面的显著提高。这进一步由也具有非常高的量的1,4加成的对比例10表明。这种氢化聚丁二烯不再可溶于油中。对低温性能的不好的影响也在其中有非常高的量的1,2加成的对比例9中表明。这种聚合物还显示出差的在-30℃下的Brookfield粘度。
在所要求保护的范围外的重均分子量,如果所述分子量高于所要求保护的范围(参见对比例8)也显示了差的剪切稳定性,和如果所述分子量低于所要求保护的范围(参见对比例13)也显示了差的粘度指数和非常差的Brookfield粘度。
实施例11表明,具有嵌段结构(其具有结晶链段)的氢化聚丁二烯,例如现有技术中已知的,产生极差的溶解度(在室温下是固体)。
实施例12是如在现有技术中公开的高分子量嵌段聚丁二烯。实施例12是极高粘度,在非极性溶剂中显示非常差的溶解度。
含有所述氢化聚丁二烯的表3中的配制剂(实施例5)具有与含有实施例PAO的配制剂相比更高的闪点。含有实施例PAMA的配制剂的闪点显示了相当的闪点。这些结果证实了,与现有技术相比,氢化聚丁二烯不具有任何缺点。
实施例1、实施例2和实施例4显示了与实施例PAMA或实施例PAO相比改进的热氧化稳定性。这些实施例具有与实施例PAMA和实施例PAO相比更高的DTG峰温度。
还将含有氢化聚丁二烯的表3中的配制剂送往60天的储存试验以确保所述配制剂组分可溶和在溶液中是稳定的。在此时间内没有观察到分离。
Claims (13)
1.氢化聚丁二烯,其中所述氢化聚丁二烯
(i)具有包括在2,000g/mol和10,000g/mol之间的范围内的重均分子量,
(ii)由基于所述氢化聚丁二烯的总重量计25至45重量%的1,4-丁二烯单体单元和55至75重量%的1,2-丁二烯单体单元组成,和
(iii)具有大于99%的氢化度。
2.根据权利要求1的氢化聚丁二烯,其中所述氢化聚丁二烯由基于所述氢化聚丁二烯的总重量计30至45重量%的1,4-丁二烯单体单元和55至70重量%的1,2-丁二烯单体单元组成。
3.根据权利要求2的氢化聚丁二烯,其中所述氢化聚丁二烯由基于所述氢化聚丁二烯的总重量计30至40重量%的1,4-丁二烯单体单元和60至70重量%的1,2-丁二烯单体单元组成。
4.根据权利要求1至3的任一项的氢化聚丁二烯,其中所述氢化聚丁二烯具有包括在1.0和1.5之间的范围内的多分散指数PDI。
5.根据权利要求4的氢化聚丁二烯,其中所述氢化聚丁二烯具有包括在1.0和1.2之间的范围内的多分散指数PDI。
6.根据权利要求1至5的任一项的氢化聚丁二烯,其中所述氢化聚丁二烯具有包括在3,000g/mol和9,000g/mol之间的范围内的重均分子量。
7.根据权利要求6的氢化聚丁二烯,其中所述氢化聚丁二烯具有包括在4,000g/mol和8,000g/mol之间的范围内的重均分子量。
8.制备如在权利要求1至7的任一项中限定的氢化聚丁二烯的方法,其中所述方法包括:
(i)在第一步骤中通过1,3-丁二烯的阴离子聚合制备聚丁二烯,和
(ii)在第二步骤中通过催化氢化将步骤(i)的聚丁二烯氢化。
9.权利要求8的方法,其中步骤(i)的阴离子聚合是在至少一种如下溶剂中,使用有机金属试剂作为引发剂和在没有任何氧和质子试剂的存在下进行的,所述溶剂选自脂族、脂环族或芳族烃溶剂或极性的杂脂族溶剂或它们的混合物。
10.权利要求8或9的方法,其中所述有机金属试剂选自有机钠、有机锂或有机钾。
11.包含基础油和至少一种如在权利要求1至7的任一项中限定的氢化聚丁二烯的润滑油组合物。
12.如在权利要求11中所述的润滑油组合物,其中所述润滑油组合物包含基于所述润滑组合物的总重量计在50和99.9重量%之间的至少一种基础油和在0.01和50重量%之间的至少一种如在权利要求1至7的任一项中限定的氢化聚丁二烯。
13.如在权利要求1至7的任一项中限定的氢化聚丁二烯作为润滑油添加剂或合成基础流体在自动传动流体、手动传动流体、无级变速传动流体、发动机油、齿轮油配制剂、工业齿轮油配制剂、轴流体配制剂、双离合器传动流体、专用混合动力传动流体中或在液压油中的用途。
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US11453837B2 (en) | 2018-11-13 | 2022-09-27 | Evonik Operations Gmbh | Random copolymers for use as base oils or lubricant additives |
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