CN1408737A - Catalytic system for ethylene and acrylic ester copolymerization - Google Patents

Catalytic system for ethylene and acrylic ester copolymerization Download PDF

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CN1408737A
CN1408737A CN 02130960 CN02130960A CN1408737A CN 1408737 A CN1408737 A CN 1408737A CN 02130960 CN02130960 CN 02130960 CN 02130960 A CN02130960 A CN 02130960A CN 1408737 A CN1408737 A CN 1408737A
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catalyst system
ethene
mol
copolymerization
methyl
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刘靖宇
郑毅
李悦生
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

Of the catalyst system for ethylene and acrylic ester copolymerization, the main catalyst is pyridyl ferric imine compound and the cocatalyst is organic aluminum compound. Under the action of methyl alum oxane, modified methyl alum oxane or other organic aluminium compound, the catalyst can catalyze the copolymerization of ethylene and acrylic ester to obtain the copolymer.

Description

A kind of catalyst system that is used for ethene and acrylic ester copolymerization
Technical field
The present invention relates to a kind of catalyst system that is used for ethene and acrylic ester copolymerization.
The invention still further relates to the preparation method of above-mentioned catalyst system.
The invention still further relates to the application of above-mentioned catalyst system in ethene and acrylic ester copolymerization.
Background technology
Polyolefine is the important macromolecular material of a class, accounts for 50% of institute's plastics, is widely used in industry, agricultural, national defence, communications and transportation and the daily life.Polyolefine is a non-polar polymeric material, introduces the chemical physics performance that the polar functionalities group can effectively improve product in its molecular chain, can increase polyolefinic wetting ability, the surface tension of goods, and the intermiscibility of increase and polar polymer is widened 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 olefinic polyreaction, yet, can not be used for alkene and the monomeric copolymerization of acrylate isopolarity because this type of catalyzer has higher oxytropism.Metallocene calalyst for polymerization of olefine has very high activity, but is difficult to catalyzed ethylene and the monomeric copolymerization of acrylate isopolarity; Though the cationic metallocene catalyst of single component also can catalysis (methyl) acrylic ester polymerization, be difficult to catalyzed ethylene and (methyl) acrylic ester copolymerization.Rear transition metal has lower oxytropism, and heteroatoms in the polar monomer is shown inertia, but the copolymerization of catalyzed ethylene and acrylate.1996, human alpha-diimine Pd (II) catalyzed ethylene and acrylic ester copolymerizations such as Brookhart obtained the multipolymer of ethene and acrylate, but very low (the J Am Chem Soc 118 (1996): 11664-11665) of catalytic activity.
Summary of the invention
The method that the purpose of this invention is to provide a kind of ethene and acrylic ester copolymerization.Preparation of Catalyst convenience, good stability, low price that the present invention uses, and catalyzed ethylene and acrylic ester copolymer is active high.
For achieving the above object, catalyst system provided by the invention is made up of Primary Catalysts pyridine diimine Fe (II) title complex and promotor organo-aluminium compound, and the structure of Primary Catalysts is as follows:
Figure A0213096000061
X is Cl or Br in the formula; R is H or methyl; R 1, R 2Be respectively methyl, ethyl, sec.-propyl or the tertiary butyl, preferred sec.-propyl; R 1, R 2Can be identical or different.
Described promotor is methylaluminoxane or modified methylaluminoxane, preferred modified methylaluminoxane.
Primary Catalysts provided by the invention prepares according to the following procedure:
Under Catalyzed by p-Toluenesulfonic Acid, under the refluxing toluene condition, carry out 2, the condensation reaction of 6-diacetyl pyridine and substituted aromatic amines, the pyridine diimine compound that obtains replacing.Under the room temperature, in tetrahydrofuran (THF), carry out pyridine diimine compound and FeX 2Coordination reaction, obtain pyridine diimine Fe (II) title complex, its reaction as shown in the formula: X is Cl or Br in the formula; R is H or methyl; R 1, R 2Be respectively methyl, ethyl, sec.-propyl or the tertiary butyl; R 1, R 2Can be identical or different.
Above-mentioned catalyst system is used for the copolymerization of ethene and acrylate, in organic solvent, the mol ratio of acrylate and Primary Catalysts pyridine diimine Fe (II) title complex is 200-5000, the mol ratio of promotor organo-aluminium compound and Primary Catalysts pyridine diimine Fe (II) title complex is 100-2000, reaction times 0.1-2 hour, pressure is the 1-10 normal atmosphere, and temperature is 0-50 ℃.The organic solvent that adopts is a dry toluene.
Embodiment
Press in the Primary Catalysts of embodiment 1 described method preparation, because of different its symbolic significances of catalyzer that prepare of its substituting group are:
A：R＝CH 3，R 1＝R 2＝i-Pr，X＝Cl
B：R＝CH 3，R 1＝R 2＝CH 3，X＝Cl
C：R＝CH 3，R 1＝R 2＝C 2H 5，X＝Cl
D：R＝CH 3，R 1＝R 2＝i-Pr，X＝Br
E：R＝CH 3，R 1＝i-Pr，R 2＝CH 3，X＝Cl
F：R＝CH 3，R 1＝t-Bu，R 2＝H，X＝Cl
G：R＝H，R 1＝R 2＝i-Pr，X＝Cl
Embodiment 1
In the 250ml reaction flask, add 2,6-diacetyl pyridine 0.5g, 2,6 diisopropyl aniline 1.08g, tosic acid 0.01g, 100ml toluene, back flow reaction 3 days gets 1.4g light yellow crystal (productive rate 94%) through column chromatography.In above-mentioned product, add 0.56gFeCl again 24H 2O, under the room temperature, coordination reaction is 6 hours in 100ml THF, De Lanse catalyzer 1.5g, productive rate 90%.
Embodiment 2
Normal pressure under the ethene atmosphere, in the time of 0 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.68g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.63g (catalytic efficiency 2.52 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.2%.
Embodiment 3
Normal pressure under the ethene atmosphere, in the time of 15 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.68g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.63g (catalytic efficiency 2.52 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.3%.
Embodiment 4
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.68g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.60g (catalytic efficiency 2.40 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.9%.
Embodiment 5
Normal pressure under the ethene atmosphere, in the time of 45 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.68g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.61g (catalytic efficiency 2.42 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.8%.
Embodiment 6
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.17g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.59g (catalytic efficiency 2.36 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.1%.
Embodiment 7
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.63g (catalytic efficiency 2.52 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.7%.
Embodiment 8
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 1.02g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.61g (catalytic efficiency 2.44 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.5%.
Embodiment 9
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds methyl acrylate 1.7g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.60g (catalytic efficiency 2.40 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.3%.
Embodiment 10
Normal pressure is under the ethene atmosphere, in the time of 30 ℃, the MAO 3ml that in the 100ml reaction flask, adds 2M, catalyst A 3.04mg (5 μ mol), toluene 30ml, methyl acrylate 0.34g, copolymerization 30min, reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.31g (catalytic efficiency 1.24 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.0%.
Embodiment 11
Normal pressure is under the ethene atmosphere, in the time of 30 ℃, the MAO 3ml that in the 100ml reaction flask, adds 2M, catalyst A 3.04mg (5 μ mol), toluene 30ml, methyl acrylate 0.68g, copolymerization 30min, reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.26g (catalytic efficiency 1.04 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.1%.
Embodiment 12
In the 100ml autoclave, 30 ℃, under the ethene atmosphere, add the MAO 3ml of 2M, catalyst A 3.04mg (5 μ mol), toluene 30ml, reaction 2min adds methyl acrylate 1.7g again, is forced into 5atm, copolymerization 30min, reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 2.56g (catalytic efficiency 2.56 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.7%.
Embodiment 13
In the 100ml autoclave, 0 ℃, under the ethene atmosphere, add the MAO 3ml of 2M, catalyst A 3.04mg (5 μ mol), toluene 30ml, reaction 2min adds methyl acrylate 1.7g again, is forced into 5atm, copolymerization 30min, reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 2.5g (catalytic efficiency 2.5 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.1%.
Embodiment 14
In the 100ml autoclave, 30 ℃, under the ethene atmosphere, add the MAO 3ml of 2M, catalyst A 3.04mg (5 μ mol), toluene 30ml, reaction 2min adds methyl acrylate 1.7g again, is forced into 5atm, copolymerization 30min, reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 2.57g (catalytic efficiency 1.71 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.5%.
Embodiment 15
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst B 2.48mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.31g (catalytic efficiency 1.24 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.9%.
Embodiment 16
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyzer C 2.26mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.42g (catalytic efficiency 1.68 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.3%.
Embodiment 17
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyzer D 3.49mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.58g (catalytic efficiency 2.32 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.8%.
Embodiment 18
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyzer E 2.76mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.49g (catalytic efficiency 1.96 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.1%.
Embodiment 19
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyzer F 2.76mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.50g (catalytic efficiency 2.00 * 10 5G/mol Feh), methyl acrylate insertion rate is 2.4%.
Embodiment 20
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyzer G 2.90mg (5 μ mol), and toluene 30ml adds methyl acrylate 0.34g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.25g (catalytic efficiency 1.00 * 10 5G/mol Feh), methyl acrylate insertion rate is 1.0%.
Embodiment 21
Normal pressure under the ethene atmosphere, in the time of 30 ℃, adds the MAO 3ml of 2M in the 100ml reaction flask, catalyst A 3.04mg (5 μ mol), and toluene 30ml adds butyl acrylate 0.56g, copolymerization 30min behind the feeding ethene 3min.Reaction solution in the alcohol hydrochloric acid mixed solution, precipitate multipolymer 0.86g (catalytic efficiency 3.44 * 10 5G/mol Feh), butyl acrylate insertion rate is 2.9%.

Claims (8)

1, a kind of catalyst system that is used for ethene and acrylic ester copolymerization, Primary Catalysts are pyridine diimine Fe (II) title complex, and promotor is an organo-aluminium compound, the structure of Primary Catalysts as shown in the formula:
Figure A0213096000021
X is Cl or Br in the formula; R is H or methyl; R 1, R 2Be respectively methyl, ethyl, sec.-propyl or the tertiary butyl.
2, catalyst system as claimed in claim 1 is characterized in that, described R 1And R 2Can be identical.
3, catalyst system as claimed in claim 1 is characterized in that, described R is a methyl, R 1, R 2Be sec.-propyl.
4, catalyst system as claimed in claim 1 is characterized in that, described promotor is methylaluminoxane or modified methylaluminoxane, and the mol ratio of promotor and Primary Catalysts is 100-2000.
As claim 1 or 4 described catalyst system, it is characterized in that 5, described promotor is a modified methylaluminoxane.
6, a kind of method for preparing the described catalyst system of claim 1, its reaction formula is as follows Its key step is:
A, under Catalyzed by p-Toluenesulfonic Acid, under the refluxing toluene condition, carry out 2, the condensation reaction of 6-diacetyl pyridine and substituted aromatic amines, the pyridine diimine compound that obtains replacing is pyridine diimine Fe (II) catalyst precursor;
Under B, the room temperature, the product that steps A is made in tetrahydrofuran (THF) with FeX 2Carry out coordination reaction, obtain pyridine diimine Fe (II) title complex;
X is Cl or Br in the formula; R is H or methyl; R 1, R 2Be respectively methyl, ethyl, sec.-propyl or the tertiary butyl.
7, preparation method as claimed in claim 6 is characterized in that, described R 1And R 2Can be identical.
8, as each described catalyst system application in ethene and acrylic ester copolymerization in the claim 1 to 5.
CN 02130960 2002-09-23 2002-09-23 Catalytic system for ethylene and acrylic ester copolymerization Pending CN1408737A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101878232B (en) * 2007-11-28 2013-05-22 Lg化学株式会社 Catalytic composition for producing 1-alkene and acrylates copolymer and method for producing 1-alkene and acrylates copolymer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101878232B (en) * 2007-11-28 2013-05-22 Lg化学株式会社 Catalytic composition for producing 1-alkene and acrylates copolymer and method for producing 1-alkene and acrylates copolymer

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