CN101633707B - Method for copolymerizing ethylene and methyl methacrylate - Google Patents
Method for copolymerizing ethylene and methyl methacrylate Download PDFInfo
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- CN101633707B CN101633707B CN200810117105XA CN200810117105A CN101633707B CN 101633707 B CN101633707 B CN 101633707B CN 200810117105X A CN200810117105X A CN 200810117105XA CN 200810117105 A CN200810117105 A CN 200810117105A CN 101633707 B CN101633707 B CN 101633707B
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- methyl methacrylate
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000005977 Ethylene Substances 0.000 title abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002466 imines Chemical class 0.000 claims description 23
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 230000002045 lasting effect Effects 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 31
- 229920000642 polymer Polymers 0.000 abstract description 9
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000006698 induction Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 244000144992 flock Species 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 125000005574 norbornylene group Chemical group 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for polymerizing or copolymerizing ethylene and methyl methacrylate, which takes a bis-salicylaldehyde imine nickel catalyst as a main catalyst, takes methylaluminoxane as a cocatalyst, takes the molar ratio of aluminum in the cocatalyst to Ni in the main catalyst to be 50-1000: 1, and is carried out at the constant temperature of 0-80 ℃ during polymerization or copolymerization, wherein ethylene is saturated and is continuously introduced at the pressure of 1-60atm, the molar ratio of methyl methacrylate to Ni in the bis-salicylaldehyde imine nickel catalyst is 100-10000: 1, and the reaction is terminated for 0.5-6 hr; the catalyst can adjust the molecular weight, molecular weight distribution, polymer structure and component proportion of ethylene and methyl methacrylate polymer and copolymer of ethylene and methyl methacrylate by adjusting polymerization conditions and catalyst structure.
Description
Technical field
The present invention relates to the method that a kind of ethene and methyl methacrylate copolymer close.
Background technology
Although polyolefine, particularly polyethylene and polypropylene are very outstanding polymer materialss, can be used as the material of relevant high-mechanical property, yet they there is the weak point of surface property, for example: adhesion, impressionability, dyeability also has special weak point to be: and the compatibility and the functionalized (oxidation inhibitor of polar polymer, fire retardant etc.) affinity is bad, and these shortcomings make them can not use in some place.Therefore study alkene, polar monomer polymerization, and both copolymerization are significant.
Yet, for traditional Ziegler-Natta catalyst and metallocene catalyst, contained heteroatoms on the polar monomer, as O, N, S or halogen etc., can reduce the polycoordination reactive behavior of alkene greatly, even form stable title complex with central metal coordination on the catalyzer, stop further carrying out of polyreaction.Therefore, this two classes catalyzer all can not make the polar monomer polymerization, can not make polar monomer and alkene carry out copolymerization.For the latter, normally earlier polar monomer is carried out copolymerization with alkene again after chemoproection and space protection.In recent years, late transition metal catalyst for olefin polymerization has lower oxytropism because of it, and polar group is had stronger tolerance, thereby both can make that alpha-olefin, polar monomer can polymerizations, but also can make both copolymerization to become possibility.1998, the Grubbs group of California Inst Tech USA has reported a class salicylic alidehyde imine nickel complex, but catalyzed ethylene polymerization not only, but the norbornylene of catalyzed ethylene and hydroxyl (norbornylene-4 one alcohol), ethene and contain the copolymerization (Science of the norbornylene (norbornylene 4 one methyl-formiates) of ester group, 2000,287,460-462).But this class catalyst structure must connect big steric hindrance substituting group at the ortho position of part phenolic hydroxyl group, is difficult for preparation and introduce big steric hindrance substituting group.With salicylic alidehyde imine nickel catalyzator structure similar, Carlini group has reported two (N-sec.-propyl) salicylic alidehyde imine nickel complexes and two (3,5-dinitrobenzene-N-2, the 6-diisopropyl phenyl) salicylic alidehyde imine nickel complex, under MAO causes, can carry out polymerization to ethene, methyl methacrylate equally, and both are carried out copolymerization.Vinyl polymerization is obtained oligopolymer or superpolymer, and catalytic activity is higher.But to methyl methacrylate polymerization, catalytic activity is general, and obtains the very wide PMMA of molecular weight distribution; Ethene and methyl methacrylate copolymer are closed, and catalytic activity gained molecular weight of copolymer is medium, and (Mn is 2.77 * 10
5), molecular weight distribution is wide, wherein MMA content be 50-80% (mol) (Macromol.Chem.Phys., 2002,203:1606-1613).CN1463959A and CN1510014A disclose a kind of two (salicylic alidehyde imine) nickel complex, are mainly used in propylene dimerization and prepare six carbenes.This catalyzer mainly is an aluminum alkyls at organoaluminum, or organophosphorus causes down, and catalytic activity can reach 240000molC
3 =/ mol Ni h, the selectivity of six carbon olefins reaches 90%, 2, and the selectivity of 3-neohexene reaches 64%.
Summary of the invention
The object of the present invention is to provide and a kind ofly finish ethene, methyl methacrylate polymerization with the Bis (salicylaldehyde) imine nickel as catalyst agent, and the method for both copolymerizations.
The present invention adopts thisly is used for the Bis (salicylaldehyde) imine nickel as catalyst agent that ethene, methyl methacrylate polymerization and both copolymerizations are used, and its structure has following general formula
In the formula (I), Xn is one or two alkyl that C1～C6 replaces, or phenyl.
The present invention realizes the method for ethene, methyl methacrylate polymerization and both copolymerizations with the Bis (salicylaldehyde) imine nickel as catalyst agent: be Primary Catalysts with the Bis (salicylaldehyde) imine nickel as catalyst agent when ethene, methyl methacrylate polymerization and both copolymerizations, with the methylaluminoxane is promotor, and the mol ratio of Ni is 50～1000: 1 (preferred 100-500: 1) in aluminium in the promotor and the Primary Catalysts.When polymerization or copolymerization, under 0～80 ℃ of constant temperature, carry out (preferred 20～40 ℃), ethene is saturated and continues to feed with the pressure of 1-60atm (preferred 10-30atm), the mol ratio of Ni is 100-10000 in methyl methacrylate and the Bis (salicylaldehyde) imine nickel as catalyst agent: 1 (preferred 100-5000: 1), reaction 0.5-6hr (preferred 1-3hr) termination.
Ethylene polymerisation process is: add polymerization in the autoclave under ethene atmosphere with solvent and nickel catalyzator, stir, after logical ethene is extremely saturated, add promotor, continuing to feed ethylene gas and keep ethylene pressure is 1-60atm, behind the reaction 0.5-6hr, stop to feed ethylene gas, polymer fluid is airtight, and place the refrigerator subcooling immediately, behind the 0.5hr, the adding volume fraction is 5% ethanol solution hydrochloride termination reaction, and adding 1mL positive heptan as interior mark, the clear liquid that takes a morsel after mixing carries out GC-MS to be analyzed, and measures possible oligopolymer composition and content.If in remaining mixture, there is superpolymer to exist, then after filtration, washing, dry, obtain superpolymer.
The methyl methacrylate polymerization process is: add nickel catalyzator in polymerization bottle, the argon filling of finding time seals for several times, add polymerization solvent and methyl methacrylate (MMA) monomer successively, mix the back and add MAO, behind polymerase 10 .5～6hr, add volume fraction and be 5% ethanol solution hydrochloride termination reaction, after filtration, washing, drying, obtain polymkeric substance.
Ethene and the methyl methacrylate copolymer process of closing are: add polymerization solvent and nickel catalyzator in the autoclave under ethene atmosphere, logical ethene is to saturated, stir, add methyl methacrylate, add promotor, continuing to feed ethylene gas and keep ethylene pressure is 1-60atm, stop to feed ethylene gas behind the reaction 0.5-6hr, add volume fraction after the release and be 5% ethanol solution hydrochloride termination reaction, after filtration, washing, drying, obtain multipolymer.
The polymerization solvent of dissolving Bis (salicylaldehyde) imine nickel as catalyst agent is an aromatic hydrocarbons in polymerization or the copolymerization process, halogenated aryl hydrocarbon, alkane, or halogenated alkane, preferred toluene, normal hexane, methylene dichloride.
The present invention compared with prior art has following obvious advantage:
Catalyzer provided by the invention not only can be used for ethene, methyl methacrylate polymerization, but also can be used for both copolymerization.By regulating polymerizing condition, catalyst structure realizing to ethene, methyl methacrylate polymer, and ethene and methylmethacrylate copolymer molecular weight, molecular weight distribution, polymer architecture, and each component ratio of multipolymer is regulated.
Embodiment
Embodiment 1
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add normal hexane 50mL, and two [3-methyl-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 60 ℃ of oil bath constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, add MAO (1.53M, 1.3mL), continue to feed ethylene gas, and the maintenance ethylene pressure is 30atm, behind the reaction 1hr, stop to feed ethylene gas, polymer fluid is airtight, and place under the refrigerator low temperature freezing immediately, 0.5hr after, add volume fraction and be 5% ethanol solution hydrochloride termination reaction, and add 1mL positive heptan as interior mark, get clear liquid after mixing and carry out the GC-MS analysis, composition and the content of measuring oligopolymer are: C4:68.85%, C6:25.15%, C8:6.0%.Activity of such catalysts is 2.13 * 10
3G/molNihr.
Embodiment 2
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add methylene dichloride 50mL, and two [3-sec.-propyl-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 80 ℃ of oil bath constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, and adding MAO (1.53M, 26mL), continue to feed ethylene gas, and to keep ethylene pressure be 20am, behind the reaction 2hr, stop to feed ethylene gas, polymer fluid is airtight, and place under the refrigerator low temperature freezing immediately, 0.5hr after, add volume fraction and be 5% ethanol solution hydrochloride termination reaction, and add 1mL positive heptan as interior mark, get clear liquid after mixing and carry out the GC-MS analysis, composition and the content of measuring oligopolymer are: C4:24.8%, C6:31.6%, C8:22.1%.Activity of such catalysts is 155 * 10
3G/molNihr.
Embodiment 3
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add toluene 50mL, and two [the 3-tertiary butyl-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 20 ℃ of oil bath constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, and adding MAO (1.53M, 13mL), continue to feed ethylene gas, and to keep ethylene pressure be 60atm, behind the reaction 6hr, stop to feed ethylene gas, polymer fluid is airtight, and place under the refrigerator low temperature freezing immediately, 0.5hr after, add volume fraction and be 5% ethanol solution hydrochloride termination reaction, and add 1mL positive heptan as interior mark, get clear liquid after mixing and carry out the GC-MS analysis, composition and the content of measuring oligopolymer are: C4:33.8%, C6:45.8%, C8:20.3%.Activity of such catalysts is 21 * 10
3G/molNihr.
Embodiment 4
In 50ml cleaning exsiccant polymerization bottle, the general is two, and [3-phenyl-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) (20 μ mol) is dissolved in the chlorobenzene (21.9mL), (2.34mmol 0.236g), mixes 10min under the room temperature to add MMA, add MAO (1.53M then, 1.3mL Al/Ni=100), the even back of remix is in 20 ℃ of following polyase 13 hr.Pour in the ethanolic soln that volume fraction is 5% hydrochloric acid after polymerization finishes and stop, the polymkeric substance flocks that is white in color, after filtration, washing, decompressing and extracting obtain polymkeric substance 0.12g, transformation efficiency 50.8%, viscosity-average molecular weight 117.5 ten thousand, a normality 68.45%.
Embodiment 8
In 50ml cleaning exsiccant polymerization bottle, two [3,5-two bromo-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) (20 μ mol) are dissolved in the normal hexane (0.5mL), add MMA (11.7mmol, 1.18g, 1.25ml), mix 10min under the room temperature, add MAO (1.53M then, 2.6mL Al/Ni=200), the even back of remix is in 40 ℃ of following polymerization 2hr.Pour in the ethanolic soln that volume fraction is 5% hydrochloric acid after polymerization finishes and stop, the polymkeric substance flocks that is white in color, after filtration, washing, decompressing and extracting obtain polymkeric substance 0.83g, transformation efficiency 70%, viscosity-average molecular weight 95.3 ten thousand, a normality 73.65%.
Embodiment 10
In 50ml cleaning exsiccant polymerization bottle, with two [3,5-dimethyl-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) (20 μ mol) is dissolved in the normal hexane (13.9mL), adds MMA (23.4mmol, 2.36g), mix 10min under the room temperature, add MAO (1.53M, 7.0mL then, Al/Ni=500), the even back of remix is in 60 ℃ of following polymerization 1hr.Pour in the ethanolic soln that contains 5% hydrochloric acid after polymerization finishes and stop, the polymkeric substance flocks that is white in color, after filtration, washing, decompressing and extracting obtain polymkeric substance 1.64g, transformation efficiency 70%, viscosity-average molecular weight 81.8 ten thousand, a normality 70.91%.
Embodiment 11
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add chlorobenzene (21.9mL), two [the 3-tertiary butyl-N-(phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 0 ℃ of following constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, and the adding methyl methacrylate (2.34mmol, 0.236g), (1.53M 1.3mL), continues to feed ethylene gas to MAO, and the maintenance ethylene pressure is 60atm, behind the reaction 6hr, stopping to feed ethylene gas, is the processing of 5% ethanol solution hydrochloride with volume fraction after the release, through washing, filter, drying obtains multipolymer 0.1g.
Embodiment 12
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add chlorobenzene 47.4mL, two [5-methyl-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 20 ℃ of oil bath constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, add methyl methacrylate 10mmol, MAO (1.53M, 26mL), continue to feed ethylene gas, and to keep ethylene pressure be 30atm, behind the reaction 3hr, stop to feed ethylene gas, be that 5% ethanol solution hydrochloride is handled with volume fraction after the release,, filter through washing, drying obtains multipolymer 0.6g.
Embodiment 13
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add normal hexane 44.8mL, two [3,5-two bromo-N-(2-Phenoxyphenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 40 ℃ of oil bath constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, add methyl methacrylate 20mmol, add MAO (1.53M, 2.6mL), continue to feed ethylene gas, and to keep ethylene pressure be 20atm, behind the reaction 2hr, stop to feed ethylene gas, be that 5% ethanol solution hydrochloride is handled with volume fraction after the release,, filter through washing, drying obtains copolymer 1 .7g.
Embodiment 14
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add methylene dichloride 42.2mL, two [N-(2-p-methoxy-phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene places 80 ℃ of oil bath constant temperature simultaneously, and starts induction stirring to saturated.After treating that ethene is saturated, add methyl methacrylate 50mmol, add MAO (1.53M, 13mL), continue to feed ethylene gas, and to keep ethylene pressure be 1atm, behind the reaction 0.5hr, stop to feed ethylene gas, be that 5% ethanol solution hydrochloride is handled with volume fraction after the release,, filter through washing, drying obtains multipolymer 3.1g.
Embodiment 15
In 150mL cleaning exsiccant autoclave, under ethene atmosphere, add toluene 24mL, two [3,5-dinitrobenzene-N-(2, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni (II) 40 μ mol, logical ethene is to saturated, place 60 ℃ of oil bath constant temperature simultaneously, and start induction stirring.After treating that ethene is saturated, add methyl methacrylate 50mmol, add MAO (1.53M, 7.8mL), continue to feed ethylene gas, and to keep ethylene pressure be 10atm, behind the reaction 1hr, stop to feed ethylene gas, be that 5% ethanol solution hydrochloride is handled with volume fraction after the release,, filter through washing, drying obtains multipolymer 3.8g.
Claims (1)
1. ethene and the methyl methacrylate copolymer method of closing, it is characterized in that: this method is to be Primary Catalysts with the Bis (salicylaldehyde) imine nickel as catalyst agent, with the methylaluminoxane is promotor, the mol ratio of Ni is 50～1000: 1 in aluminium in the promotor and the Primary Catalysts, during copolymerization, under 0～80 ℃ of constant temperature, carry out, ethene is saturated and feeds so that the pressure of 1-60atm is lasting, the mol ratio of Ni is 100-10000 in methyl methacrylate and the Bis (salicylaldehyde) imine nickel as catalyst agent: 1, and reaction 0.5-6hr stops; This catalyst structure is:
In the formula (I), Xn is one or two phenyl, or halogen;
Wherein i-Pr is a sec.-propyl.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864010B (en) * | 2010-06-21 | 2011-08-10 | 北京大学 | Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization |
| CN107868158A (en) * | 2016-09-22 | 2018-04-03 | 中国石油天然气股份有限公司 | Method for copolymerizing ethylene and ester |
| CN108264595B (en) * | 2016-12-30 | 2021-01-29 | 中国石油天然气股份有限公司 | Copolymerization method of ethylene and vinyl ester |
| CN108264594B (en) * | 2016-12-30 | 2021-03-30 | 中国石油天然气股份有限公司 | Copolymerization method of ethylene and vinyl ester |
| CN116410379A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Catalyst for copolymerization of ethylene and methyl methacrylate and application thereof |
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