CN117659099A - Alpha-carboxyl-beta-diimine nickel complex, preparation method and application thereof, and preparation method of ethylene-methyl acrylate copolymer - Google Patents
Alpha-carboxyl-beta-diimine nickel complex, preparation method and application thereof, and preparation method of ethylene-methyl acrylate copolymer Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 132
- 229920006225 ethylene-methyl acrylate Polymers 0.000 title claims abstract description 123
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title abstract description 36
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 43
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003780 insertion Methods 0.000 claims abstract description 35
- 230000037431 insertion Effects 0.000 claims abstract description 35
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 26
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims abstract description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000004519 manufacturing process Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 33
- 230000008018 melting Effects 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 31
- 239000005977 Ethylene Substances 0.000 claims description 31
- 230000003197 catalytic effect Effects 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 27
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000828 alnico Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 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
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- 229920001577 copolymer Polymers 0.000 abstract description 44
- 150000003254 radicals Chemical class 0.000 abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Chemical group 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000012718 coordination polymerization Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010516 chain-walking reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- SERHXTVXHNVDKA-UHFFFAOYSA-N pantolactone Chemical compound CC1(C)COC(=O)C1O SERHXTVXHNVDKA-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- LVLZXBIWQHFREA-UHFFFAOYSA-N phenol;phosphane Chemical compound [PH4+].[O-]C1=CC=CC=C1 LVLZXBIWQHFREA-UHFFFAOYSA-N 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides an alpha-carboxyl-beta-diimine nickel complex, a preparation method and application thereof, and a preparation method of an ethylene-methyl acrylate copolymer. The alpha-carboxyl-beta-diimine nickel complex has a structure shown in a general formula (I):in the general formula (I), ar is selected from 2, 6-dialkyl phenyl; x is chlorine or bromine; l is acetonitrile or benzonitrile. The preparation method of the alpha-carboxyl-beta-diimine nickel complex comprises the following steps: acetylacetone reacts with 2, 6-dialkylaniline, then reacts with ammonium formate under the action of alkyl lithium, and then reacts with halogenated hydrocarbonThe nickel salt reacts in acetonitrile or benzonitrile solvent to obtain the alpha-carboxyl-beta-diimine nickel complex. The invention also provides a preparation method of the ethylene-methyl acrylate copolymer, which adopts the alpha-carboxyl-beta-diimine nickel complex as a main catalyst. The invention improves the molecular weight of the copolymer and the insertion rate of methyl acrylate, so that the prepared EMA is similar to a commercial branching structure prepared by a free radical process.
Description
Technical Field
The invention relates to an alpha-carboxyl-beta-diimine nickel complex, a preparation method and application thereof, and a preparation method of an ethylene-methyl acrylate copolymer, belonging to the technical field of olefin catalytic polymerization.
Background
Polyolefin is a material with excellent performance, is widely applied to various fields of automobiles, electronics, pipes, medical treatment, military industry and the like, and is a polymer material widely applied in daily life of people. However, the non-polarity of polyolefin materials limits its wider application. The polar groups are introduced into the polymer chain, so that the properties of adhesiveness, dyeability, compatibility and the like of the polyolefin material can be remarkably improved. For example, ethylene-methyl acrylate copolymers (EMA) containing 10 to 30% Methyl Acrylate (MA) have good mechanical properties and compatibility and are widely used in a variety of fields. The industrial EMA is obtained by free radical copolymerization under the severe conditions of high temperature (150-300 ℃) and high pressure (150-300 MPa), and the branched chain structure of the copolymer is uncontrollable.
Compared with the severe conditions of free radical copolymerization, the coordination polymerization can catalyze the direct copolymerization of olefin and polar monomer under mild conditions and obtain the functional polyolefin with controllable branched chain structure, which is a simple, direct and effective method. Polar monomers MA generally have poisoning effects on metal catalysts, in particular pre-transition metal catalysts, which are generally deactivated in the presence of methyl acrylate and cannot be copolymerized. Thus, the preparation of ethylene-methyl acrylate copolymers by direct copolymerization via catalytic coordination polymerization is very challenging.
The late transition metal nickel-palladium catalyst has better tolerance to polar groups due to weak electrophilic and oxophilic properties, and can catalyze the copolymerization of ethylene and polar monomers. Cationic alpha-diimine palladium is capable of catalyzing the copolymerization of ethylene and MA, and due to the rapid chain walking process, highly branched, amorphous copolymers with MA at the end of the branches are generally prepared, with a degree of branching between 97 and 106 branches/1000C (J.Am. Chem. Soc.1998,120, 888-899). In addition, neutral phosphine phenol type nickel catalysts are capable of catalyzing the copolymerization of ethylene and MA to give highly linear copolymers with MA inserted into the backbone, which is very different from commercial free radical prepared EMA branched structures. Thus, preparing EMA copolymer with low branching structure and regulating microstructure through catalytic coordination polymerization is still a great challenge and needs to break through.
CN105968027A, CN105968027A, CN113651909A, CN113603611A, CN112538098A and the like disclose the latest research results, and it can be seen that the existing nickel-palladium catalyst catalyzes the ethylene-methyl acrylate copolymer prepared by copolymerizing ethylene and methyl acrylate, while the structure of the copolymer can be regulated by the catalyst structure and the like, the copolymer has the problems of low molecular weight and MA monomer insertion rate, low copolymerization activity and the like, and compared with the EMA copolymer obtained by a commercial free radical process, the branched structure of the copolymer has a difference.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an alpha-carboxyl-beta-diimine nickel complex, a preparation method and application thereof. The alpha-carboxyl-beta-diimine nickel complex provided by the invention can be used as a catalyst in olefin polymerization, is particularly suitable for catalyzing ethylene and Methyl Acrylate (MA) to be copolymerized, can enable a product to have a low-branching structure, and can improve the copolymerization efficiency.
It is another object of the present invention to provide a method for preparing an ethylene-methyl acrylate copolymer. The catalyst provided by the invention can improve the efficiency of catalyzing the copolymerization of ethylene and Methyl Acrylate (MA), and improve the molecular weight of the copolymer and the insertion rate of MA, so that the prepared ethylene-methyl acrylate copolymer (EMA) has obvious melting temperature and is similar to a commercial branching structure prepared by a free radical process.
To achieve the above object, the first aspect of the present invention provides an α -carboxy- β -diimine nickel complex having a structure represented by general formula (I):
in the general formula (I), two Ar are the same or different, and Ar is selected from 2, 6-dialkyl phenyl; x is a chlorine atom or a bromine atom; l is acetonitrile or benzonitrile.
In the above-mentioned α -carboxy- β -diimine nickel complex, preferably, in the general formula (I), two Ar are the same or different, and Ar is selected from 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl. More preferably, in the general formula (I), two Ar are the same, and Ar is 2, 6-diisopropylphenyl or 2, 6-dimethylphenyl. It is particularly preferred that in the general formula (I), both Ar are the same and are 2, 6-diisopropylphenyl groups.
In the above-mentioned- β -diimine nickel complex, preferably, in the general formula (I), two Ar are the same, each is 2, 6-diisopropylphenyl, X is a bromine atom, and L is acetonitrile.
According to the invention, carboxyl is introduced into the framework structure of the cationic beta-diimine type nickel catalyst, so that a novel diimine type nickel complex is obtained. The alpha-carboxyl-beta-diimine nickel complex can be used as a catalyst for olefin polymerization, is particularly suitable for catalyzing ethylene and Methyl Acrylate (MA) copolymerization, and can realize the promotion of a low-branching structure and copolymerization efficiency of a copolymerization product due to the introduction of carboxyl on a framework structure. Specifically, due to the introduction of carboxyl on the skeleton structure, on one hand, the nickel active center of which the cationic nickel center is changed into neutral is realized, and the tolerance of the nickel active center to methyl acrylate is improved; on the other hand, the active center of the center also reduces the chain running process in the copolymerization process, and the low-branching copolymer can be prepared.
The second aspect of the invention provides a preparation method of the alpha-carboxyl-beta-diimine nickel complex, which comprises the following steps:
(1) Reacting acetylacetone with 2, 6-dialkylaniline to obtain a 2, 6-dialkylphenyl-substituted beta-diimine compound;
(2) The 2, 6-dialkylphenyl substituted beta-diimine compound is subjected to substitution reaction with ammonium formate under the action of alkyl lithium to obtain alpha-carboxyl-beta-diimine lithium salt;
(3) And (3) carrying out coordination reaction on the alpha-carboxyl-beta-diimine lithium salt and halogenated nickel salt in acetonitrile or benzonitrile solvent to obtain the alpha-carboxyl-beta-diimine nickel complex.
In the above method for preparing an α -carboxy- β -diimine nickel complex, the 2, 6-dialkylaniline preferably includes 2, 6-diisopropylaniline and/or 2, 6-dimethylaniline. More preferably, the 2, 6-dialkylaniline is 2, 6-diisopropylaniline.
In the preparation method of the alpha-carboxyl-beta-diimine nickel complex, the step (1) is a ketoamine condensation reaction, and the specific reaction conditions are well known in the art; for example, the molar ratio of the acetylacetone to the 2, 6-dialkylaniline can be 1:2; the reaction temperature of acetylacetone and 2, 6-dialkylaniline can be 90 ℃ and the reaction time can be 72h.
In the above-mentioned method for producing an α -carboxy- β -diimine nickel complex, preferably, in the step (2), the alkyl lithium is butyl lithium, more preferably n-butyl lithium.
In the above method for producing an α -carboxy- β -diimine nickel complex, in the step (2), the molar ratio of the 2, 6-dialkylphenyl-substituted β -diimine compound, the alkyl lithium, and the ammonium formate is preferably 1 (1.0 to 1.5): 1.2 to 2.0.
In the above-mentioned method for producing an α -carboxy- β -diimine nickel complex, in the step (2), the substitution reaction is a strongly exothermic reaction, and the reaction conditions thereof are dependent on the reaction scale. The temperature and time of the substitution reaction can be adjusted by those skilled in the art according to the scale of the reaction. For example, a low heat mode can be adopted in a laboratory, the reaction temperature can be between-80 and 40 ℃, and the reaction time can be between 1 and 10 hours.
In the above-mentioned method for producing an α -carboxy- β -diimine nickel complex, preferably, in the step (3), the halogenated nickel salt includes nickel bromide and/or nickel chloride, more preferably nickel bromide.
In the above method for producing an α -hydroxy- β -diimine nickel complex, in the step (3), the α -hydroxy- β -diimine lithium salt and the halogenated nickel salt are preferably subjected to a complexation reaction in an acetonitrile solvent.
In the above method for producing an α -carboxy- β -diimine nickel complex, it is preferable that in the step (3), the molar ratio of the α -carboxy- β -diimine lithium salt to the halogenated nickel salt is 1 (1.0 to 1.5).
In the above-mentioned method for producing an α -carboxy- β -diimine nickel complex, acetonitrile or benzonitrile is used as both the solvent and the complexing molecule in the step (3), and thus the amount thereof is excessive. The amount of the present invention is not particularly limited, and may be adjusted conventionally by those skilled in the art.
In the above method for preparing an α -carboxy- β -diimine nickel complex, preferably, in the step (3), the reaction temperature of the coordination reaction is 0 to 50 ℃ and the reaction time is 8 to 48 hours. More preferably, the reaction temperature of the coordination reaction is 20-40 ℃ and the reaction time is 12-24 h.
In the preparation method of the α -carboxy- β -diimine nickel complex of the present invention, both steps (1) and (2) may be carried out in an organic solvent, and the present invention is not particularly limited to the specific organic solvent used, and those skilled in the art may routinely select them. And after the corresponding products of the step (1), the step (2) and the step (3) are obtained, one or more steps of separating, crystallizing, concentrating, washing, drying and the like can be carried out on the products respectively, and the steps can be conventional operation in the field, and the invention is not limited in particular.
In a third aspect, the invention provides the use of an α -carboxy- β -diimine nickel complex as described above as a catalyst in the polymerization of olefins.
In the above applications, preferably, the olefin polymerization comprises copolymerization of an olefin with a polar monomer.
In the above application, preferably, the olefin is polymerized as a copolymerization of ethylene with an acrylic monomer. More preferably, the olefin is polymerized as a copolymerization of ethylene with methyl acrylate.
In the above application, preferably, the α -carboxy- β -diimine nickel complex is used as a main catalyst in olefin polymerization and an organoaluminum compound is used as a cocatalyst.
In the above application, preferably, the organoaluminum compound includes one or a combination of several of Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), isobutylaluminoxane (BAO), triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, triisobutylaluminum and the like. More preferably, the organoaluminum compound includes one or a combination of several of Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), isobutylaluminoxane (BAO), and the like.
In the above application, the molar ratio of the cocatalyst to the procatalyst of alnico is preferably (500 to 3000): 1, more preferably (1000 to 2000): 1.
In a fourth aspect, the present invention provides a method for preparing an ethylene-methyl acrylate copolymer, the method employing the above-described α -carboxy- β -diimine nickel complex as a main catalyst.
According to a specific embodiment of the present invention, preferably, the preparation method of the ethylene-methyl acrylate copolymer comprises the steps of:
the alpha-carboxyl-beta-diimine nickel complex is used as a main catalyst, an organic aluminum compound is used as a cocatalyst, ethylene and methyl acrylate monomers are subjected to copolymerization reaction in a solvent, and after the reaction is finished, the ethylene-methyl acrylate copolymer is obtained.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, the reaction temperature of the copolymerization reaction is preferably 0 to 100 ℃, more preferably 50 to 80 ℃.
In the above method for producing an ethylene-methyl acrylate copolymer, the reaction pressure of the copolymerization is preferably 0.5 to 2.0MPa. It will be appreciated by those skilled in the art that the pressure of the copolymerization reaction of the present invention is ethylene pressure.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, the reaction time of the copolymerization is preferably 0.5 to 24 hours, more preferably 2 to 8 hours.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, the molar ratio of the methyl acrylate monomer to the main catalyst α -carboxy- β -diimine nickel complex is preferably (266 to 1600): 1, more preferably (500 to 1066): 1. The molar ratio of the methyl acrylate monomer to the main catalyst alpha-carboxyl-beta-diimine nickel complex is calculated by the molar quantity of nickel in the main catalyst being 1.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, preferably, the organoaluminum compound includes one or a combination of several of Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), isobutylaluminoxane (BAO), and the like.
In the above method for producing an ethylene-methyl acrylate copolymer, the molar ratio of the cocatalyst to the main catalyst is preferably (500 to 3000): 1, more preferably (1000 to 2000): 1.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, preferably, the solvent includes one or a combination of several of 1, 2-dichloroethane, n-hexane, chlorobenzene, toluene, xylene, and the like.
According to a specific embodiment of the present invention, preferably, the above-mentioned method for preparing an ethylene-methyl acrylate copolymer further comprises the steps of: and after the reaction is finished, adding a terminator to terminate the reaction, thereby obtaining the ethylene-methyl acrylate copolymer. The specific choice and amount of the terminator may be adjusted by those skilled in the art according to the actual circumstances.
In the preparation method of the ethylene-methyl acrylate copolymer, after the termination agent is added to terminate the reaction, the preparation method can further comprise the steps of washing, filtering, drying and the like on a reaction product to obtain the ethylene-methyl acrylate copolymer. Washing, filtration and drying may be conventional in the art, and the present invention is not particularly limited.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, it is preferable that the weight average molecular weight of the produced ethylene-methyl acrylate copolymer is 13.2 to 100.3kg/mol.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, it is preferable that the degree of branching of the produced ethylene-methyl acrylate copolymer is 25 to 51 branches/1000C.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, it is preferable that the ethylene-methyl acrylate copolymer produced has a methyl acrylate insertion rate of 2.5 to 36.4 ω% (based on 100% of the total weight of the ethylene-methyl acrylate copolymer).
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, it is preferable that the melting temperature of the produced ethylene-methyl acrylate copolymer is 81.3 to 125.3 ℃.
In the above-mentioned method for producing an ethylene-methyl acrylate copolymer, it is preferable that the ethylene-methyl acrylate copolymer produced has a molecular weight distribution index of 1.28 to 2.63.
In the above method for producing an ethylene-methyl acrylate copolymer, preferably, the catalyst activity of the procatalyst, namely, the alpha-carboxyl-beta-diimine nickel complex, is 0.89X 10 4 -18.1×10 4 g EMA/(mol Ni·h)。
The preparation method of the alpha-carboxyl-beta-diimine nickel complex and the ethylene-methyl acrylate copolymer provided by the invention comprises the following excellent technical effects:
the beneficial effects 1 are that: the invention adopts the alpha-carboxyl-beta-diimine nickel complex as a main catalyst, provides a method for preparing EMA by directly copolymerizing ethylene and methyl acrylate with high efficiency, and adopts the alpha-carboxyl-beta-diimine nickel complex main catalyst to realize that the insertion rate of MA reaches 36.4 omega percent and the molecular weight of the copolymer reaches 100kg/mol.
The beneficial effects are 2: the EMA prepared by the method provided by the invention has the characteristics of low branching and obvious melting temperature, is different from the highly branched amorphous and completely linear prepared by the prior nickel-palladium catalyst, has a similar branched structure with the EMA copolymer prepared by commercial free radicals, and has obvious commercial prospect.
The beneficial effects are 3: the preparation process of the alpha-carboxyl-beta-diimine nickel complex main catalyst provided by the invention is simple, and the catalyst is stable in air; compared with the preparation of EMA by industrial free radical copolymerization, the preparation method of the ethylene-methyl acrylate copolymer provided by the invention has the advantages of mild reaction conditions and controllable branched structure.
In summary, the invention provides a novel alpha-carboxyl-beta-diimine nickel complex main catalyst and a preparation method of an ethylene-methyl acrylate copolymer, aiming at the defects or defects of branching structure difference, lower copolymer molecular weight and MA monomer insertion rate and the like existing in the existing nickel-palladium catalyst for catalyzing ethylene and Methyl Acrylate (MA) to be copolymerized and compared with the EMA copolymer obtained by a commercial free radical process. The catalyst of the invention can obviously improve the efficiency of catalyzing the copolymerization of ethylene and MA, and improve the molecular weight of the copolymer and the insertion rate of MA, so that the prepared EMA copolymer has obvious melting temperature and is similar to a commercial branching structure prepared by a free radical process, thereby having good application prospect.
Drawings
FIG. 1 is a DSC of the EMA copolymer prepared in example 21.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the EMA copolymer prepared in example 21.
FIG. 3 is a GPC chart of the EMA copolymer prepared in example 21.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting 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.
1. Preparation of alpha-carboxy-beta-diimine nickel complexes
Example 1
The embodiment provides an alpha-carboxyl-beta-diimine nickel complex Ni-1, which is prepared by the following steps:
(1) Raw material 2, 6-diisopropylaniline (15.1 g,85.2 mmol), acetylacetone (4.1 g,41 mmol), hydrochloric acid (12M, 6 mL), ethanol (300 mL) were added to a 500mL round bottom flask, and the mixture was heated to reflux for 72h; the reaction solvent was dried in vacuo to give a brown solid, 300mL of dichloromethane was added, and the mixture was washed with saturated sodium bicarbonate to neutralize excess acid; the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, the filtrate was collected, the organic phase was spin-dried, and methanol was added to recrystallize to obtain 8.25g of a white needle-like solid. 1 H NMR(CDCl 3 ,400MHz)δ(ppm):12.11(s,1H,NH),7.13(m,6H,Ar-H),4.87(s,H,α-CH),3.08(m,4H,CHMe 2 ),1.72(s,6H,CH 3 ),1.21(d,12H,CH(CH 3 ) 2 ),1.11(d,12H,CH(CH 3 ) 2 ). 13 C NMR(CDCl 3 100 MHz) delta (ppm): 161.34,142.62,140.89,125.24,123.15,93.41,28.35,24.35,23.34,20.90. Which is a 2, 6-diisopropylphenyl substituted beta-diimine compound.
(2) Under nitrogen atmosphere, the steps are carried outThe synthesized 2, 6-diisopropylphenyl substituted beta-diimine compound (3.86 g,9.24 mmol) in step (1) is dissolved in 50mL of anhydrous tetrahydrofuran to form colorless clear liquid, 4.3mL of n-butyllithium (2.5M, 10.75 mmol) is slowly added dropwise at-78 ℃ to form yellow clear liquid, the reaction liquid is stirred continuously at-78 ℃ for 1 hour, and then the reaction liquid is displaced to room temperature and returns to the temperature for 30 minutes; 0.698g ammonium formate (11.088 mmol) was added at-78℃and slowly returned to room temperature and the reaction stirred overnight; the mixture was filtered, concentrated and frozen at-30℃to give 4.97g of a white solid ligand lithium salt precipitate. 1 H NMR(DMSO-d 6 ,400MHz)δ(ppm):7.50-7.20(m,6H,Ar-H),2.84(m,4H,CHMe 2 ),2.72(s,1H,α-CH),1.94(s,6H,CH 3 ),1.16(m,24H,CH(CH 3 ) 2 ). 13 C NMR(DMSO-d 6 100 MHz) delta (ppm) 175.4, 164.6,143.2,136.7,123.3,122.3,56.0,28.8,23.3,22.9,14.7. Which is an alpha-carboxy-beta-diimine lithium salt.
(3) Under nitrogen atmosphere, the ligand alpha-carboxyl-beta-diimine lithium salt (0.281g, 0.61 mmol) synthesized in the step (2) is sequentially added with NiBr 2 ·3H 2 O (0.216 g,0.74 mmol), acetonitrile solvent (40 mL) are mixed and stirred for 30min at-40 ℃, and the mixture is stirred for reaction for 24h at room temperature to obtain suspension; the reaction solution was concentrated, filtered to give a solid, which was washed with n-hexane (3X 5 mL), the residual ligand was removed, the residual solvent was drained off, and dried to give a green powder solid in 65% yield. Nuclear magnetic analysis: 1 H NMR(DMSO-d 6 ,400MHz)δ(ppm):7.45-7.15(m,6H,Ar-H),2.81(m,4H,CHMe2),2.70(s,1H,α-CH),1.91(s,6H,CH 3 ),1.13(m,24H,CH(CH 3 ) 2 ). 13 C NMR(DMSO-d 6 100 MHz) delta (ppm) 175.1, 164.3,143.0,136.4,123.0,122.0,55.7,28.5,23.0,22.4,14.5. Elemental analysis (C) 32 H 44 BrN 3 NiO 2 (percent) theoretical value C,59.93; h,6.92; n,6.55. Measured value C,59.78; h,6.78; n,6.38.
The alpha-carboxyl-beta-diimine nickel complex Ni-1 provided by the embodiment has a structure shown in a formula (II):
in formula (II), two Ar's are the same and are both 2, 6-diisopropylphenyl.
Example 2
This example provides an α -carboxy- β -diimine nickel complex Ni-2 prepared in substantially the same manner as example 1 except that: niBr in step (3) of example 1 2 ·3H 2 O (0.216 g,0.74 mmol) was replaced with NiCl 2 ·6H 2 O (0.175 g,0.74 mmol). The yield was 56%. Nuclear magnetic analysis: 1 H NMR(DMSO-d 6 ,400MHz)δ(ppm):7.46-7.17(m,6H,Ar-H),2.82(m,4H,CHMe2),2.72(s,1H,α-CH),1.92(s,6H,CH 3 ),1.14(m,24H,CH(CH 3 ) 2 ). 13 C NMR(DMSO-d 6 100 MHz) delta (ppm): 175.3,164.4,143.1,136.5,123.1,122.1,55.8,28.6,23.1,22.3,14.6. Elemental analysis (C) 32 H 44 ClN 3 NiO 2 (percent) theoretical value C,64.39; h,7.43; n,7.04. Measured value C,64.18; h,7.18; n,6.97.
The alpha-carboxyl-beta-diimine nickel complex Ni-2 provided by the embodiment has a structure shown in a formula (III):
in formula (III), two Ar's are the same and are both 2, 6-diisopropylphenyl.
Example 3
This example provides an α -carboxy- β -diimine nickel complex Ni-3, which is prepared in substantially the same manner as example 1, except that: the acetonitrile solvent (40 mL) in step (3) of example 1 was replaced with benzonitrile solvent (40 mL). The yield thereof was found to be 53%. Nuclear magnetic analysis: 1 H NMR(DMSO-d 6 ,400MHz)δ(ppm):7.92(s,2H,PhCN-H),7.62(s,1H,PhCN-H),7.48(s,2H,PhCN-H),7.48-7.22(m,6H,Ar-H),2.86(m,4H,CHMe 2 ),2.75(s,1H,α-CH),1.95(s,6H,CH 3 ),1.18(m,24H,CH(CH 3 ) 2 ). 13 C NMR(DMSO-d 6 ,100MHz)δ(ppm):175.5,164.7,143.4,136.8,132.2,129.5,123.4,122.5,116.5,112.6,55.9,28.8,23.5,22.5,14.9. Elemental analysis (C) 37 H 46 BrN 3 NiO 2 (percent) theoretical value C,63.18; h,6.59; n,5.97. Measured value C,63.01; h,6.42; n,5.73.
The alpha-carboxyl-beta-diimine nickel complex Ni-3 provided by the embodiment has a structure shown in a formula (IV):
in formula (IV), two Ar's are the same and are both 2, 6-diisopropylphenyl.
Example 4
This example provides an α -carboxy- β -diimine nickel complex Ni-4 prepared in substantially the same manner as example 1 except that: niBr in step (3) of example 1 2 ·3H 2 O (0.216 g,0.74 mmol) was replaced with NiCl 2 ·6H 2 O (0.175 g,0.74 mmol); and acetonitrile solvent (40 mL) in step (3) was replaced with benzonitrile solvent (40 mL). The product was a pale yellow powder solid in 52% yield. Nuclear magnetic analysis: 1 H NMR(DMSO-d 6 ,400MHz)δ(ppm):7.94(s,2H,PhCN-H),7.65(s,1H,PhCN-H),7.49(s,2H,PhCN-H),7.49-7.23(m,6H,Ar-H),2.85(m,4H,CHMe 2 ),2.74(s,1H,α-CH),1.94(s,6H,CH 3 ),1.17(m,24H,CH(CH 3 ) 2 ). 13 C NMR(DMSO-d 6 100 MHz) delta (ppm): 175.7,164.9,143.6,136.9,132.5,129.8,123.7,122.6,116.7,112.8,56.0,28.9,23.8,22.5,15.1. Elemental analysis (C) 37 H 46 ClN 3 NiO 2 (percent) theoretical value C,67.44; h,7.04; n,6.38. Measured value C,67.31; h,7.02; n,6.15.
The alpha-carboxyl-beta-diimine nickel complex Ni-4 provided in the embodiment has a structure shown in a formula (V):
in formula (V), two Ar's are the same and are both 2, 6-diisopropylphenyl.
2. Preparation of ethylene-methyl acrylate copolymer
In the following examples, the weight average molecular weight of the copolymer obtained was determined by gel permeation chromatography (GPC chart), the melting temperature of the copolymer was determined by differential scanning calorimeter (DSC chart), and the branching degree of the copolymer and the insertion rate of methyl acrylate monomer were calculated by nuclear magnetic resonance spectroscopy.
Example 5
This example provides a method for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as a main catalyst, comprising the steps of:
vacuum heating and drying the autoclave, cooling to room temperature, and repeatedly replacing ethylene for three times; dried toluene (40 mL) was added to the dried autoclave, methyl acrylate (0.72 mL,8mmol, ma/ni=266:1), promoter methylaluminoxane (MAO, 10mL,45mmol,Al/ni=1500:1) stirred at constant temperature 50 ℃; adding toluene solution of a main catalyst Ni-1 (19.5 mg,30 mu mol) into a reaction kettle to initiate copolymerization; maintaining ethylene pressure of 0.5MPa and carrying out copolymerization reaction for 4h at 50 ℃; terminating the reaction by using 100mL of ethanol hydrochloride solution with the volume fraction of 5%; the copolymer was obtained by filtration and washed three times with ethanol and dried under vacuum at 50℃to constant weight.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 8.14X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 44.2kg/mol, the molecular weight distribution index was 1.32, the insertion rate of methyl acrylate was 7.8. Omega., the melting temperature was 100.1℃and the branching degree was 36/1000 ℃.
Example 6
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-2 provided in example 2 as a main catalyst, the specific steps of the process being the same as those of example 5.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-2 in this example was 6.95X10 4 g EMA/(mol Ni.h), weight of the copolymer producedThe average molecular weight was 39.1kg/mol, the molecular weight distribution index was 1.38, the insertion rate of methyl acrylate was 7.2. Omega., the melting temperature was 98.1℃and the branching degree was 37/1000 ℃.
Example 7
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-3 provided in example 3 as a main catalyst, the specific steps of the process being the same as those of example 5.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-3 in this example was 4.75X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 41.1kg/mol, the molecular weight distribution index was 1.28, the insertion rate of methyl acrylate was 6.8. Omega., the melting temperature was 97.1℃and the branching degree was 35/1000 ℃.
Example 8
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-4 provided in example 4 as the main catalyst, the specific procedure of this process being the same as that of example 5.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-4 in this example was 4.35X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 43.1kg/mol, the molecular weight distribution index was 1.42, the insertion rate of methyl acrylate was 6.5. Omega., the melting temperature was 100.1℃and the branching degree was 36/1000 ℃.
Example 9
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the cocatalyst methylaluminoxane in example 5 (MAO, 10mL,45mmol,Al/ni=1500:1) was replaced by a modified methylaluminoxane (MMAO, 10mL,45mmol,Al/ni=1500:1).
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 7.55X10 4 g EMA/(mol Ni.h), preparationThe weight average molecular weight of the resulting copolymer was 58.1kg/mol, the molecular weight distribution index was 1.36, the insertion rate of methyl acrylate was 6.2. Omega., the melting temperature was 102.1℃and the branching degree was 35/1000 ℃.
Example 10
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the cocatalyst methylaluminoxane in example 5 (MAO, 10mL,45mmol,Al/ni=1500:1) was replaced by isobutylaluminoxane (BAO, 10mL,45mmol,Al/ni=1500:1).
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 6.15X10 4 g EMA/(mol Ni.h), the weight average molecular weight of the copolymer obtained was 48.6kg/mol, the molecular weight distribution index was 1.43, the insertion rate of methyl acrylate was 6.1. Omega., the melting temperature was 102.1℃and the branching degree was 37/1000 ℃.
Example 11
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the molar ratio of cocatalyst to procatalyst, al-Ni, in example 5 was adjusted to 500:1.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 2.51X10 4 g EMA/(mol Ni.h), the weight average molecular weight of the copolymer obtained was 18.2kg/mol, the molecular weight distribution index was 1.45, the insertion rate of methyl acrylate was 6.9. Omega., the melting temperature was 98.1℃and the branching degree was 38/1000 ℃.
Example 12
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the molar ratio of promoter to procatalyst, al-Ni, in example 5 was adjusted to 1000:1.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 7.72X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 38.2kg/mol, the molecular weight distribution index was 1.39, the insertion rate of methyl acrylate was 7.1. Omega., the melting temperature was 96.8℃and the branching degree was 39/1000 ℃.
Example 13
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the molar ratio of promoter to procatalyst, al-Ni, in example 5 was adjusted to 3000:1.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 11.2X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 13.2kg/mol, the molecular weight distribution index was 1.47, the insertion rate of methyl acrylate was 6.7ω%, the melting temperature was 100.8deg.C, and the branching degree was 35/1000C.
Example 14
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the temperature of the copolymerization reaction in example 5 was adjusted from 50℃to 0 ℃.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 2.38X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 22.1kg/mol, the molecular weight distribution index was 1.53, the insertion rate of methyl acrylate was 2.5. Omega., the melting temperature was 125.3℃and the branching degree was 28/1000 ℃.
Example 15
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the temperature of the copolymerization reaction in example 5 was adjusted from 50℃to 25 ℃.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 4.21X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 35.3kg/mol, the molecular weight distribution index was 1.41, the insertion rate of methyl acrylate was 5.8. Omega., the melting temperature was 120.3℃and the branching degree was 33/1000 ℃.
Example 16
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the temperature of the copolymerization reaction in example 5 was adjusted from 50℃to 80 ℃.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 5.95X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 38.6kg/mol, the molecular weight distribution index was 1.83, the insertion rate of methyl acrylate was 9.6. Omega., the melting temperature was 89.3℃and the branching degree was 46/1000 ℃.
Example 17
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the temperature of the copolymerization reaction in example 5 was adjusted from 50℃to 100 ℃.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 3.55X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 19.7kg/mol, the molecular weight distribution index was 2.63, the insertion rate of methyl acrylate was 11.8. Omega., the melting temperature was 81.3℃and the branching degree was 51/1000 ℃.
Example 18
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the ethylene pressure of the copolymerization reaction in example 5 was adjusted from 0.5MPa to 1.0MPa.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 10.2X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 68.7kg/mol, the molecular weight distribution index was 1.47, the insertion rate of methyl acrylate was 4.6. Omega., the melting temperature was 106.5℃and the branching degree was 31/1000 ℃.
Example 19
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the ethylene pressure of the copolymerization reaction in example 5 was adjusted from 0.5MPa to 2.0MPa.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 18.1X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 100.3kg/mol, the molecular weight distribution index was 1.41, the insertion rate of methyl acrylate was 2.8. Omega., the melting temperature was 113.3℃and the branching degree was 25/1000 ℃.
Example 20
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the concentration of methyl acrylate in example 5 was adjusted to 0.4mol/L and the molar ratio of methyl acrylate to procatalyst was 533:1.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 4.51X10 4 g EMA/(mol Ni·h) The weight average molecular weight of the copolymer obtained was 42.1kg/mol, the molecular weight distribution index was 1.36, the insertion rate of methyl acrylate was 13.8. Omega., the melting temperature was 96.1℃and the branching degree was 40/1000 ℃.
Example 21
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the concentration of methyl acrylate in example 5 was adjusted to 0.8mol/L and the molar ratio of methyl acrylate to procatalyst was 1066:1.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 2.73X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 27.1kg/mol, the molecular weight distribution index was 1.31, the insertion rate of methyl acrylate was 30.5. Omega., the melting temperature was 92.5℃and the branching degree was 44/1000 ℃.
The DSC chart of the copolymer prepared in this example is shown in FIG. 1, the nuclear magnetic hydrogen spectrum is shown in FIG. 2, and the GPC spectrum is shown in FIG. 3.
Example 22
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the concentration of methyl acrylate in example 5 was adjusted to 1.2mol/L and the molar ratio of methyl acrylate to procatalyst was 1600:1.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 0.89X 10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 18.6kg/mol, the molecular weight distribution index was 1.40, the insertion rate of methyl acrylate was 36.4. Omega., the melting temperature was 94.2℃and the branching degree was 46/1000 ℃.
Example 23
This example provides a process for preparing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex Ni-1 provided in example 1 as the main catalyst, the specific steps of the process being substantially the same as those of example 5, except that: the solvent toluene in example 5 was replaced with 1, 2-dichloroethane with the same amount.
The catalytic activity of the alpha-carboxyl-beta-diimine nickel complex Ni-1 in this example was 9.09X 10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 43.1kg/mol, the molecular weight distribution index was 1.36, the insertion rate of methyl acrylate was 5.8. Omega., the melting temperature was 101.1℃and the branching degree was 34/1000 ℃.
Example 24
The embodiment provides a preparation method of an ethylene-methyl acrylate copolymer, which adopts an alpha-carboxyl-beta-diimine nickel complex Ni-1 provided in the embodiment 1 as a main catalyst, and the specific steps of the preparation method are basically the same as those of the embodiment 5, except that: the solvent toluene in example 5 was replaced with n-hexane in a constant amount.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 7.19X10 4 g EMA/(mol Ni.h), the weight average molecular weight of the copolymer obtained was 39.6kg/mol, the molecular weight distribution index was 1.42, the insertion rate of methyl acrylate was 5.5. Omega., the melting temperature was 99.1℃and the branching degree was 36/1000 ℃.
Example 25
The embodiment provides a preparation method of an ethylene-methyl acrylate copolymer, which adopts an alpha-carboxyl-beta-diimine nickel complex Ni-1 provided in the embodiment 1 as a main catalyst, and the specific steps of the preparation method are basically the same as those of the embodiment 5, except that: the solvent toluene in example 5 was replaced with chlorobenzene in a constant amount.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 9.75X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 46.3kg/mol, the molecular weight distribution index was 1.36, the insertion rate of methyl acrylate was 5.9. Omega., the melting temperature was 101.1℃and the branching degree was 38/1000 ℃.
Example 26
The embodiment provides a preparation method of an ethylene-methyl acrylate copolymer, which adopts an alpha-carboxyl-beta-diimine nickel complex Ni-1 provided in the embodiment 1 as a main catalyst, and the specific steps of the preparation method are basically the same as those of the embodiment 5, except that: the solvent toluene in example 5 was replaced with xylene in a constant amount.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 8.03X10 4 g EMA/(mol Ni.h), the weight-average molecular weight of the copolymer obtained was 56.9kg/mol, the molecular weight distribution index was 1.35, the insertion rate of methyl acrylate was 6.1. Omega., the melting temperature was 101.1℃and the branching degree was 39/1000 ℃.
Example 27
The embodiment provides a preparation method of an ethylene-methyl acrylate copolymer, which adopts an alpha-carboxyl-beta-diimine nickel complex Ni-1 provided in the embodiment 1 as a main catalyst, and the specific steps of the preparation method are basically the same as those of the embodiment 5, except that: the solvent toluene in example 5 was replaced with a mixed solvent of chlorobenzene and toluene (50% v/v) in an unchanged amount.
The catalytic activity of the alpha-carboxy-beta-diimine nickel complex Ni-1 in this example was 8.23X10 4 g EMA/(mol Ni.h), the weight average molecular weight of the copolymer obtained was 45.6kg/mol, the molecular weight distribution index was 1.53, the insertion rate of methyl acrylate was 6.8. Omega., the melting temperature was 101.1℃and the branching degree was 39/1000 ℃.
The following comparative examples were prepared by copolymerizing ethylene with methyl acrylate using a beta-diimine type nickel main catalyst, an alpha-diimine type palladium main catalyst and a phosphine sulfonic acid type palladium main catalyst, respectively.
Comparative example 1
This comparative example provides a process for the preparation of ethylene-methyl acrylate copolymer using a beta-diimine type nickel procatalyst having the structure represented by formula (VI) prepared according to the process of literature Organometallics 1997,16,1514.
Heating the autoclave to 150 ℃ and vacuumizing for 2 hours, cooling to room temperature in a vacuumizing state, and repeatedly replacing ethylene for three times; dried toluene (40 mL) was added to the autoclave, methyl acrylate (2.8 mL,32mmol, ma/ni=1066:1), promoter methylaluminoxane (MAO, 10mL,45mmol,Al/ni=1500:1) was stirred at constant temperature 50 ℃; adding toluene solution of beta-diimine type nickel main catalyst (19.2 mg,30 mu mol) with a structure shown in a formula (VI) into a reaction kettle to initiate copolymerization; the ethylene pressure of 0.5MPa is maintained, the copolymerization reaction is carried out for 4 hours at 50 ℃, and 100mL of ethanol solution of hydrochloric acid with the volume fraction of 5% is used for stopping the reaction. No solid polymer was found to be obtained. The copolymerization activity of the beta-diimine type nickel main catalyst in this comparative example was zero.
Comparative example 2
This comparative example provides a process for the preparation of an ethylene-methyl acrylate copolymer using an α -diimine-type palladium procatalyst having the structure represented by formula (VII) which is prepared according to the process of document j.am.chem.soc.1996,118, 267.
Heating the autoclave to 150 ℃ and vacuumizing for 2 hours, cooling to room temperature in a vacuumizing state, and repeatedly replacing ethylene for three times; dry toluene (40 mL) was added to the autoclave, and methyl acrylate (2.8 mL,32mmol, ma/pd=1066:1) was stirred at constant temperature 50 ℃; an alpha-diimine palladium main catalyst (16.9 mg,30 mu mol) with a structure shown in a formula (VII) is activated by a promoter sodium tetra (3, 5-bis (trifluoromethyl) phenyl) borate (NaBArF, 36 mu mol, B/Pd=1.2:1) and then added into a reaction kettle; maintaining ethylene pressure at 0.5MPa and carrying out copolymerization reaction for 4h at 50 ℃, and stopping the reaction by using 100mL of ethanol solution of hydrochloric acid with volume fraction of 5%; the copolymer was obtained by filtration and washed three times with ethanol and dried under vacuum at 50℃to constant weight.
The catalytic activity of the α -diimine type palladium procatalyst in this comparative example was 9.4X10 3 g EMA/(mol Pd.h), the weight average molecular weight of the copolymer prepared was 10.2kg/mol, the molecular weight distribution index was 1.52, the insertion rate of methyl acrylate was 9.8. Omega.%, the branching degree was 110/1000C, and no obvious melting temperature was found.
Comparative example 3
This comparative example provides a process for the preparation of an ethylene-methyl acrylate copolymer using a phosphine sulfonic acid type palladium procatalyst having the structure represented by formula (VIII) prepared according to the process provided in literature polym.chen.,2017,8,2405-2409.
Heating the autoclave to 150 ℃ and vacuumizing for 2 hours, cooling to room temperature in a vacuumizing state, and repeatedly replacing ethylene for three times; dried toluene (40 mL) was added to the autoclave, methyl acrylate (2.8 mL,32mmol, ma/pd=1066:1), cocatalyst methylaluminoxane (MAO, 10mL,45mmol,Al/pd=1500:1) was stirred at constant temperature 50 ℃; adding toluene solution of a phosphonic acid type palladium main catalyst (19.2 mg,30 mu mol) with a structure shown in a formula (VIII) into a reaction kettle; maintaining ethylene pressure at 0.5MPa and carrying out copolymerization reaction for 4h at 50 ℃, and stopping the reaction by using 100mL of ethanol solution of hydrochloric acid with volume fraction of 5%; the copolymer was obtained by filtration and washed three times with ethanol and dried under vacuum at 50℃to constant weight.
The catalyst activity of the phosphonic acid type palladium main catalyst in this comparative example was 3.08X10 3 g EMA/(mol Pd.h), the weight-average molecular weight of the copolymer obtained was 5.5kg/mol, the molecular weight distribution index was 1.81, the insertion rate of methyl acrylate was 16.8. Omega., the melting temperature was 123.9℃and the branching degree was 3/1000 ℃.
The results of the copolymerization of ethylene and methyl acrylate catalyzed in example 5 and comparative examples 1-3 are compared as shown in Table 1.
TABLE 1 comparison of the copolymerization results of ethylene and methyl acrylate catalyzed by different catalysts
As can be seen from Table 1, the alpha-carboxyl-beta-diimine nickel complex main catalyst can be used for catalyzing the copolymerization of ethylene and methyl acrylate more efficiently, and the activity of the catalytic copolymerization and the molecular weight and insertion rate of the product are obviously improved. In comparison, the α -diimine palladium catalyst produced highly branched ethylene methyl acrylate copolymers, the product having no melting temperature; and the palladium phosphine sulfonate catalyst is prepared into a completely linear copolymer. The EMA copolymer prepared by taking the alpha-carboxyl-beta-diimine nickel complex of the embodiment 5 of the invention as a main catalyst is a copolymer with low branching degree, has a melting temperature of 100.1 ℃ and branching degree of 36/1000 ℃, and is similar to an EMA branching structure prepared by commercial free radical.
Claims (10)
1. An alpha-carboxyl-beta-diimine nickel complex having the structure of formula (I):
in the general formula (I), two Ar are the same or different, and Ar is selected from 2, 6-dialkyl phenyl; x is a chlorine atom or a bromine atom; l is acetonitrile or benzonitrile.
2. The α -carboxy- β -diimine nickel complex of claim 1, wherein in formula (I), two Ar are the same or different and Ar is selected from 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl;
Preferably, in formula (I), two Ar are the same and Ar is 2, 6-diisopropylphenyl or 2, 6-dimethylphenyl;
more preferably, both Ar are the same and are both 2, 6-diisopropylphenyl.
3. A process for preparing the α -carboxy- β -diimine nickel complexes of claims 1 or 2, comprising the steps of:
(1) Reacting acetylacetone with 2, 6-dialkylaniline to obtain a 2, 6-dialkylphenyl-substituted beta-diimine compound;
(2) The 2, 6-dialkylphenyl substituted beta-diimine compound is subjected to substitution reaction with ammonium formate under the action of alkyl lithium to obtain alpha-carboxyl-beta-diimine lithium salt;
(3) And (3) carrying out coordination reaction on the alpha-carboxyl-beta-diimine lithium salt and halogenated nickel salt in acetonitrile or benzonitrile solvent to obtain the alpha-carboxyl-beta-diimine nickel complex.
4. Use of the α -carboxy- β -diimine nickel complexes of claims 1 or 2 as catalysts in olefin polymerization reactions;
preferably, the olefin polymerization comprises copolymerization of an olefin with a polar monomer;
preferably, the olefin is polymerized as a copolymerization of ethylene with an acrylic monomer; more preferably, the olefin is polymerized as a copolymerization of ethylene with methyl acrylate;
Preferably, the alpha-carboxy-beta-diimine nickel complexes are used as a primary catalyst in olefin polymerization reactions and an organoaluminum compound is used as a cocatalyst.
5. The use according to claim 4, wherein the organoaluminum compound comprises one or a combination of several of methylaluminoxane, modified methylaluminoxane, isobutylaluminoxane, triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and triisobutylaluminum;
preferably, the organic aluminum compound comprises one or a combination of several of methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane;
preferably, the molar ratio of the cocatalyst to the main catalyst of alnico is (500 to 3000): 1, more preferably (1000 to 2000): 1.
6. A method for producing an ethylene-methyl acrylate copolymer using the α -carboxy- β -diimine nickel complex of claim 1 or 2 as a main catalyst.
7. The method for producing an ethylene-methyl acrylate copolymer according to claim 6, wherein the method for producing comprises the steps of:
the alpha-carboxyl-beta-diimine nickel complex is used as a main catalyst, an organic aluminum compound is used as a cocatalyst, ethylene and methyl acrylate monomers are subjected to copolymerization reaction in a solvent, and after the reaction is finished, the ethylene-methyl acrylate copolymer is obtained.
8. The method for producing an ethylene-methyl acrylate copolymer according to claim 7, wherein the reaction temperature of the copolymerization reaction is 0 to 100 ℃, preferably 50 to 80 ℃;
preferably, the reaction pressure of the copolymerization reaction is 0.5-2.0 MPa;
preferably, the reaction time of the copolymerization reaction is 0.5 to 24 hours, more preferably 2 to 8 hours.
9. The process for producing an ethylene-methyl acrylate copolymer according to claim 7, wherein the molar ratio of said methyl acrylate monomer to said main catalyst α -carboxy- β -diimine nickel complex is (266 to 1600): 1, preferably (500 to 1066): 1;
preferably, the organic aluminum compound comprises one or a combination of several of methylaluminoxane, modified methylaluminoxane and isobutylaluminoxane;
preferably, the molar ratio of the cocatalyst to the main catalyst of alnico is (500 to 3000): 1, more preferably (1000 to 2000): 1;
preferably, the solvent comprises one or a combination of several of 1, 2-dichloroethane, n-hexane, chlorobenzene, toluene and xylene.
10. The method for producing an ethylene-methyl acrylate copolymer according to any one of claims 6 to 9, wherein the weight average molecular weight of the produced ethylene-methyl acrylate copolymer is 13.2 to 100.3kg/mol;
Preferably, the branching degree of the prepared ethylene-methyl acrylate copolymer is 25-51 branched chains/1000C;
preferably, the methyl acrylate insertion rate of the ethylene-methyl acrylate copolymer is 2.5-36.4 percent;
preferably, the melting temperature of the prepared ethylene-methyl acrylate copolymer is 81.3-125.3 ℃;
preferably, the molecular weight distribution index of the prepared ethylene-methyl acrylate copolymer is 1.28-2.63;
preferably, the catalytic activity of the main catalyst alpha-carboxyl-beta-diimine nickel complex is 0.89×10 4 -18.1×10 4 g EMA/(mol Ni·h)。
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