CN1544493A - Method for synthesizing copolymer of ethylene and methyl methacrylate - Google Patents
Method for synthesizing copolymer of ethylene and methyl methacrylate Download PDFInfo
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- CN1544493A CN1544493A CNA2003101158368A CN200310115836A CN1544493A CN 1544493 A CN1544493 A CN 1544493A CN A2003101158368 A CNA2003101158368 A CN A2003101158368A CN 200310115836 A CN200310115836 A CN 200310115836A CN 1544493 A CN1544493 A CN 1544493A
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- trifluoromethyl
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Abstract
The invention provides a process for synthesizing ethylene with methyl methacrylate copolymer comprising accelerating the copolymerization of ethylene and methyl methacrylate by catalytic system in organic solvent, wherein the catalytic system comprises organic nickel complex and organic aluminoxane as catalyst promoter, the primary catalyst has the formula disclosed in the specification, wherein L is triphenylphosphine, R is phenyl, R1 is phenyl, tertiary-butyl or trifluoromethyl, R2 is methyl or trifluoromethyl, R3 and R4 can be identical or different, which is methyl, isopropyl or tertiary-butyl. The catalyst promoter employed is methyl aluminoxane or modified methyl aluminoxane.
Description
Technical field
The present invention relates to the synthetic method of a kind of ethene and acrylate copolymer.
Background technology
Polyolefine is typical non-polar polymeric material, this feature limits its application in some aspects.Polar group or the molecule segment of introducing 2-5% in the molecular polyolefin chain can change its physical and chemical performance effectively, give its wetting ability, dyeability, colourability, impressionability, with the consistency of polar polymer, increase the surface tension of goods and to the clinging power of polar material etc., improve its added value, widen range of application.At present, industry still adopts traditional high-pressure free radical polymerization technique to prepare the multipolymer of ethene and polar monomer (vinyl acetate, acrylate etc.), and this method requires high-tension apparatus, and one-time investment is big.
Though Ziegler-Natta catalyst has been widely used in catalysed olefin polymerization, yet, be difficult to catalyzed alkene and the monomeric copolymerization of (methyl) acrylate isopolarity because this type of catalyzer has higher oxytropism.Metallocene/MAO catalytic systems for polymerization of olefins has very high activity, but also is difficult to catalyzed alkene and the monomeric copolymerization of (methyl) acrylate isopolarity; Though the polyreaction that the cationic metallocene catalyst of single component also can catalysis (methyl) acrylate is difficult to the copolymerization of catalysis alkene alkene and (methyl) acrylate.Rear transition metal has lower oxytropism, and heteroatoms in the polar monomer is shown stronger tolerance, but the copolymerization of catalyzed ethylene and acrylate.Calendar year 2001, human P such as Gibson, the copolymerization of O coordinate neutral nickel catalyzed ethylene and methacrylic ester, obtain lower molecular weight, hanged down the multipolymer (less than 1%) of polar monomer insertion rate, the polar structure unit is positioned at the macromole end of the chain (J Chem Soc, Chem Commun 2001,1964-1965).
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing organic nickel Preparation of Catalyst high molecular weight ethylene and methyl methacrylate copolymer to close.Preparation of Catalyst convenience, good stability, low price that the present invention uses, and the active height of catalyzed ethylene and methyl methacrylate copolymer, the polar monomer insertion rate of gained multipolymer is higher.
For achieving the above object, the synthetic method that the invention provides ethene and methylmethacrylate copolymer is: under the ethene atmosphere, in reactor, add toluene, Primary Catalysts, methyl methacrylate and promotor successively, the mol ratio of aluminium is 100-500 in Primary Catalysts and the promotor, be forced into 10-50atm, copolymerization 1-4 hour, reaction mixture be poured in the alcohol hydrochloric acid mixed solution, filter, drying, obtain the multipolymer of ethene and methyl methacrylate.
The Primary Catalysts that adopts in the above-mentioned reaction is the organic nickel title complex, and its structure is as follows:
In the formula: L is a triphenylphosphine; R is a phenyl; R
1Be phenyl, the tertiary butyl or trifluoromethyl, recommend the phenyl or the tertiary butyl, preferred phenyl; R
2Be methyl or trifluoromethyl, preferred trifluoromethyl; R
3And R
4Can be identical or inequality, be respectively methyl, sec.-propyl or the tertiary butyl, preferred sec.-propyl.
Described promotor is an Organoaluminoxy alkane, as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) etc., and preferred modified methylaluminoxane.
The organic nickel Preparation of catalysts process that the present invention adopts is as follows:
A) under the formic acid effect, in alcoholic solution, carry out the condensation reaction of the substituted aromatic amines shown in methyl ethyl diketone analogue and the following formula,
Obtain the western Buddhist alkali shown in the following formula,
B) under the anhydrous and oxygen-free condition, carry out the reaction of above-mentioned western Buddhist alkali and sodium hydride, obtain the negative ion part shown in the following formula
C) under the anhydrous and oxygen-free condition, carry out the coordination reaction of two (triphenyl phosphorus) nickelous chlorides of above-mentioned negative ion part and trans phenyl, the organic nickel norbornene polymerization catalyst agent that obtains being shown below
L is a triphenylphosphine in the formula; R is a phenyl; R
1Be phenyl, the tertiary butyl or trifluoromethyl; R
2Be methyl or trifluoromethyl; R
3And R
4Can be identical or different, be respectively methyl, sec.-propyl or the tertiary butyl.
Preparation of Catalyst provided by the invention is convenient, stable in properties, and under the activation of methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), but catalyzed ethylene and methacrylic ester copolymerization prepare the multipolymer of high molecular weight ethylene and methacrylic ester.
Embodiment
Now the invention will be further described by following embodiment.Because all catalyzer of the present invention play an important role in reaction, for ease of narration, describe Preparation of catalysts earlier, and then describe polyreaction.Thus, embodiment 1-5 describes the preparation of Primary Catalysts precursor west Buddhist alkali; Embodiment 6-10 describes and prepares Primary Catalysts with western Buddhist alkali; Embodiment 11-19 describes the synthetic method of ethene and methylmethacrylate copolymer.Need to prove that these embodiment just are used for and further specify, rather than restriction protection scope of the present invention.
Embodiment 1
In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-phenyl-1,3-dimethyl diketone 5.0g (23mmol), 2,6-diisopropyl aniline 5.32g (30mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 90h.The cooling reaction solution has clear crystal to separate out, and filters, with after the cold methanol washing for several times 60 ℃ of vacuum-drying 48h, De Xifo alkali (C
22H
24NOF
3) 4.78g, yield 55%.
1H?NMR(CDCl
3)：δ1?2.07(s，1H，O-H)，7.99(d，2H，Ph-H)，7.58-7.48(m，3H，Ph-H)，7.34(t，1H，Ph-H)，7.19(d，2H，Ph-H)，6.45(s，1H，＝CH)，3.11(m，2H，iPr-CH)，1.26-1.13(dd，12H，iPr-CH
3)。
Embodiment 2
In exsiccant 100mL reaction flask, add 1-phenyl-1,3-dimethyl diketone 3.24g (20mmol), 2,6-diisopropyl aniline 5.32g (30mmol), methyl alcohol 15mL, formic acid 0.6mL, room temperature reaction 24h.The cooling reaction solution has clear crystal to separate out, and filters, with after the cold methanol washing for several times 60 ℃ of vacuum-drying 48h, De Xifo alkali (C
22H
27NO) 4.76g, yield 74%.
1H?NMR(CDCl
3)：δ12.63(s，1H，O-H)，7.96(d，2H，Ph-H)，7.46-7.42(m，3H，Ph-H)，7.32(t，1H，Ph-H)，7.20(d，2H，Ph-H)，5.93(s，1H，＝CH)，3.12-3.06(m，2H，iPr-CH)，1.79(s，3H，CO-CH
3)，1.24-1.16(dd，12H，iPr-CH
3)。
Embodiment 3
In exsiccant 100mL reaction flask, add 1,1,1-three fluoro-2,4-diacetylmethane 4.0g (26mmol), 2,6-diisopropyl aniline 7.10g (64mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 24h.The cooling reaction solution has clear crystal to separate out, and filters, with after the cold methanol washing for several times 60 ℃ of vacuum-drying 48h, De Xifo alkali (C
16H
22NOF
3) 3.75g, yield 46%.
1H?NMR(CDCl
3)：δ12.22(s，1H，O-H)，7.46(t，1H，Ph-H)，7.22(d，2H，Ph-H)，5.59(s，1H，＝CH)，3.02-2.91(m，2H，iPr-CH)，1.84(s，3H，CO-CH
3)，1.27-1.18(dd，12H，iPr-CH
3)。
Embodiment 4
In exsiccant 100mL reaction flask, add 1,1,1-three fluoro-5,5-dimethyl-2,4-diacetylmethane 3.92g (20mmol), 2,6-diisopropyl aniline 5.31g (30mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 24h.The cooling reaction solution has clear crystal to separate out, and filters, with after the cold methanol washing for several times 60 ℃ of vacuum-drying 48h, De Xifo alkali (C
20H
28F
3NO) 3.77g, yield 53%.
1H?NMR(CDCl
3)：δ12.28(s，1H，O-H)，7.52(t，1H，Ph-H)，7.26(d，2H，Ph-H)，5.63(s，1H，＝CH)，3.10-2.94(m，2H，iPr-CH)，1.92(s，9H，t-Bu)，1.31-1.20(dd，12H，iPr-CH
3)。
Embodiment 5
In exsiccant 100mL reaction flask, add 4,4,4-three fluoro-1-phenyl-1,3-dimethyl diketone 4.32g (20mmol), 2-methyl-6-tert butyl aniline 4.96g (28mmol), methyl alcohol 15mL, formic acid 1mL, heating reflux reaction 90h.The cooling reaction solution has clear crystal to separate out, and filters, with after the cold methanol washing for several times 60 ℃ of vacuum-drying 48h, De Xifo alkali (C
22H
24NOF
3) 3.98g, yield 53%.
1H?NMR(CDCl
3)：δ12.09(s，1H，O-H)，8.01(d，2H，Ph-H)，7.59-7.50(m，3H，Ph-H)，7.36(t，1H，Ph-H)，7.20(d，2H，Ph-H)，6.46(s，1H，＝CH)，2.2(s，3H，CH
3)，1.28(s，9H，t-Bu)。
Embodiment 6
Under nitrogen protection; in exsiccant 50mL reaction flask, add western Buddhist alkali 0.50g (1.3mmol) and the tetrahydrofuran (THF) 20mL that sodium hydride 70mg (2.8mmol), embodiment 1 obtain; stirring at room reaction 2h; leach excessive sodium hydride, steam solvent; sodium salt with a small amount of exsiccant pentane washing generation; vacuum-drying obtains sodium salt 0.40g (1.0mmol).Sodium salt and two (triphenylphosphine) nickelous chloride 0.58g (0.95mmol) of trans phenyl are joined in the Schlenk bottle, add exsiccant benzene 20mL, stirring at room reaction 8h, after the vacuum filtration, filtrate is concentrated into 5mL, adds exsiccant pentane 30mL, place 2h, have red crystals to separate out, vacuum filtration, drying get red crystalline organic nickel title complex (C
46H
43F
3NniOP) 0.65g.
1H?NMR(C
6D
6)：δ7.62-6.40(m，29H，Ph-Hand＝CH)，3.85(m，2H，iPr-CH)，1.49-1.16(dd，12H，iPr-CH
3)。
Embodiment 7
Under nitrogen protection; in exsiccant 50mL reaction flask, add western Buddhist alkali 0.51g (1.6mmol) and the tetrahydrofuran (THF) 20mL that sodium hydride 80mg (3.2mmol), embodiment 2 obtain; stirring at room reaction 2h; leach excessive sodium hydride, steam solvent; sodium salt with a small amount of exsiccant pentane washing generation; vacuum-drying obtains sodium salt 0.42g (1.22mmol).Sodium salt and two (triphenylphosphine) nickelous chloride 0.70g (1.15mmol) of trans phenyl are joined in the Schlenk bottle, add exsiccant benzene 20mL, stirring at room reaction 8h, after the vacuum filtration, filtrate is concentrated into 5mL, adds exsiccant pentane 30mL, place 2h, have red crystals to separate out, vacuum filtration, drying get red crystalline organic nickel title complex (C
46H
46NNiOP) 0.61g.
1H?NMR(C
6D
6)：δ7.74-6.41(m，28H，Ph-H)，6.12(s，1H，＝CH)，3.96-3.92(m，2H，iPr-CH)，1.83(s，3H，CO-CH
3)，1.42-1.33(dd，12H，iPr-CH
3)。
Embodiment 8
Under nitrogen protection; in exsiccant 50mL reaction flask, add western Buddhist alkali 0.72g (2.3mmol) and the tetrahydrofuran (THF) 20mL that sodium hydride 110mg (4.6mmol), embodiment 3 obtain; stirring at room reaction 2h; leach excessive sodium hydride, steam solvent; sodium salt with a small amount of exsiccant pentane washing generation; vacuum-drying obtains sodium salt 0.69g (2.07mmol).Sodium salt and two (triphenylphosphine) nickelous chloride 1.21g (1.95mmol) of trans phenyl are joined in the Schlenk bottle, add exsiccant benzene 20mL, stirring at room reaction 8h, after the vacuum filtration, filtrate is concentrated into 5mL, adds exsiccant pentane 30mL, place 2h, have red crystals to separate out, vacuum filtration, drying get red crystalline organic nickel title complex (C
41H
41F
3NNiOP) 1.13g.
1H?NMR(C
6D
6)：δ7.64-6.36(m，23H，Ph-H)，5.77(s，1H，＝CH)，3.71-3.67(m，2H，iPr-CH)，1.52(s，3H，CO-CH
3)，1.31-1.16(dd，12H，iPr-CH
3)。
Embodiment 9
Under nitrogen protection; in exsiccant 50mL reaction flask, add western Buddhist alkali 0.53g (1.5mmol) and the tetrahydrofuran (THF) 20mL that sodium hydride 110mg (4.6mmol), embodiment 4 obtain; stirring at room reaction 2h; leach excessive sodium hydride, steam solvent; sodium salt with a small amount of exsiccant pentane washing generation; vacuum-drying obtains sodium salt 0.49g (1.3mmol).Sodium salt and two (triphenylphosphine) nickelous chloride 0.76g (1.1mmol) of trans phenyl are joined in the Schlenk bottle, add exsiccant benzene 20mL, stirring at room reaction 8h, after the vacuum filtration, filtrate is concentrated into 5mL, adds exsiccant pentane 30mL, place 2h, have red crystals to separate out, vacuum filtration, drying get red crystalline organic nickel title complex (C
46H
46F
3NNiOP) 0.73g.
1H?NMR(C
6D
6)：δ7.42-6.45(m，23H，Ph-H)，5.51(s，1H，＝CH)，3.01-2.96(m，2H，iPr-CH)，1.84(s，9H，t-Bu)，1.30-1.97(dd，12H，iPr-CH
3)。
Embodiment 10
Under nitrogen protection; in exsiccant 50mL reaction flask, add western Buddhist alkali 0.50g (1.3mmol) and the tetrahydrofuran (THF) 20mL that sodium hydride 70mg (2.8mmol), embodiment 5 obtain; stirring at room reaction 2h; leach excessive sodium hydride, steam solvent; sodium salt with a small amount of exsiccant pentane washing generation; vacuum-drying obtains sodium salt 0.39g (1mmol).Sodium salt and two (triphenylphosphine) nickelous chloride 0.58g (0.95mmol) of trans phenyl are joined in the Schlenk bottle, add exsiccant benzene 20mL, stirring at room reaction 8h, after the vacuum filtration, filtrate is concentrated into 5mL, adds exsiccant pentane 30mL, place 2h, have red crystals to separate out, vacuum filtration, drying get red crystalline organic nickel title complex (C
46H
43F
3NNiOP) 0.63g.
1H?NMR(CDCl
3)：δ7.78-6.33(m，39H，Ph-H?and＝CH)，1.98(s，3H，CH
3)，1.0(s，9H，t-Bu)。
Embodiment 11
Under room temperature and the ethene atmosphere, in the 100mL autoclave, add catalyzer 50 μ mol, methyl methacrylate 4.0mL that toluene 30mL, embodiment 6 obtain and modified methylaluminoxane (MMAO) the n-heptane solution 4mL of 2M successively, be forced into 20atm, behind the copolymerization 2h, reaction mixture is poured in the 200mL alcohol hydrochloric acid mixed solution, filtration, drying get thick product multipolymer 0.73g, catalytic efficiency 7.3kg/mol
NiH.In order to remove the micro-polymethylmethacrylate that may be mixed with in the multipolymer, multipolymer is put into 20mL 1,2, in the 4-trichlorobenzene and be heated to 120 ℃ and make it to dissolve fully, pour into then in the tetrahydrofuran (THF) of 100mL, same step repeats secondary, obtain the random copolymers 0.72g of purified ethene and methyl methacrylate, the insertion rate of methyl methacrylate is 6.7mol%, weight-average molecular weight 4.3 ten thousand, molecular weight distributing index 5.6.
1H?NMR(o-C
6D
4Cl
2)：δ1.36，1.20，0.93，3.63，2.03?1.15；
13C?NMR(o-C
6D
4Cl
2)：δ37.8，33.5，30.6，30.2，27.7?20.2，177.5，54.9，51.5，45.9，27.6，18.6。
Embodiment 12
The organic nickel catalyzer that the organic nickel catalyzer that obtains with embodiment 7 replaces embodiment 6 to prepare, operation gets thick product copolymer 1 .77g, catalytic efficiency 17.7kg/mol with embodiment 11
NiH.Refining back (process is with embodiment 11) gets the random copolymers 1.77g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 0.8mol%, weight-average molecular weight 9.9 ten thousand, molecular weight distributing index 4.1.
Embodiment 13
The organic nickel catalyzer that the organic nickel catalyzer that obtains with embodiment 8 replaces embodiment 6 to prepare, the consumption of MMAO is 8mL, operation must get thick product multipolymer 0.31g, catalytic efficiency 3.1kg/mol with embodiment 11
NiH.Refining back (process is with embodiment 11) gets the random copolymers 0.28g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 16.7mol%, weight-average molecular weight 15.5 ten thousand, molecular weight distributing index 21.
Embodiment 14
The organic nickel catalyzer that the organic nickel catalyzer that obtains with embodiment 9 replaces embodiment 6 to prepare, polymerization pressure is 10atm, operation gets thick product multipolymer 0.33g, catalytic efficiency 3.3kg/mol with embodiment 11
Ni.h.Refining back (process is with embodiment 11) gets the random copolymers 0.32g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 3.4mol%, weight-average molecular weight 3.9 ten thousand, molecular weight distributing index 4.6.
Embodiment 15
The organic nickel catalyzer that the organic nickel catalyzer that obtains with embodiment 10 replaces embodiment 6 to prepare, operation gets thick product multipolymer 0.73g, catalytic efficiency 7.3kg/mol with embodiment 11
NiH.Refining back (process is with embodiment 11) gets the random copolymers 0.72g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 7.8mol%, weight-average molecular weight 5.3 ten thousand, molecular weight distributing index 5.6.
Embodiment 16
The organic nickel catalyzer that obtains with embodiment 8 replaces the organic nickel catalyzer of embodiment 6 preparations, and polyreaction is carried out under 50atm and 40 ℃, and operation is with embodiment 11, thick product copolymer 1 .63g, catalytic efficiency 16.3kg/mol
NiH.Refining back (process is with embodiment 11) gets the random copolymers 1.62g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 2.4mol%, weight-average molecular weight 9.3 ten thousand, molecular weight distributing index 5.3.
Embodiment 17
With the modified methylaluminoxane in methylaluminoxane (MAO) the n-heptane solution 4mL alternate embodiment 11 of 2M, operation gets thick product multipolymer 0.70g catalytic efficiency 7.0kg/mol with embodiment 11
NiH.Refining back (process is with embodiment 11) gets the random copolymers 0.68g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 7.1mol%, weight-average molecular weight 4.8 ten thousand, molecular weight distributing index 5.8.
Embodiment 18
The organic nickel catalyzer that the organic nickel catalyzer that obtains with embodiment 8 replaces embodiment 6 to prepare, the consumption of MMAO is 2.5mL, operation must get thick product multipolymer 0.23g, catalytic efficiency 2.3kg/mol with embodiment 11
NiH.Refining back (process is with embodiment 11) gets the random copolymers 0.23g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 15.4mol%, weight-average molecular weight 16.4 ten thousand, molecular weight distributing index 18.
Embodiment 19
The organic nickel catalyzer that obtains with embodiment 8 replaces the organic nickel catalyzer of embodiment 6 preparations, and the consumption of MMAO is 12.5mL, and polyreaction is carried out under 50atm and 15 ℃, and operation is with embodiment 11, thick product copolymer 1 .44g, catalytic efficiency 14.4kg/mol
NiH.Refining back (process is with embodiment 11) gets the random copolymers 1.40g of ethene and methyl methacrylate, and the insertion rate of methyl methacrylate is 1.6mol%, weight-average molecular weight 7.4 ten thousand, molecular weight distributing index 4.3.
Claims (5)
1, the synthetic method of a kind of ethene and methylmethacrylate copolymer, under the ethene atmosphere, in reactor, add toluene, Primary Catalysts, methyl methacrylate and promotor successively, the mol ratio of aluminium is 100-500 in Primary Catalysts and the promotor, be forced into 10-50atm, copolymerization 1-4 hour, obtain the multipolymer of ethene and methyl methacrylate;
Described Primary Catalysts is the organic nickel title complex, and its structure is as follows:
In the formula: L is a triphenylphosphine; R is a phenyl; R
1Be phenyl, the tertiary butyl or trifluoromethyl; R
2Be methyl or trifluoromethyl; R
3And R
4Can be identical, be respectively methyl, sec.-propyl or the tertiary butyl;
Described promotor is methylaluminoxane or modified methyl machine aikyiaiurnirsoxan beta.
2, according to the described catalyzer of claim 1, R is a phenyl; R
1Be phenyl, the tertiary butyl or trifluoromethyl; R
2Be methyl or trifluoromethyl; R
3And R
4Be sec.-propyl, promotor is MAO or MMAO, and copolymerization carries out in dry toluene.
3, according to the described catalyzer of claim 1, R is a phenyl; R
1Be the phenyl or the tertiary butyl; R
2Be trifluoromethyl; R
3And R
4Be sec.-propyl, promotor is MMAO, and copolymerization carries out in dry toluene.
4, according to the described catalyzer of claim 1, R is a phenyl; R
1Be phenyl; R
2Be trifluoromethyl; R
3And R
4Be sec.-propyl, promotor is MMAO, and copolymerization carries out in dry toluene.
5, organic nickel Preparation of catalysts method according to claim 1, its key step is:
A) under the formic acid effect, carry out the condensation reaction of the substituted aromatic amines shown in methyl ethyl diketone and the following formula in the alcoholic solution,
Obtain the western Buddhist alkali shown in the following formula,
B) under the anhydrous and oxygen-free condition, carry out the reaction of above-mentioned western Buddhist alkali and sodium hydride, obtain the negative ion part shown in the following formula
C) under the anhydrous and oxygen-free condition, carry out the coordination reaction of two (triphenyl phosphorus) nickelous chlorides of above-mentioned negative ion part and trans phenyl, the organic nickel olefin polymerization catalysis that obtains being shown below
L is a triphenylphosphine in the formula; R is a phenyl; R
1Be phenyl, the tertiary butyl or trifluoromethyl; R
2Be methyl or trifluoromethyl; R
3And R
4Can be identical, be respectively methyl, sec.-propyl or the tertiary butyl.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008510001A (en) * | 2004-08-18 | 2008-04-03 | コーネル・リサーチ・ファンデーション・インコーポレイテッド | Alkene polymerization using β-ketoiminato metal complex |
| CN106589180A (en) * | 2016-09-26 | 2017-04-26 | 天津大学 | Large-steric-hindrance neutral nickel catalyst, preparation method and application in preparation of ethylene/polar monomer copolymers |
| CN114206956A (en) * | 2019-08-20 | 2022-03-18 | 陶氏环球技术有限责任公司 | Bis (phosphino) -phenoxynickel (II) catalysts for copolymerization of ethylene and acrylate monomers |
| 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 |
-
2003
- 2003-11-27 CN CNA2003101158368A patent/CN1544493A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008510001A (en) * | 2004-08-18 | 2008-04-03 | コーネル・リサーチ・ファンデーション・インコーポレイテッド | Alkene polymerization using β-ketoiminato metal complex |
| CN106589180A (en) * | 2016-09-26 | 2017-04-26 | 天津大学 | Large-steric-hindrance neutral nickel catalyst, preparation method and application in preparation of ethylene/polar monomer copolymers |
| CN114206956A (en) * | 2019-08-20 | 2022-03-18 | 陶氏环球技术有限责任公司 | Bis (phosphino) -phenoxynickel (II) catalysts for copolymerization of ethylene and acrylate monomers |
| 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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