CN116948070A - Polybutene-1 and preparation method thereof, non-metallocene catalyst used in polybutene-1 and preparation method thereof - Google Patents
Polybutene-1 and preparation method thereof, non-metallocene catalyst used in polybutene-1 and preparation method thereof Download PDFInfo
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- 229920001748 polybutylene Polymers 0.000 title claims abstract description 96
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 43
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 32
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 18
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 128
- 239000003054 catalyst Substances 0.000 claims description 96
- -1 2-ethylphenyl Chemical group 0.000 claims description 70
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 239000012190 activator Substances 0.000 claims description 38
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910000071 diazene Inorganic materials 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical group C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 5
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- OIDRXSLJYDFQAZ-UHFFFAOYSA-N N[Hf].N1=CC=CC=C1 Chemical group N[Hf].N1=CC=CC=C1 OIDRXSLJYDFQAZ-UHFFFAOYSA-N 0.000 abstract description 75
- 238000009826 distribution Methods 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 24
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000002844 melting Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 25
- 238000012662 bulk polymerization Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 14
- 229910052735 hafnium Inorganic materials 0.000 description 13
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 13
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- NLNYIEUTJQPMED-UHFFFAOYSA-N N1=C(C=CC=C1)N[Hf] Chemical compound N1=C(C=CC=C1)N[Hf] NLNYIEUTJQPMED-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- YYCAWAQZKOZDEB-UHFFFAOYSA-N hafnium;pyridin-2-amine Chemical compound [Hf].NC1=CC=CC=N1 YYCAWAQZKOZDEB-UHFFFAOYSA-N 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RUJTWTUYVOEEFW-UHFFFAOYSA-N 1-(6-bromopyridin-2-yl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=N1 RUJTWTUYVOEEFW-UHFFFAOYSA-N 0.000 description 1
- QWFHFNGMCPMOCD-UHFFFAOYSA-N 6-bromopyridine-2-carbaldehyde Chemical compound BrC1=CC=CC(C=O)=N1 QWFHFNGMCPMOCD-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CPDRCKWKDRDHPW-UHFFFAOYSA-N boric acid;naphthalene Chemical compound OB(O)O.C1=CC=CC2=CC=CC=C21 CPDRCKWKDRDHPW-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000008160 pyridoxine Nutrition 0.000 description 1
- 239000011677 pyridoxine Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides polybutene-1 and a preparation method thereof, and a non-metallocene catalyst and a preparation method thereof, wherein the non-metallocene catalyst comprises a structure shown in the following formula I:wherein R is 1 、R 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, R 3 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 4 Selected from methyl, ethyl, n-propyl, ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl. The non-metallocene catalyst has a bridged pyridine amino hafnium structure, is used for catalyzing and synthesizing polybutene-1, and has higher catalytic activity and high monomer conversion rate, and the prepared polybutene-1 has higher isotacticity and narrower distribution.
Description
Technical Field
The invention relates to the technical field of olefin catalytic polymerization. More particularly, it relates to a non-metallocene catalyst and a preparation method thereof, a method for synthesizing polybutene-1 by using the non-metallocene catalyst and the prepared polybutene-1.
Background
The high isotactic polybutene-1 (PB) is a semi-crystalline polyolefin thermoplastic resin polymerized from butene-1 monomers, enjoying the reputation of "gold in plastics". PB has excellent temperature resistance, durability, chemical stability, plasticity, no smell, no toxicity and no smell, and is one of the most advanced chemical materials in the world at present. Therefore, such high-end thermoplastic resins have important applications in the fields of radiator connection, hot and cold water supply, floor heating, hot melt adhesives, and films and sheets.
Polybutene-1 is prepared by bulk polymerization of butene-1 monomers, mainly by means of a suitable catalyst. There are two main classes of catalyst systems currently used for the polymerization of butene-1 monomers: ziegler-Natta catalysts and metallocene catalysts. Early use of magnesium chloride supported ziegler-natta catalysts was able to effectively catalyze butene-1 polymerization to give polymers of high isotactic crystallinity. Because the Ziegler-Natta catalyst has high catalytic efficiency, the produced polymer has good comprehensive performance and low cost, and the catalyst for industrially producing polybutene-1 is mainly the Ziegler-Natta catalyst. As reported in european patent 82111264.6, a polybutene having properties of thermoplastic elastomer was synthesized with a modified supported titanium catalyst system having an isotacticity of 70% to 80% and a crystallinity of 25% to 40%. Its properties are similar to EPDM/PP, SEBS thermoplastic and plasticized PVC soft materials, and can be used in place of them in many applications, thereby expanding the uses and value of polybutenes. However, the molecular weight distribution of the obtained polymer is particularly broad due to the multiple active centers of the Ziegler-Natta catalyst, generally more than 10, and the mechanical properties of the low molecular weight part are poor, which limits the application thereof in the high-end field.
Metallocene catalysts are also capable of catalyzing the polymerization of butene-1, but the structure of the metallocene catalyst has an important influence on the isotacticity of the final product. The metallocene catalyst is reported to catalyze the polymerization of butene-1, and the regularity of the product is also up to more than 90%. For example, resconi (Resconi L, canurati I, malizia F.Metallocene Catalysts for 1-Butene Polymerization [ J ]. Macromolecular Chemistry & Physics,2010, 208 (4): 423-423.) synthesized dimethylsilyl bridged zirconium dichloride Catalysts containing indene ligands of different substituents, MAO as a cocatalyst, studied the effect of different ligand Catalysts on butene-1 polymerization and polymers. It was found that the catalytic activity at 70℃in bulk polymerization was at most 195.0kg PB/g mc.h (mc=metalocene), the Mw was higher than 4.0 x 105g/mol, the molecular weight distribution was 2.1-2.7, the polymer isotacticity was related to the indenyl complex and the isotacticity was at most 98.5%. Because of the single metal center, the molecular weight distribution of polybutene-1 prepared by the metallocene catalyst is relatively narrow and is generally lower than 3. However, metallocene catalysts are sterically bulky, the large sterically hindered butene-1 monomer is difficult to intercalate, the activity of the metallocene catalyst for catalyzing butene-1 is lower than that of Ziegler-Natta catalysts by more than 10 times.
Currently, polybutene-1 has been successfully commercialized by Basell and Sanjing Japan Petroleum companies (i.e., sanjing chemical company today), but polybutene is not produced in China, and the products are all imported and expensive. Meanwhile, the domestic butene-1 has surplus capacity and extremely low utilization rate, and more than 75% of the butene-1 is sold as fuel oil component, so that how to improve the added value of the butene-1 is a great difficulty to be solved.
Disclosure of Invention
The invention mainly aims to provide polybutene-1 and a preparation method thereof, and a non-metallocene catalyst used in the method and the preparation method thereof, so as to overcome the defects that the molecular weight distribution of polybutene-1 prepared by catalysis of a Ziegler-Natta catalyst is wide, and the molecular weight and activity of polybutene-1 prepared by catalysis of a metallocene catalyst are low in the prior art.
In order to achieve the above object, the present invention provides a non-metallocene catalyst for catalyzing butene-1 polymerization, comprising the structure of formula I:
wherein R is 1 、R 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, R 3 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 4 Selected from methyl, ethyl, n-propyl, ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl.
The non-metallocene catalyst of the invention, wherein R 1 、R 2 Selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkylene groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms; the aliphatic hydrocarbon groups in the aliphatic hydrocarbon group-substituted phenyl groups have 1 to 6 carbon atoms, and the aliphatic hydrocarbon groups in the aliphatic hydrocarbon group-substituted naphthyl groups have 1 to 6 carbon atoms.
The non-metallocene catalyst of the invention, wherein R 1 、R 2 Selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl; said aliphatic hydrocarbyl-substituted phenyl groupWherein the aliphatic hydrocarbon group in the aliphatic hydrocarbon group-substituted naphthyl group is an alkyl group having 1 to 6 carbon atoms; r is R 3 Selected from methyl, ethyl, n-propyl, isopropyl; r is R 4 Selected from methyl groups.
The non-metallocene catalyst of the invention, wherein when Ar is phenyl or naphthyl, R 1 Is hydrogen, R 2 Is 2-isopropylphenyl, or R 1 Is methyl, R 2 Is methyl.
In order to achieve the above object, the present invention also provides a method for preparing a non-metallocene catalyst for catalyzing butene-1 polymerization, comprising the steps of:
Step 1, carrying out coupling reaction on a pyridone (aldehyde) compound and arylboronic acid to obtain an aryl substituted 2-aryl-pyridone (aldehyde) compound;
step 2, performing condensation reaction on the 2, 2-aryl-pyridone (aldehyde) compound and 3, 3-disubstituted-4, 4-biphenyldiamine to obtain a pyridine diimine compound;
step 3, carrying out reduction reaction on the pyridine diimine compound and a reducing agent to obtain a bridged substituted pyridine amino compound ligand;
step 4, deprotonating the bridged substituted pyridine amino compound ligand, and then reacting with hafnium tetrachloride to obtain the bridged substituted pyridine amino hafnium chloride compound;
step 5, reacting the bridged substituted pyridine amino hafnium chloride compound with alkyl magnesium bromide to obtain a bridged pyridine amino hafnium alkyl compound;
wherein R is 1 、R 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, R 3 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 4 Selected from methyl, ethyl, n-propyl, ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl, n is 1,2 or 3, and M is a metal.
The invention relates to a preparation method of a non-metallocene catalyst, wherein the reducing agent is trialkylaluminum or aryl lithium.
In order to achieve the above purpose, the present invention further provides a method for preparing polybutene-1, wherein butene-1 is used as a monomer, and the above non-metallocene catalyst is used as a catalyst for polymerization reaction to obtain polybutene-1.
The preparation method of polybutene-1 of the present invention, wherein an activator is also added in the polymerization reaction, and the molar ratio of the catalyst to the activator is 1:1-10; the activator is a composition of triphenylcarbenium tetra (pentafluorophenyl) borate and aluminum alkyl, and the molar ratio of the triphenylcarbenium tetra (pentafluorophenyl) borate to the aluminum alkyl is 1:50-300.
The preparation method of polybutene-1, provided by the invention, comprises the steps that the molar ratio of the butene-1 monomer to the sum of the amounts of the catalyst and the activator is 1-60000:1; the temperature of the polymerization reaction is 25-100 ℃.
In order to achieve the above purpose, the invention also provides polybutene-1 prepared by the preparation method.
The invention has the beneficial effects that:
the invention provides a non-metallocene catalyst which has a bridged pyridine amino hafnium structure, is used for catalyzing and synthesizing polybutene-1, and has the advantages of higher catalytic activity and high monomer conversion rate, and the prepared polybutene-1 has higher isotacticity and narrower distribution. Further, the polybutene-1 prepared by the non-metallocene catalyst has the weight average molecular weight exceeding 30 ten thousand, narrower molecular weight distribution, lower than 3.0, better mechanical property and thermal stability, the highest isotacticity reaching more than 99 percent and the melting temperature reaching 170 ℃. In addition, the catalyst is used for catalyzing and synthesizing polybutene-1, and has mild reaction condition and high and controllable polymerization reaction.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of polybutene-1 prepared in example 1 of the present invention.
FIG. 2 is a GPC chart of polybutene-1 prepared in example 1 of the present invention.
FIG. 3 is a reaction scheme of the hafnium pyridinaminyl complex of the present invention.
FIG. 4 is a structural formula of a comparative example 20 zirconocene catalyst of the present invention.
FIG. 5 shows a pyridinaminyl hafnium complex Hf4 according to the present invention 1 H NMR spectrum.
FIG. 6 is a mass spectrum of a hafnium pyridinaminyl complex Hf4 of the present invention.
FIG. 7 shows a pyridinaminyl hafnium complex Hf1 of the present invention 1 H NMR spectrum.
FIG. 8 is a mass spectrum of a hafnium pyridinaminyl complex Hf1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples. The examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The invention discloses a non-metallocene catalyst, which is used for catalyzing butene-1 polymerization reaction, and comprises a structure shown in the following formula I:
wherein R is 1 、R 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, R 3 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 4 Selected from methyl, ethyl, n-propyl, ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl.
Wherein Ar and Hf (hafnium) are bonded by a single bond, ar and carbon at the 2-position in the pyridine group are bonded by a single bond, and in addition, hf and carbon at the 2-position in the pyridine group are respectively connected with two adjacent carbons on the same benzene ring as Ar, when Ar is phenyl or phenyl substituted by aliphatic hydrocarbon, the non-metallocene catalyst of the present invention can be represented by the following formula, wherein R is an aliphatic hydrocarbon substituent, and the present invention is not particularly limited to the position and number of the aliphatic hydrocarbon substituent, for example, 1, 2, 3 or 4 substituents are provided on each benzene ring.
When Ar is a naphthyl group or an aliphatic hydrocarbon-substituted naphthyl group, the non-metallocene catalyst of the present invention may be represented by the following formula, wherein R is an aliphatic hydrocarbon-based substituent, the number and position of the aliphatic hydrocarbon-based substituent are not particularly limited in the present invention, and may be on any benzene ring of the naphthyl group, and 1, 2, 3, 4, 5 or 6 substituents may be provided on each naphthalene ring.
Compared with a metallocene catalyst, the non-metallocene bridged pyridine amino hafnium catalyst provided by the invention has a wider space, is favorable for the coordination insertion of a butene-1 monomer with large steric hindrance, and can improve the polymerization activity and the molecular weight of a product; on the other hand, the non-metallocene bridged pyridine amino hafnium catalyst is a single-site catalyst system, and can prepare a polymer with narrower distribution compared with a Ziegler-Natta catalyst. In addition, the non-metallocene bridged pyridine amino hafnium catalyst controls the polymerization of butene-1 through a metal chiral center, so that a high-isotactic polymer can be obtained. Therefore, the catalyst of the invention can prepare polybutene-1 with high molecular weight, narrow distribution and high isotacticity with high activity, and the obtained polymer has better mechanical property and thermal stability.
In one embodiment, the aliphatic hydrocarbon group (R) in the aliphatic hydrocarbon-substituted phenyl group has 1 to 6 carbon atoms, and the aliphatic hydrocarbon group (R) in the aliphatic hydrocarbon-substituted naphthyl group has 1 to 6 carbon atoms; in another embodiment, the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted phenyl group is an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc., and the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted naphthyl group is an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc.
In one embodiment, R of the invention 1 、R 2 Selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkylene groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms; in another embodiment, R of the present invention 1 、R 2 Selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl; r is R 3 Selected from methyl, ethyl, n-propyl, isopropyl; r is R 4 Selected from methyl; in yet another embodiment, ar of the present invention is phenyl or naphthyl, R 1 Is hydrogen, R 2 Is 2-isopropylphenyl; or Ar is phenyl or naphthyl, R 1 Is methyl, R 2 Is methyl.
In the catalyst of the invention, the group R is linked with the active center 4 Where the steric hindrance is small, catalysisThe catalyst has higher catalytic activity, and when the catalyst is used for catalyzing olefin polymerization, the olefin can be more rapidly introduced into the main chain, so the R of the invention 4 More preferably, the group is methyl.
The invention also provides a preparation method of the non-metallocene catalyst, which comprises the steps of firstly carrying out coupling reaction on a pyridone (aldehyde) compound and aryl boric acid to obtain an aryl substituted 2-aryl-pyridone (aldehyde) compound, then carrying out condensation reaction on the 2-aryl-pyridone (aldehyde) compound and 3, 3-disubstituted-4, 4-biphenyldiamine to obtain a pyridine diimine compound, carrying out reduction reaction on the obtained pyridine diimine compound and a strong reducing agent to obtain a bridged substituted pyridine amino compound ligand, carrying out deprotonation reaction on the bridged substituted pyridine amino compound ligand, then adding hafnium tetrachloride to obtain a corresponding bridged substituted pyridine amino hafnium chloride compound, and finally carrying out reaction on the bridged substituted pyridine amino hafnium chloride compound and alkyl magnesium bromide to obtain the corresponding bridged pyridine amino hafnium alkyl compound, namely the non-metallocene catalyst.
In one embodiment, the method for preparing the non-metallocene catalyst of the present invention comprises the steps of:
step 1, carrying out coupling reaction on a pyridone (aldehyde) compound and arylboronic acid to obtain an aryl substituted 2-aryl-pyridone (aldehyde) compound;
wherein R is 1 Selected from hydrogen, hydrocarbyl groups having 1 to 10 carbon atoms; in another embodiment, R 1 Selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkylene groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms; in yet another embodiment, R 1 Selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl.
Wherein Ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl. In another embodiment, the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted phenyl group is an alkyl group having 1 to 6 carbon atoms, and the aliphatic hydrocarbon group in the aliphatic hydrocarbon-substituted naphthyl group is an alkyl group having 1 to 6 carbon atoms.
The condition for the coupling reaction of the pyridone (aldehyde) compound and the arylboronic acid in the present invention is not particularly limited, as long as the two can be reacted to produce the aryl-substituted 2-aryl-pyridone (aldehyde) compound. In one embodiment, the catalyst in the reaction is bis (triphenylphosphine) palladium dichloride and the reaction temperature is the temperature at which toluene is refluxed.
Step 2, performing condensation reaction on the 2, 2-aryl-pyridone (aldehyde) compound and 3, 3-disubstituted-4, 4-biphenyldiamine to obtain a pyridine diimine compound;
wherein R is 3 Selected from hydrogen, hydrocarbyl groups having 1 to 10 carbon atoms; in one embodiment, R3 is selected from methyl, ethyl, n-propyl, isopropyl. The condition for the condensation reaction of the 2-aryl-pyridone (aldehyde) compound and 3, 3-disubstituted-4, 4-biphenyldiamine is not particularly limited in the present invention, as long as the two can be reacted to produce a pyridine diimine compound. In one embodiment, the reaction temperature is the temperature at which toluene is refluxed.
Step 3, carrying out reduction reaction on the pyridine diimine compound and a reducing agent to obtain a bridged substituted pyridine amino compound ligand;
wherein R is 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, M is a metal, n is 1,2 or 3; in another embodiment, R 2 Selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkylene groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms; in yet another embodimentIn embodiments, R 2 Selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl. In yet another embodiment, the reducing agent (R 2 ) n M is a strong reducing agent, for example trialkylaluminum or aryllithium.
The condition for the reduction reaction of the dipyridyl diimine compound and the reducing agent in the present invention is not particularly limited, as long as the two can be reacted to produce the dipyridyl diimine compound. In one embodiment, the mixing temperature of the pyridine diimine compound and the reducing agent is-40 ℃ to 25 ℃ and the reaction temperature is a temperature at which toluene is refluxed.
Step 4, deprotonating the bridged substituted pyridine amino compound ligand, and then reacting with hafnium tetrachloride to obtain the bridged substituted pyridine amino hafnium chloride compound;
in one embodiment, the bridged substituted pyridinaminyl compound ligand undergoes a proton removal reaction under the action of n-butyllithium and then reacts with hafnium tetrachloride to yield a bridged substituted pyridinaminyl hafnium chloride compound. The reaction conditions for the deprotonation and the reaction with hafnium tetrachloride are not particularly limited, and in one embodiment, the reaction temperature is a temperature at which toluene is refluxed.
Step 5, reacting the bridged substituted pyridine amino hafnium chloride compound with alkyl magnesium bromide to obtain a bridged pyridine amino hafnium alkyl compound;
wherein R is 4 Selected from methyl, ethyl, n-propyl. The reaction conditions of the bridged substituted pyridylaminohafnium chloride compound and the alkyl magnesium bromide are not particularly limited in the present invention, so long as the two can be reacted to obtain the bridged pyridylaminohafnium alkyl The compound is obtained. In one embodiment, the reaction temperature is room temperature, such as 20-30 ℃. In one embodiment, the preparation of the bridged pyridinamino hafnium alkyl compound of the present invention is carried out under the protection of an inert gas, and the kind of inert gas is not particularly limited in the present invention, for example, nitrogen, argon, etc.
The bridged pyridine amino hafnium alkyl compound prepared by the invention is used as a catalyst for butene-1 polymerization reaction, has higher polymerization activity and higher monomer conversion rate, even can reach 100 percent, and has mild reaction conditions and high and controllable reaction efficiency.
In one embodiment, the polybutene-1 is used as monomer and the non-metallocene catalyst is used as catalyst to perform polymerization reaction to obtain polybutene-1 at 25-100 deg.c. In another embodiment, the polymerization reaction is a bulk polymerization.
In another embodiment, an activator is also added in the polymerization reaction, and the molar ratio of the non-metallocene catalyst to the activator is 1:1-10; the activator is a combination of triphenylcarbenium tetra (pentafluorophenyl) borate and aluminum alkyl, the molar ratio of the triphenylcarbenium tetra (pentafluorophenyl) borate to the aluminum alkyl is 1:50-300, and the molar ratio of the butene-1 monomer to the sum of the amounts of non-metallocene catalyst and activator species is 100-60000:1. Further, the alkylaluminum may be trimethylaluminum, triethylaluminum, triisobutylaluminum or the like.
The polybutene-1 obtained by the method has the weight average molecular weight not lower than 30 ten thousand, the molecular weight distribution not higher than 3.0, the isotacticity not lower than 98 percent and the melting temperature not lower than 150 ℃, so that the polybutene-1 has better mechanical property and thermal stability.
In one embodiment, the polybutene-1 prepared by the method has a weight average molecular weight of 30-70 ten thousand, a dispersion coefficient of 2.0-3.0, an isotacticity of more than or equal to 98% and a melting temperature of 155-170 ℃.
The non-metallocene catalyst is used for synthesizing polybutene-1 from butene-1, can solve the problems of surplus capacity and extremely low utilization rate of domestic butene-1, and can be sold as fuel oil component by more than 75%, thereby improving the added value of butene-1 products; in addition, the polybutene-1 obtained by the method has good mechanical property and thermal stability, and can meet the production requirements of radiator connection, hot and cold water supply, floor heating, hot melt adhesive, film and sheet fields and the like, so that monopoly can be broken.
The technical scheme of the invention will be further described through specific examples. The activators used in the examples below were as follows:
activator A1: the composition of triphenylcarbonium tetra (pentafluorophenyl) borate and trimethylaluminum comprises the following components in molar ratio: 1:67;
Activator A2: the composition of triphenylcarbonium tetra (pentafluorophenyl) borate and triethylaluminum comprises the following components in mole ratio: 1:67;
activator A3: the composition of triphenylcarbonium tetra (pentafluorophenyl) borate and triisobutylaluminum comprises the following components in mole ratio: 1:67;
activator A4: the composition of triphenylcarbonium tetra (pentafluorophenyl) borate and triisobutylaluminum comprises the following components in mole ratio: 1:50;
activator A5: the composition of triphenylcarbonium tetra (pentafluorophenyl) borate and triisobutylaluminum comprises the following components in mole ratio: 1:150;
activator A6: the composition of triphenylcarbonium tetra (pentafluorophenyl) borate and triisobutylaluminum comprises the following components in mole ratio: 1:300.
The following provides a specific synthesis method of a pyridine amino hafnium complex, and the reaction route is not shown in fig. 3.
Under the nitrogen atmosphere, firstly 10mmol of 6-bromopyridine-2-formaldehyde/2-acetyl-6-bromopyridine, 10mmol of naphthalene boric acid/phenylboric acid, 15mg of bis (triphenylphosphine) palladium dichloride and 3g of potassium carbonate are sequentially added into a branched bottle, then 30mL of ethanol, 20mL of toluene and 10mL of water are added into the branched bottle by a syringe, and reflux reaction is carried out for 24h. After separation, extracted with ethyl acetate, naHCO 3 Washing with anhydrous Na 2 SO 4 Drying and spin drying to obtain 2-aryl-pyridone (aldehyde) compound.
10mmol of 2-aryl-pyridone (aldehyde) compound, 5.5mmol of 2,2 '-di-tert-butyl-1, 1' -diaminobiphenyl and 10mg of p-toluenesulfonic acid were dissolved in 50mL of toluene under nitrogen atmosphere, and the mixture was refluxed with water for 48 hours. Spin-drying the solvent, eluting with ethanol, and drying to obtain the pyridine diimine compound.
The pyridine diimine compound was dissolved in dry tetrahydrofuran. 2-isopropyllithium/trimethylaluminum was slowly added dropwise to the solution at-40℃and after stirring for 1h, the solution was slowly returned to room temperature and heated to 90℃overnight under reflux. NH under ice-water bath 4 Quench with aqueous Cl, separate, extract with ethyl acetate, wash with brine, dry Na 2 SO 4 And drying and spin-drying to obtain the pyridine amino compound ligand.
In a reaction flask filled with nitrogen, 1.7mmol of the pyridoxine ligand was weighed, dissolved in 20mL of dry toluene, and 1.14mL of an n-butyllithium solution was added dropwise at 0℃and the mixture was heated under reflux for 3 hours. Toluene was drained, washed with n-hexane, and the supernatant was decanted to give a yellow lithium salt. Redissolving the lithium salt with toluene, hfCl 4 0.61g was transferred into the reaction system and heated to 90℃and refluxed overnight. The solution temperature was then reduced to room temperature, 2.13mL of MeMgBr solution was added dropwise, and stirred at room temperature for 3h. The solvent was drained off, the solid was washed 3 times with n-hexane, and the n-hexane filtrate was collected after filtration. The solvent was concentrated to about 3mL and crystallized at-35 ℃ overnight. The crystals were filtered, washed with frozen n-hexane and dried. Obtain the pyridine amino hafnium methyl compound.
The bridged pyridine amino hafnium compound obtained by the method has the following structural formula:
wherein, the pyridine amino hafnium complex Hf1: ar represents a naphthalene ring, R 1 Represents hydrogen, R 2 Represents 2-isopropylphenyl;
hafnium pyridinaminyl complex Hf2: ar represents a naphthalene ring, R 1 Represents methyl, R 2 Represents methyl;
hafnium pyridinaminyl complex Hf3: ar represents a benzene ring, R 1 Represents hydrogen, R 2 Represents 2-isopropylphenyl;
hafnium pyridinaminyl complex Hf4: ar represents a benzene ring, R 1 Represents methyl radicals、R 2 Represents methyl.
FIG. 5 shows a pyridinaminyl hafnium complex Hf4 according to the present invention 1 An H NMR spectrum, FIG. 6 is a mass spectrum of a hafnium pyridinaminyl complex Hf4 of the present invention, FIG. 7 is a hafnium pyridinaminyl complex Hfl of the present invention 1 An H NMR spectrum, FIG. 8 is a mass spectrum of a hafnium pyridinaminyl complex Hfl of the present invention. As shown in FIGS. 5 to 8, the method for synthesizing a hafnium pyridinaminyl complex according to the present invention can obtain a target compound.
The composition ratios of the pyridine amino hafnium catalyst and the activator in each example are as follows:
hafnium pyridinamine based catalyst C1-1: the molar ratio of the combination of the activator A1 and the pyridinium hafnium amino complex Hf1 (the activator is calculated by triphenylcarbonium tetrakis (pentafluorophenyl) borate) is as follows: 1.5:1;
pyridine amino hafnium catalyst C1-2: the mole ratio of the composition of the activator A2 and the pyridine amino hafnium complex Hf1 is as follows: 1.5:1;
Pyridine amino hafnium catalyst C1-3: the mole ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf1 is as follows: 1.5:1;
pyridine amino hafnium catalyst C1-4: the mole ratio of the composition of the activator A4 and the pyridine amino hafnium complex Hf1 is as follows: 1.5:1;
pyridine amino hafnium catalyst C1-5: the mole ratio of the composition of the activator A5 and the pyridine amino hafnium complex Hf1 is as follows: 1.5:1;
pyridine amino hafnium catalyst C1-6: the mole ratio of the composition of the activator A6 and the pyridine amino hafnium complex Hf1 is as follows: 1.5:1;
pyridine amino hafnium catalyst C1-7: the mole ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf1 is as follows: 1.0:1;
pyridine amino hafnium catalyst C1-8: the mole ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf1 is as follows: 3.0:1;
pyridine amino hafnium catalyst C1-9: the mole ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf1 is as follows: 5.0:1;
pyridine amino hafnium catalyst C2-1: the mole ratio of the composition of the activator A1 and the pyridine amino hafnium complex Hf2 is as follows: 1.5:1;
pyridine amino hafnium catalyst C2-2: the mol ratio of the composition of the activator A2 and the pyridine amino hafnium complex Hf2 is 1.5:1;
Pyridine amino hafnium catalyst C2-3: the mol ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf2 is 1.5:1;
pyridine amino hafnium catalyst C3-3: the mole ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf3 is as follows: 1.5:1;
pyridine amino hafnium catalyst C4-3: the mole ratio of the composition of the activator A3 and the pyridine amino hafnium complex Hf4 is as follows: 1.5:1;
example 1
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by a bridged pyridine amino hafnium catalyst C1-3, and comprises the following steps:
10L reaction kettle N 2 Continuously replacing for 30min to ensure that the water oxygen in the kettle is removed; 400g of butene-1 monomer (molar ratio of monomer to catalyst C1-3 24000:1) were then added, the polymerization temperature was maintained at 60℃and stirred for half an hour. Subsequently, 292. Mu. Mol of a bridged hafnium pyridinamine-based catalyst C1-3 containing a hafnium pyridinamine complex (Hf 1 in this example) was added to the system to initiate polymerization, and after 60 minutes of polymerization, 10vol% hydrochloric acid acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, then washed three times with ethanol and dried in vacuo to constant weight.
FIG. 1 is a nuclear magnetic resonance spectrum of polybutene-1 prepared in example 1 of the present invention. FIG. 2 is a GPC chart of polybutene-1 prepared in example 1 of the present invention. As shown in FIG. 1, the absorption peak of the methylene of the main chain of polybutene-1 was 39.4ppm, the absorption peak of the methine of the main chain of polybutene-1 was 36.9ppm, the absorption peak of the branched methylene of polybutene-1 was 27.8ppm, and the absorption peak of the branched methyl of polybutene-1 was 11.7 ppm; as shown in FIG. 2, polybutene-1 had a weight average molecular weight of 58 ten thousand and a molecular weight distribution index of 2.2.
Therefore, the catalyst activity of the bridged pyridine amino hafnium catalyst C1-3 in this example was 19.6kg polymer/(mmol Hf.h), the weight average molecular weight of the prepared polybutene-1 was 58 ten thousand, the molecular weight distribution index was 2.2, the melting temperature was 166℃and the isotacticity was > 99%.
Example 2
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-3. The experimental procedure in example 1 was followed, but the polymerization temperature was varied to 25 ℃.
In this example, the catalyst activity of the bridged pyridine amino hafnium catalyst C1-3 was 5.8kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 31 ten thousand, the molecular weight distribution index was 3.0, the melting temperature was 161℃and the isotacticity was 97%.
Example 3
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-3. The polymerization temperature was 80℃according to the experimental procedure in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-3 was 12.9kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 49 ten thousand, the molecular weight distribution index was 1.6, the melting temperature was 162℃and the isotacticity was 97%.
Example 4
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C2-3. The procedure was followed as in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C2-3 was 11.6kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 45 ten thousand, the molecular weight distribution index was 3.0, the melting temperature was 167℃and the isotacticity was 95%.
Example 5
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by a bridged pyridine amino hafnium catalyst C3-3. The procedure was followed as in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C3-3 was 28.3kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 34 ten thousand, the molecular weight distribution index was 2.0, the melting temperature was 166℃and the isotacticity was 97%.
Example 6
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by a bridged pyridine amino hafnium catalyst C4-3. The procedure was followed as in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C4-3 was 4.6kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 61 ten thousand, the molecular weight distribution index was 2.8, the melting temperature was 170℃and the isotacticity was 98%.
Example 7
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-3. The butene-1 monomer was added in an amount of 2g (molar ratio of monomer to catalyst C1-3: 100:1) according to the procedure of example 1.
In this example, the catalyst activity of the bridged pyridine amino hafnium catalyst C1-3 was 9.5kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 36 ten thousand, the molecular weight distribution index was 1.0, the melting temperature was 169℃and the isotacticity was 99%.
Example 8
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-3. The butene-1 monomer was added at 20g (molar ratio of monomer to catalyst C1-3: 1000:1) according to the procedure described in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-3 was 34.3kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 33 ten thousand, the molecular weight distribution index was 1.2, the melting temperature was 169℃and the isotacticity was 99%.
Example 9
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-3. The butene-1 monomer was added at 160g (molar ratio of monomer to catalyst C1-3 8000:1) according to the procedure described in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-3 was 23.4kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 41 ten thousand, the molecular weight distribution index was 1.3, the melting temperature was 158℃and the isotacticity was 98%.
Example 10
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-3. The butene-1 monomer was added at 800g (molar ratio of monomer to catalyst C1-3 40000:1) according to the procedure described in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-3 was 57.3kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 64 ten thousand, the molecular weight distribution index was 1.7, the melting temperature was 168℃and the isotacticity was 98%.
Example 11
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by a bridged pyridine amino hafnium catalyst C1-7. According to the experimental method in example 1, the amount of the bridged pyridine amino hafnium complex added was 292. Mu. Mol, and the amount of the triphenylcarbonium tetrakis (pentafluorophenyl) borate was changed to 292. Mu. Mol (the molar ratio of the triphenylcarbonium tetrakis (pentafluorophenyl) borate to the bridged pyridine amino hafnium complex in the activator was 1:1).
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-7 was 12.4kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 49 ten thousand, the molecular weight distribution index was 1.5, the melting temperature was 168℃and the isotacticity was 98%.
Example 12
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-8. The amount of bridged pyridinium hafnium amino complex added was 292. Mu. Mol, and the amount of triphenylcarbonium tetrakis (pentafluorophenyl) borate was changed to 876. Mu. Mol (molar ratio of triphenylcarbonium tetrakis (pentafluorophenyl) borate to bridged pyridinium hafnium amino complex 1 in the activator was 3:1) according to the experimental procedure in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-8 was 14.6kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 59 ten thousand, the molecular weight distribution index was 1.6, the melting temperature was 168℃and the isotacticity was 98%.
Example 13
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-9. According to the experimental procedure in example 1, the amount of bridged pyridinium hafnium amino complex added was 292. Mu. Mol, and the amount of triphenylcarbonium tetrakis (pentafluorophenyl) borate was changed to 1160. Mu. Mol (molar ratio of triphenylcarbonium tetrakis (pentafluorophenyl) borate to bridged pyridinium hafnium amino complex 1 in the activator: 5:1).
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-9 was 19.3kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 62 ten thousand, the molecular weight distribution index was 1.7, the melting temperature was 168℃and the isotacticity was 98%.
Example 14
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by a bridged pyridine amino hafnium catalyst C1-4. According to the experimental procedure in example 1, the amount of bridged pyridinium hafnium amino complex added was 292. Mu. Mol, the amount of triphenylcarbonium tetrakis (pentafluorophenyl) borate was 438. Mu. Mol, and the amount of triisobutylaluminum was changed to 21900. Mu. Mol (molar ratio of triphenylcarbonium tetrakis (pentafluorophenyl) borate to triisobutylaluminum was 1:50).
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-4 was 15.1kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 39 ten thousand, the molecular weight distribution index was 1.8, the melting temperature was 162℃and the isotacticity was 98%.
Example 15
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-5. According to the experimental procedure in example 1, the amount of bridged pyridinium hafnium amino complex added was 292. Mu. Mol, the amount of triphenylcarbonium tetrakis (pentafluorophenyl) borate was 438. Mu. Mol, and the amount of triisobutylaluminum was changed to 65700. Mu. Mol (molar ratio of triphenylcarbonium tetrakis (pentafluorophenyl) borate to triisobutylaluminum was 1:150).
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-5 was 19.1kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 50 ten thousand, the molecular weight distribution index was 2.0, the melting temperature was 159℃and the isotacticity was 98%.
Example 16
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by a bridged pyridine amino hafnium catalyst C1-6. According to the experimental procedure in example 1, the amount of bridged pyridinium hafnium amino complex added was 292. Mu. Mol, the amount of triphenylcarbonium tetrakis (pentafluorophenyl) borate was 438. Mu. Mol, and the amount of triisobutylaluminum was changed to 131400. Mu. Mol (molar ratio of triphenylcarbonium tetrakis (pentafluorophenyl) borate to triisobutylaluminum was 1:300).
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-6 was 15.6kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 38 ten thousand, the molecular weight distribution index was 2.5, the melting temperature was 160℃and the isotacticity was 98%.
Example 17
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-1. The aluminum alkyl added was trimethylaluminum according to the experimental procedure in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-1 was 11.5kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 37 ten thousand, the molecular weight distribution index was 2.0, the melting temperature was 168℃and the isotacticity was 98%.
Example 18
The embodiment provides a preparation process of polybutene-1, which is prepared by catalyzing bulk polymerization of butene-1 by using a bridged pyridine amino hafnium catalyst C1-2. The aluminum alkyl added was triethylaluminum according to the experimental procedure in example 1.
In this example, the catalytic activity of the bridged pyridine amino hafnium catalyst C1-2 was 19.9kg polymer/(mmol Hf.h), and the weight average molecular weight of the prepared polybutene-1 was 46 ten thousand, the molecular weight distribution index was 1.8, the melting temperature was 164℃and the isotacticity was 98%.
To better illustrate the benefits of the present patent, ziegler-Natta catalysts, zirconocene catalysts were used as comparative examples to catalyze butene-1 polymerization.
Comparative example 19
The comparative example provides a polybutene-1 preparation process, which is prepared by catalyzing butene-1 homopolymerization through a Ziegler-Natta catalyst, and comprises the following steps:
10L reaction kettle N 2 Continuously replacing for 30min to ensure that the water oxygen in the kettle is removed; 400g of butene-1 monomer and 2ml of triethylaluminum were then added, stirred, the temperature was kept at 60℃and stirred for half an hour. 200mg of Ziegler-Natta catalyst was then added to the reaction system and the polymerization was timed, and after 60 minutes of polymerization, 10% hydrochloric acid acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, then washed three times with ethanol and dried in vacuo to constant weight. The Ziegler-Natta catalyst used in this comparative example was the catalyst disclosed in Chinese patent CN 201510954492.2.
The Ziegler-Natta catalyst in this comparative example had a catalytic activity of 2.2kg polymer/(mmol Ti.h) and the polybutene-1 prepared had a weight average molecular weight of 16 ten thousand, a molecular weight distribution index of 13.7, a melting temperature of 127℃and an isotacticity of 96%.
Comparative example 20
The comparative example provides a preparation process of polybutene-1, which is prepared by catalyzing butene-1 homopolymerization through a metallocene catalyst, and comprises the following steps:
10L reaction kettle N 2 Continuously replacing for 30min to ensure that the water oxygen in the kettle is removed; 400g of butene-1 monomers were then added and2ml of Methylaluminoxane (MAO), stirred, the temperature was kept at 60℃and stirred for half an hour. Subsequently, 300. Mu. Mol of a zirconocene catalyst (the structure of the zirconocene catalyst is shown in FIG. 4) was added to the reaction system and the polymerization was continued for 60 minutes, and then, a 10% hydrochloric acid-acidified ethanol solution was added to terminate the polymerization. The polymer was filtered, then washed three times with ethanol and dried in vacuo to constant weight.
The catalytic activity of the zirconocene catalyst in this comparative example was 0.9kg polymer/(mmol Zr.h), the weight average molecular weight of the prepared polybutene-1 was 38 ten thousand, the molecular weight distribution index was 1.9, the melting temperature was 149℃and the isotacticity was 90%.
The results of the examples and the comparative examples show that the polymerization activity of the non-metallocene catalyst for catalyzing the butene-1 is as high as 19.6kg polymer/(mmol Hf.h), the weight average molecular weight of the prepared polybutene-1 is 58 ten thousand, the molecular weight distribution index is 2.2, the melting temperature is 166 ℃, the isotacticity is more than 99%, and the temperature resistance is good. The Ziegler-Natta catalyst is used for catalyzing the polymerization of butene-1, the catalytic activity is reduced by only 2.2kg polymer/(mmol Ti.h), the distribution of the polymer is obviously widened due to multiple active centers, the molecular weight distribution index is 13.7, the melting temperature of the obtained polymer is obviously reduced by only 127 ℃, meanwhile, the metallocene catalyst is used for catalyzing the polymerization of butene-1, the steric hindrance is large, the butene-1 monomer is difficult to insert, and the polymerization activity is further reduced by only 0.9kg polymer/(mmol Zr.h).
The invention provides a bridged pyridine amino hafnium catalyst, which is synthesized into a bridged pyridine amino hafnium alkyl compound mainly through a Suzuki coupling reaction, a Schiff base reaction and a reduction reaction, and the non-metallocene catalyst has a wider space, is favorable for coordination insertion of a large-steric-hindrance butene-1 monomer, so that the polymerization activity and the molecular weight of a product can be improved; the non-metallocene bridged pyridine amino hafnium complex is a single-active-site catalyst system, and polymerization of butene-1 is controlled through a metal chiral center, so that a polymer with narrower distribution and higher isotacticity can be prepared. Thereby overcoming the defects or shortages of wide molecular weight distribution of polybutene-1 prepared by Ziegler-Natta catalyst and low molecular weight and low activity of polybutene-1 prepared by metallocene catalyst. Meanwhile, the invention also provides a preparation technology of the non-metallocene catalyst polybutene-1, which has the advantages of mild polymerization reaction conditions, high polymerization activity, highest monomer conversion rate and high and controllable whole polymerization reaction. The technology can effectively break technical monopoly of foreign polybutene-1 products, and optimize the industrial structure of butene-1 resources for high-end utilization.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A non-metallocene catalyst for catalyzing the polymerization of butene-1, the non-metallocene catalyst comprising the structure of formula I:
wherein R is 1 、R 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, R 3 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 4 Selected from methyl, ethyl, n-propyl, ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl.
2. The non-metallocene catalyst of claim 1, wherein R 1 、R 2 Selected from hydrogen, alkyl groups having 1 to 6 carbon atoms, alkylene groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms; the aliphatic hydrocarbon groups in the aliphatic hydrocarbon group-substituted phenyl groups have 1 to 6 carbon atoms, and the aliphatic hydrocarbon groups in the aliphatic hydrocarbon group-substituted naphthyl groups have 1 to 6 carbon atoms.
3. The non-metallocene catalyst according to claim 2, wherein R 1 、R 2 Selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, neobutyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl; the fatty alkyl in the fatty alkyl substituted phenyl is alkyl with 1-6 carbon atoms, and the fatty alkyl in the fatty alkyl substituted naphthyl is alkyl with 1-6 carbon atoms; r is R 3 Selected from methyl, ethyl, n-propyl, isopropyl; r is R 4 Selected from methyl groups.
4. The non-metallocene catalyst according to claim 3, wherein when Ar is phenyl or naphthyl, R 1 Is hydrogen, R 2 Is 2-isopropylphenyl, or R 1 Is methyl, R 2 Is methyl.
5. A preparation method of a non-metallocene catalyst is characterized in that the non-metallocene catalyst is used for catalyzing butene-1 polymerization reaction, and comprises the following steps:
step 1, carrying out coupling reaction on a pyridone (aldehyde) compound and arylboronic acid to obtain an aryl substituted 2-aryl-pyridone (aldehyde) compound;
step 2, performing condensation reaction on the 2, 2-aryl-pyridone (aldehyde) compound and 3, 3-disubstituted-4, 4-biphenyldiamine to obtain a pyridine diimine compound;
Step 3, carrying out reduction reaction on the pyridine diimine compound and a reducing agent to obtain a bridged substituted pyridine amino compound ligand;
step 4, deprotonating the bridged substituted pyridine amino compound ligand, and then reacting with hafnium tetrachloride to obtain the bridged substituted pyridine amino hafnium chloride compound;
step 5, reacting the bridged substituted pyridine amino hafnium chloride compound with alkyl magnesium bromide to obtain a bridged pyridine amino hafnium alkyl compound;
wherein R is 1 、R 2 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 1 、R 2 Identical or different, R 3 Selected from hydrogen, hydrocarbon radicals having 1 to 10 carbon atoms, R 4 Selected from methyl, ethyl, n-propyl, ar is phenyl, naphthyl, aliphatic-substituted phenyl, aliphatic-substituted naphthyl, n is 1,2 or 3, and M is a metal.
6. The method for preparing a non-metallocene catalyst according to claim 5, wherein the reducing agent is trialkylaluminum or aryllithium.
7. A method for preparing polybutene-1, which is characterized in that butene-1 is taken as a monomer, and a non-metallocene catalyst as set forth in any one of claims 1-4 is taken as a catalyst, and polymerization reaction is carried out to obtain polybutene-1.
8. The method for producing polybutene-1 according to claim 7, characterized in that an activator is further added to the polymerization reaction, the molar ratio of the catalyst to the activator being 1:1-10; the activator is a composition of triphenylcarbenium tetra (pentafluorophenyl) borate and aluminum alkyl, and the molar ratio of the triphenylcarbenium tetra (pentafluorophenyl) borate to the aluminum alkyl is 1:50-300.
9. The process for producing polybutene-1 according to claim 7, characterized in that the molar ratio of the butene-1 monomer to the sum of the amounts of the catalyst and the activator is 100 to 60000:1; the temperature of the polymerization reaction is 25-100 ℃.
10. Polybutene-1 obtainable by the process according to any one of claims 7 to 9.
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