CN116333004A - Preparation of 2, 6-diisopropylthiophenol single metallocene catalyst and application of catalyst in preparation of functionalized polyolefin - Google Patents
Preparation of 2, 6-diisopropylthiophenol single metallocene catalyst and application of catalyst in preparation of functionalized polyolefin Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ZLUAYWRNBXHCEW-UHFFFAOYSA-N 2,6-di(propan-2-yl)benzenethiol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1S ZLUAYWRNBXHCEW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 19
- 229920000098 polyolefin Polymers 0.000 title abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 11
- 239000000460 chlorine Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene, propylene, styrene Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims description 2
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Chemical group 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000003780 insertion Methods 0.000 abstract description 6
- 230000037431 insertion Effects 0.000 abstract description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002860 competitive effect Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007306 functionalization reaction Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
- C08F110/02—Ethene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
Abstract
The invention reports the preparation of a 2, 6-diisopropylthiophenol single metallocene catalyst and the application of the catalyst in preparing functionalized polyolefin. The invention introduces the anionic ligand 2, 6-diisopropylthiophenol, improves the tolerance of the catalyst to hetero atoms in the polymerization process, can conveniently regulate and control the three-dimensional effect and the electronic effect of the model metal catalyst by changing the framework configuration, realizes different catalytic performances and prepares polyolefin polymer materials with various structures and various performances. The novel thiophenol single metallocene catalyst reported by the invention has the characteristics of simple preparation, high activity and good homo-polymerization and copolymerization performances, is suitable for preparing a reactive polyolefin intermediate with external suspension type double bond units by non-conjugated diene copolymerization, and preparing a high molecular weight reactive polyolefin intermediate with wide distribution, wherein the reactive polyolefin intermediate has high comonomer insertion rate, and can realize large-scale effective control of material performance by fine adjustment of a polymer structure, thereby obtaining novel functionalized polyolefin meeting different application requirements. Therefore, the 2, 6-diisopropylthiophenol single-metallocene catalyst and the technology for preparing the functionalized polyolefin reported by the invention have original innovativeness, and can enhance the competitive capacity of participating in the international high-end polyolefin high-molecular material technical market in China.
Description
Technical Field
The invention relates to a preparation method of a 2, 6-diisopropylthiophenol single metallocene catalyst and an application of the catalyst in preparation of functionalized polyolefin.
Background
The polyolefin material has the advantages of high cost performance, good mechanical property, stable thermal property and the like, is widely applied to various fields of industrial production and daily life, and becomes the largest synthetic polymer material. However, the inherent non-polarity and inertness of polyolefin materials limits the expansion of their field of application. Therefore, the synthesis of the functionalized polyolefin improves the surface performance and the compatibility with other materials, and has important scientific significance and industrial application value (scientific report 2022,67,1881-1894). The most economical and efficient method is expected to be that the polyolefin with the reactive group is accurately and efficiently synthesized through transition metal coordination insertion, and finally the functionalized polyolefin is prepared by functionalization (prog.polym.sci.2002, 27,39-85). With the advent of "reactive polyolefin intermediates", synthesis of various functionalized polyolefins by the transition metal catalyzed copolymerization of olefins with non-conjugated dienes such as titanium, zirconium, hafnium, etc. has been achieved (Angew.Chem., int.Ed.2020,59, 14726-14735). In the course of the copolymerization, it is particularly important to design novel catalyst structures and to select comonomers with extended structures in order to produce reactive building blocks and to avoid polymers with crosslinked structures.
The invention reports the preparation of a 2, 6-diisopropylthiophenol single metallocene catalyst and the application of the catalyst in preparing functionalized polyolefin. The invention introduces the anionic ligand 2, 6-diisopropylthiophenol, improves the tolerance of the catalyst to hetero atoms in the polymerization process, can conveniently regulate and control the three-dimensional effect and the electronic effect of the model metal catalyst by changing the framework configuration, realizes different catalytic performances and prepares polyolefin polymer materials with various structures and various performances. The novel thiophenol single metallocene catalyst reported by the invention has the characteristics of simple preparation, high activity and good homo-polymerization and copolymerization performances, is suitable for preparing a reactive polyolefin intermediate with external suspension type double bond units by non-conjugated diene copolymerization, and preparing a high molecular weight reactive polyolefin intermediate with wide distribution, wherein the reactive polyolefin intermediate has high comonomer insertion rate, and can realize large-scale effective control of material performance by fine adjustment of a polymer structure, thereby obtaining novel functionalized polyolefin meeting different application requirements. Therefore, the 2, 6-diisopropylthiophenol single-metallocene catalyst and the technology for preparing the functionalized polyolefin reported by the invention have original innovativeness, and can enhance the competitive capacity of participating in the international high-end polyolefin high-molecular material technical market in China.
Disclosure of Invention
The invention aims to provide a preparation method of a 2, 6-diisopropylthiophenol single metallocene catalyst and application thereof in preparation of functionalized polyolefin.
The invention provides a 2, 6-diisopropylthiophenol single metallocene catalyst shown in a formula (I):
wherein X is selected from pentamethylcyclopentadienyl (Cp), cyclopentadienyl (Cp), indenyl (Ind); r is selected from methyl and chlorine.
The 2, 6-diisopropylthiophenol single metallocene catalyst reported by the invention is selected from any one of the following complexes:
Ti1:X＝Cp*,R＝Cl；Ti2:X＝Cp,R＝Cl；Ti3:X＝Ind,R＝Cl。
the invention provides a preparation method of the 2, 6-diisopropylthiophenol single metallocene catalyst, which comprises the following steps:
weighing 2, 6-diisopropyl thiophenol in a Schlenk bottle, vacuumizing by double rows, replacing with nitrogen for three times, and diluting with an anhydrous solvent; n-butyllithium is added in a nitrogen atmosphere at the temperature of minus 78 ℃ and stirred for 2 hours at room temperature; the above-mentioned materials are mixedSlowly introducing the suspension into XTiCl 3 In the anhydrous solvent solution of (2), reacting for 12 hours at room temperature; after filtration, the filtrate was recrystallized to give the desired catalyst.
In the preparation method, the anhydrous solvent is selected from benzene, toluene and xylene.
The invention also provides an application of the 2, 6-diisopropylthiophenol single metallocene catalyst shown in the formula (I) in preparing functionalized polyolefin.
In the application, the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, norbornene, cyclohexene, tetracyclododecene, 1, 5-hexadiene, 1, 7-octadiene and 1, 9-sunflower diene.
The catalyst is also added with a cocatalyst which is one or more of trifluorophenyl boron, triphenylcarbonium tetra (pentafluorophenyl) borate, aluminoxane, alkyl aluminum and alkyl aluminum chloride. The aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; the alkyl aluminum chloride is diethyl aluminum chloride, diethyl aluminum sesquichloride or ethyl aluminum dichloride.
In the polymerization reaction, the polymerization temperature is 0-180 ℃, the polymerization pressure is 0.1-5MPa, and the polymerization solvent is one or more of toluene, hexane and heptane.
The invention provides a preparation method of a 2, 6-diisopropylthiophenol single metallocene catalyst and an application of the compound in preparing functionalized polyolefin. The novel 2, 6-diisopropylthiophenol single metallocene catalyst reported by the invention has the characteristics of simple preparation, high activity and good homo-and copolymerization performance, and is suitable for preparing a reactive polyolefin intermediate with an external suspension double bond unit by copolymerization of non-conjugated diene, thereby synthesizing functional polyolefin.
Drawings
FIG. 1 is a crystal structure diagram of a catalyst Ti 1;
FIG. 2 is a crystal structure diagram of catalyst Ti 2;
FIG. 3 is a crystal structure diagram of catalyst Ti 3;
FIG. 4 is a high temperature hydrogen spectrum of a reactive polyolefin intermediate having external pendant double bond units;
FIG. 5 is a high temperature hydrogen spectrum of a functionalized polyolefin after functionalization.
Detailed Description
The invention is further illustrated by means of examples, but the invention is not limited thereto. Embodiments of the present invention may enable those skilled in the art to more fully understand the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
The invention is described below in the specific examples.
Example 1 preparation of catalyst Ti1
Weighing 2, 6-diisopropyl thiophenol in a Shi Laike bottle, vacuumizing by double rows, replacing with nitrogen for three times, and diluting with anhydrous and anaerobic toluene; 1.1 equivalent of n-butyllithium is added under nitrogen atmosphere at minus 78 ℃ and stirred for 2 hours at room temperature; slowly introducing the suspension into 1 equivalent Cp TiCl under nitrogen atmosphere at-78deg.C 3 Reacting in toluene solution of metal at room temperature for 12h; after filtration, the filtrate was concentrated and recrystallized to give Ti1 in 95% yield. 1 H NMR(400MHz,CDCl 3 )δ7.56(dd,J＝15.2,7.5Hz,1H),7.43(d,J＝7.7Hz,2H),3.48(dt,J＝13.7,6.8Hz,2H),2.62(s,15H),1.40(d,J＝6.8Hz,12H). 13 CNMR(101MHz,CDCl 3 )δ148.70,140.22,133.27,129.69,123.38,32.58,23.41,14.13.Anal.Calcd for C 22 H 32 Cl 2 STi:C,59.75；H,7.63.Found:C,59.80；H,7.65.
EXAMPLE 2 preparation of catalyst Ti2
As in example 1, cpTiCl was used 3 Instead of Cp TiCl 3 Ti2 was obtained in 90% yield. 1 H NMR(400MHz,CDCl 3 )δ7.41(d,J＝7.7Hz,1H),7.27(s,1H),7.25(s,1H),6.94(s,5H),3.16–3.10(m,2H),1.13(d,J＝6.8Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ148.29,140.69,130.89,123.86,120.18,32.89,23.55.Anal.Calcd for C 17 H 22 Cl 2 STi:C,55.12；H,6.42.Found:C,55.15；H,6.40.
EXAMPLE 3 preparation of catalyst Ti3
As in example 1, indTiCl was used 3 Instead of Cp TiCl 3 Ti3 was obtained in 96% yield. . 1 H NMR(400MHz,CDCl 3 )δ7.84(dd,J＝6.5,3.1Hz,2H),7.43(dd,J＝6.6,3.1Hz,2H),7.32–7.29(m,3H),7.14(d,J＝7.7Hz,2H),6.96(t,J＝3.4Hz,1H),2.95(dt,J＝13.6,6.8Hz,2H),1.06(d,J＝6.8Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ148.17,140.99,130.52,129.49,128.71,126.66,123.61,120.66,113.36,32.55,23.41.Anal.Calcd for C 21 H 24 Cl 2 STi:C,59.74；H,6.15.Found:C,59.78；H,6.20.
Example 4, ti1 catalyzed ethylene polymerization
Continuously drying 350ml polymeric bottle with magnetic stirrer at 120deg.C for more than 6 hr, hot pumping into glove box, adding appropriate amount of Ti1, and adding d-MAO/Ph 3 CB[C 6 F 5 ] 4 Al/ti=50 and b/ti=1.2. Then again, vacuum was pulled and replaced 3 times with ethylene. 50ml of toluene was injected by syringe, and the reaction was vigorously stirred at 80℃under an ethylene pressure of 5atm for 2min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization Activity 0.5X10 6 g·mol -1 (Ti)·h -1 。
Example 5, ti2 catalyzed ethylene polymerization
Continuously drying 350ml polymeric bottle with magnetic stirrer at 120deg.C for more than 6 hr, hot pumping into glove box, adding appropriate amount of Ti2, and adding d-MAO/Ph 3 CB[C 6 F 5 ] 4 Al/ti=50 and b/ti=1.2. Then again, vacuum was pulled and replaced 3 times with ethylene. 50ml of toluene was injected by syringe, and the reaction was vigorously stirred at 80℃under an ethylene pressure of 5atm for 2min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization Activity 1.2X10 6 g·mol -1 (Ti)·h -1 。
EXAMPLE 6 Ti3 catalyzed ethylene polymerization
Continuously drying 350ml polymeric bottle with magnetic stirrer at 120deg.C for more than 6 hr, hot pumping into glove box, adding Ti3, and adding d-MAO/Ph 3 CB[C 6 F 5 ] 4 Al/ti=50 and b/ti=1.2. Then again, vacuum was pulled and replaced 3 times with ethylene. 50ml of toluene was injected by syringe, and the reaction was vigorously stirred at 80℃under an ethylene pressure of 5atm for 2min. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol, vacuum drying to constant weight, and weighing. Polymerization Activity 3.8X10 6 g·mol -1 (Ti)·h -1 。
EXAMPLE 7 Ti1 catalyzed copolymerization of ethylene and 1, 7-octadiene
Continuously drying 350ml polymeric bottle with magnetic stirrer at 120deg.C for more than 6 hr, hot pumping into glove box, adding appropriate amount of Ti1, and adding d-MAO/Ph 3 CB[C 6 F 5 ] 4 Al/ti=50 and b/ti=1.2. Then again, vacuum was pulled and replaced 3 times with ethylene. 30ml of toluene, 0.5M 1, 7-octadiene was injected by syringe, and the reaction was vigorously stirred at 80℃for 10 minutes while maintaining an ethylene pressure of 5 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, centrifuging, vacuum drying to constant weight, and weighing. Polymerization Activity 8.2X10 5 g·mol -1 (Ti)·h -1 The monomer insertion rate was 13.6%.
EXAMPLE 8 Ti2 catalyzed copolymerization of ethylene and 1, 7-octadiene
Continuously drying 350ml polymeric bottle with magnetic stirrer at 120deg.C for more than 6 hr, hot pumping into glove box, adding appropriate amount of Ti2, and adding d-MAO/Ph 3 CB[C 6 F 5 ] 4 Al/ti=50 and b/ti=1.2. Then again, vacuum was pulled and replaced 3 times with ethylene. 30ml of toluene, 0.5M 1, 7-octadiene was injected by syringe, and the reaction was vigorously stirred at 80℃for 10 minutes while maintaining an ethylene pressure of 5 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, centrifuging, vacuum drying to constant weight, and weighing. Polymerization Activity 5.1X10 5 g·mol -1 (Ti)·h -1 The monomer insertion rate was 15.8%.
EXAMPLE 9 Ti3 catalyzed copolymerization of ethylene and 1, 7-octadiene
Continuously drying 350ml polymeric bottle with magnetic stirrer at 120deg.C for more than 6 hr, hot pumping into glove box, adding Ti3, and adding d-MAO/Ph 3 CB[C 6 F 5 ] 4 Al/ti=50 and b/ti=1.2. Then again, vacuum was pulled and replaced 3 times with ethylene. 30ml of toluene, 2M of 1, 7-octadiene was injected by syringe, and the reaction was vigorously stirred at 80℃for 10 minutes while maintaining an ethylene pressure of 5 atm. Neutralizing the reaction solution with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, centrifuging, vacuum drying to constant weight, and weighing. Polymerization Activity 6.8X10 5 g·mol -1 (Ti)·h -1 The monomer insertion rate was 50.8%.
EXAMPLE 10 preparation of functionalized polyethylene by reacting thioglycollic acid with copolymer of ethylene and 1, 7-octadiene
Weighing 100mg of a sample obtained by copolymerizing ethylene and 1, 7-octadiene, adding 5mL of anisole solvent into a 25mL Schlenk tube, and placing the sample into an oil bath at 100 ℃ to fully dissolve the sample for 1h, wherein the solution is transparent homogeneous liquid; adding 10 equivalents of thioglycollic acid reagent with VHX unit content in the sample, adding 0.1 equivalent of thermal initiator 2,2' -Azobisisobutyronitrile (AIBN) with double bond content in the sample, and closing the reaction system; freezing the whole system by liquid nitrogen, pumping out gas, heating and melting the reaction system by a blower, supplementing nitrogen, repeating the operation for three times, slightly degassing, and carrying out reflux reaction for 10 hours under the protection of nitrogen, wherein the whole system is transparent homogeneous liquid; slowly dripping the reaction solution into 50mL of cold methanol to precipitate, centrifuging at 10000r/min for 3min to collect polymer, drying at 60deg.C in vacuum drying oven until constant weight is reached to obtain polymer, and recording quality by adding 1, 2-tetrachloroethane-d to the polymer 2 (C 2 D 2 Cl 4 -d 2 ) Middle measurement 1 H NMR calculated the degree of functionalization. Thioglycollic acid reacts with double bonds to the extent that>99%, i.e. degree of functionalization>99％。
EXAMPLE 11 preparation of functionalized polyethylene by reacting benzyl mercaptan with copolymer of ethylene and 1, 7-octadiene
Weighing 100mg of a sample obtained by copolymerizing ethylene and 1, 7-octadiene, adding 5mL of anisole solvent into a 25mL Schlenk tube, and placing the sample into an oil bath at 100 ℃ to fully dissolve the sample for 1h, wherein the solution is transparent homogeneous liquid; adding 10 equivalents of benzyl mercaptan reagent with VHX unit content in the sample, adding 0.1 equivalent of thermal initiator 2,2' -Azobisisobutyronitrile (AIBN) with double bond content in the sample, and closing the reaction system; freezing the whole system by liquid nitrogen, pumping out gas, heating and melting the reaction system by a blower, supplementing nitrogen, repeating the operation for three times, slightly degassing, and carrying out reflux reaction for 10 hours under the protection of nitrogen, wherein the whole system is transparent homogeneous liquid; slowly dripping the reaction solution into 50mL of cold methanol to precipitate, centrifuging at 10000r/min for 3min to collect polymer, drying at 60deg.C in vacuum drying oven until constant weight is reached to obtain polymer, and recording quality by adding 1, 2-tetrachloroethane-d to the polymer 2 (C 2 D 2 Cl 4 -d 2 ) Middle measurement 1 H NMR calculated the degree of functionalization. The degree of reaction of benzyl mercaptan with double bond is 54%, i.e. the degree of functionalization is 54%.
Claims (8)
1. A2, 6-diisopropylthiophenol single metallocene catalyst has a structure shown in a formula (I):
wherein X is selected from pentamethylcyclopentadienyl (Cp), cyclopentadienyl (Cp), indenyl (Ind); r is selected from methyl and chlorine.
2. The process for preparing a 2, 6-diisopropylthiophenol single metallocene catalyst of claim 1, comprising the steps of: weighing 2, 6-diisopropyl thiophenol in a Schlenk bottle, vacuumizing by double rows, replacing with nitrogen for three times, and diluting with an anhydrous solvent; n-butyllithium is added in a nitrogen atmosphere at the temperature of minus 78 ℃ and stirred for 2 hours at room temperature; slowly introducing the suspension into XTiCl 3 Is an anhydrous solvent solution of (2)Reacting for 12 hours at room temperature; after filtration, the filtrate was recrystallized to give the desired catalyst.
3. The preparation method according to claim 2, characterized in that: the anhydrous solvent is selected from benzene, toluene and xylene.
4. A process for carrying out an olefin polymerization reaction, characterized by: the catalyst for the reaction is the 2, 6-diisopropylthiophenol single metallocene catalyst of claim 1.
5. The method according to claim 4, wherein: the olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, norbornene, cyclohexene, tetracyclododecene, 1, 5-hexadiene, 1, 7-octadiene and 1, 9-sunflower diene.
6. The method according to claim 4, wherein: the catalyst is also added with a cocatalyst which is one or more of trifluorophenyl boron, triphenylcarbonium tetra (pentafluorophenyl) borate, aluminoxane, alkyl aluminum and alkyl aluminum chloride.
7. The method according to claim 6, wherein: the aluminoxane is methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; the alkyl aluminum chloride is diethyl aluminum chloride, diethyl aluminum sesquichloride or ethyl aluminum dichloride.
8. The method according to claim 4, wherein: the polymerization temperature is 0-180 ℃, the polymerization pressure is 0.1-5MPa, and the polymerization solvent is one or more of toluene, hexane and heptane.
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