CN101633707A - Method for polymerizing or copolymerizing ethylene and methyl methacrylate - Google Patents
Method for polymerizing or copolymerizing ethylene and methyl methacrylate Download PDFInfo
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- CN101633707A CN101633707A CN200810117105A CN200810117105A CN101633707A CN 101633707 A CN101633707 A CN 101633707A CN 200810117105 A CN200810117105 A CN 200810117105A CN 200810117105 A CN200810117105 A CN 200810117105A CN 101633707 A CN101633707 A CN 101633707A
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Abstract
The invention relates to a method for polymerizing or copolymerizing ethylene and methyl methacrylate. The method uses a bisalicylaldehyde nickel imine catalyst as a main catalyst and uses methylaluminoxane as a co-catalyst, wherein the molar ratio of aluminum in the co-catalyst to Ni in the main catalyst is 50-1,000: 1; and the polymerization or copolymerization is carried out at the constant temperature of between 0 and 80 DEG C, the ethylene is saturated and introduced continuously under the pressure of 1 to 60atm, the molar ratio of the methyl methacrylate to the Ni in the bisalicylaldehyde nickel imine catalyst is 100-10,000:1, and the reaction is finished after 0.5 to 6 hours. The catalyst can realize adjustment of the molecular weight, the molecular weight distribution, polymer structure and the proportion of components of the copolymers which are a polymer of the ethylene and the methyl methacrylate, and a copolymer of the ethylene and the methyl methacrylate.
Description
Technical field
The present invention relates to the method for a kind of ethene, methyl methacrylate polymerization or copolymerization.
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. the method for an ethene, methyl methacrylate polymerization or copolymerization, 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, when polymerization or 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 alkyl that C1～C6 replaces, or phenyl, or halogen; Wherein i-Pr is a sec.-propyl.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864010A (en) * | 2010-06-21 | 2010-10-20 | 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 | A kind of ethene and the method for ester copolymerization |
| CN108264594A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of copolymerization process of ethylene and vinyl esters |
| CN108264595A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of copolymerization process of ethylene and vinyl esters |
| WO2023124965A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Catalyst for copolymerization of ethylene and methyl methacrylate, and application of catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2550641B2 (en) * | 1988-02-29 | 1996-11-06 | 住友化学工業株式会社 | Method for dimerizing lower α-olefins |
| CN1114497C (en) * | 2001-06-26 | 2003-07-16 | 中国科学院长春应用化学研究所 | Preparation method of self-solidified 'after cyclopentadiene' nickel base olefinic polymerization catalyst |
| CN1167720C (en) * | 2002-07-18 | 2004-09-22 | 中国科学院化学研究所 | Polymeric catalyst system of norbornaene and its preparing process |
| CN101092459A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Load type polymerization catalyzed system, preparation method and application |
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2008
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864010A (en) * | 2010-06-21 | 2010-10-20 | 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 | A kind of ethene and the method for ester copolymerization |
| CN108264594A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of copolymerization process of ethylene and vinyl esters |
| CN108264595A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of copolymerization process of ethylene and vinyl esters |
| 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 |
| WO2023124965A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Catalyst for copolymerization of ethylene and methyl methacrylate, and application of catalyst |
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