Catalytic composition for the polymerization- olefins, the catalyst for polymerization- olefins and a method of producing polymers- olefins


C08F4/82 - pi-Allyl complexes

 

(57) Abstract:

Offers a catalyst comprising a catalytic mixture, resulting from the interaction of the following compounds (at least one from each group): compounds of pyridine, clay and michelangelesque compounds. In addition, it is proposed a method of producing polymers of olefins, which consists in the fact that in the conditions of polymerization of at least one olefin is brought into contact with a catalytic mixture formed by the interaction of at least one compound from each group of the following compounds: compounds of pyridine, clay and michelangelesque compounds. The proposed method for the polymerization of olefins provides the ability to control the molecular weight of the target product of the polyolefin, and the use of new catalytic composition improves the properties of the obtained polymers. 3 C. and 25 C.p. f-crystals, 5 PL.

The present invention relates to the field of polymerization SSS-olefins.

In the technique known various methods of polymerization. For example, for the polymerization of ethylene is known catalytic systems based on chromium and titanium-based. However, even these two accepted the Yu search of new and better systems of polymerization.

One of the important properties of the polymer is the molecular weight of the polymer. For example, the molecular weight polyethylene may affect the following properties of the polymer: ultimate tensile strength; tear resistance; strength at low temperatures; softening temperature; toughness; resistance to cracking under the influence of the environment; the fluidity of the melt; and the ability of the melt to the extrusion. So are constantly searching for methods that would provide the ability to control the molecular weight of polyolefins.

Summary of the invention.

The aim of the present invention is to provide an improved method of polymerization.

Another objective of the present invention is to propose an improved method of polymerization, which provides improved control over molecular weight.

Another objective of the present invention is to provide an improved catalytic system.

Another objective of the present invention is to provide an improved catalytic system, which provides improved control over molecular weight.

The composition corresponding to the present invention, not only the one connection from each group of the following compounds: compounds of pyridine, clay and michelangelesque connection.

Another variant implementation of the invention is a method lies in the fact that in the conditions of polymerization of at least one - olefin contractive with a catalytic mixture, formed by bringing into contact at least one connection from each group of the following compounds: compounds of pyridine, clay and michelangelesque connection.

Detailed description of the invention

Compounds of pyridine

The pyridine compounds suitable for the present invention are compounds which are represented by the following formula:

< / BR>
where each R independently is selected from the group consisting of hydrogen and -- COOH, provided that at least one R represents a group-COOH. Examples of suitable compounds are, but not limited to pyridine-2-carboxylic acid /also known as picolina acid, pyridine-3-carboxylic acid /also known as nicotinic acid, pyridine-4-carboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid and pyridine-2,4,6-tricarboxylic acid. The preferred compounds are monopedigree acid component to the Nickel originally should lie in the range from 0.01 to 2. Preferably, when the molar ratio of acid component to Nickel is in the area of from 0.25 to 1.75, and most preferably when it is in the range from 0.5 to 1.5, inclusive. These intervals during the initial contact of the reactants catalyst are important due to the impact on the complex reactions occurring in the contact.

Clay

Different clays can contribute to the formation of polymer with high molecular weight. The initial weight ratio of clay to Nickel is usually in the range from 1 to 500. Preferably, when the weight ratio of clay to Nickel is in the range from 10 to 300, and most preferably in the range from 25 to 200, inclusive. These intervals during the initial contact of the reactants catalyst are important due to the impact on the complex reactions occurring in the contact, and due to various economic considerations and the effect on the polymer.

The main classes of clays suitable for the present invention are aluminum silicates, magnesium silicates or alumomagnesium silicates. Examples of suitable clays suitable for the present invention are the>/BR>/3/ halloysite, aluminium silicate;

/4/ hectorite, magnesium silicate;

/5/ kaolinite, aluminum silicate;

/6/ montmorillonite, aluminum silicate;

/7/ pyrophyllite, aluminum silicate;

/8/ serialset, magnesium silicate;

/9/ talc, magnesium silicate;

/10/ vermiculite, alumomagnesium silicate.

Particularly preferred clay carriers for catalysts are silicates of magnesium, such as sepiolite.

Preferably, before use clay was improved. This improvement is that the clay is subjected to processing at a temperature in the range from 200o800oC, preferably from 300o700oC, and most preferably from 400o600oC. Clay should be maintained such that improves the physical condition of a temperature from 5 minutes to 50 hours, preferably from 30 minutes to 25 hours, and most preferably from 1 hour to 10 hours.

Michelangelesque connection

These compounds have the following characteristic properties. Nickel component compounds, to the formation of an active Nickel component must already be in a state with zero valence or be able subjected to what Obedinenie. Examples of Nickel compounds suitable for the present invention is bis/1,5-cyclooctadiene/Nickel/hereinafter referred to here (COD)2Ni/.

These three components of the catalytic mixture /compound pyridine, clay and michelangelesque connection/ can be brought into contact in any order and by any method known in the art.

- Olefins

The olefins which can be polymerized according to the method of the present invention, are such - olefins which have from 2 to 16 carbon atoms in the molecule. Preferably, when the molecule - olefins have from 2 to 12 carbon atoms, and most preferably when they have 2 to 8 carbon atoms. In addition, these olefins can be either linear or branched. Examples of olefins suitable for the present invention include, but are not limited to, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-penten, 3-methyl-1-penten, 4-methyl-1-penten, 1-hexene, 3-ethyl-1-hexene, 1-octene, 1-mission. In the scope of the present invention also includes the copolymerization of the above monomers with any other monomer.

The conditions of polymerization

The reaction temperature can be maintained in the range of 0oC to 300oC to 60oC inclusive. The pressure in the reaction may be in the range from 7103n/m2up to 7103n/m2from 10 to 10,000 lb/in2/. Preferably, when it is supported in the interval from 3,5104n/m2up to 7105n/m2/from 50 to 1000 f/d2/ and the most preferred range from 7104n/m2to 4,2105n/m2/from 100 to 600 f/d2/. The duration of reaction is in the range from 1 minute to 100 hours. Preferably, when the reaction time ranges from 5 minutes to 60 hours, and the most preferred range from 1 to 10 hours.

Examples

The examples are intended to help professionals to understand the present invention. Certain reagents, conditions, etc. are mentioned, generally speaking, as the explanation of the present invention, and should not be construed as limitations acceptable incidence of the present invention.

In each experiment, which is mentioned below, ethylene lead in contact with (COD)2Ni pikolinos acid, if used, or bentonite, or sepiolite, depending on what is used. The reaction is carried out in a 1-liter reactor made of stainless may adversely affect the polymerization reaction.

First charged to the reactor, the solvent and / or bentonite, or sepiolite, depending on what is used. These components after purging with ethylene are mixed for a short time. Then in the reactor to this mixture add (COD)2Ni and Pikalyovo acid, if used. The chemicals in the reactor and then stirred for 15 minutes. Then the reactor is fed under pressure ethylene, alone or with co monomer, if used. The pressure of ethylene was then supported approximately at a constant level. The reaction is then stopped by releasing excess ethylene. Any resulting solid is separated and removed. Usually, the recovered solid is washed with toluene and/or methanol and then dried and weighed. Then determine the characteristic properties of the obtained solid material.

The results are presented in tables 1-A, 1-B, 1-C, 1-D and 1-E. the Number of experiments in each table refer to the same experience, i.e. experience in table 1. 1-A is also experience in table 1. 1-B/.

As you can see from the above data, the connection of pyridine is very important for polymerization. This is evident from the experience under the number 2, which shows Chimera 13 and 14. From these experiments it follows that without clay makes a very low productivity. It should be noted that the example under number 10 is considered anomalous experience, which does not combine with the present invention.

The data table. 1-E shows that a very low melt indexes are achieved thanks to the clay. This is evident from experiments 2, 3, 5 to 9 and 11 when compared with experiments 13 and 14.

1. Catalytic composition for the polymerization of olefins containing organic compound with Nickel in a state with zero valentinetti or be able to restore to a state with zero valency, characterized in that it contains at least one compound from each group of compounds: pyridine compounds, clay and organonitrogen compounds in a weight ratio of acid and Nickel 0.02 to 4 : 1 and the weight ratio of clay and Nickel, 1 to 500 : 1.

2. The composition according to p. 1, characterized in that the connection of pyridine selected from the group consisting of pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,4,6-tricarboxylic acid and mixtures thereof.

3. The composition of paragraph pyridine-3-carboxylic acid, pyridine-4-carboxylic acid, and mixtures thereof.

4. The composition according to p. 1, characterized in that the compound of the pyridine is a pyridine-2-carboxylic acid.

5. The composition according to p. 1, wherein the clay is selected from the group consisting of aluminosilicate clays, minielectric clays, aluminasilicate clays and mixtures thereof.

6. The composition according to p. 1, wherein the clay is selected from the group consisting of attapulgite, bentonite, halloysite, Hector-ITA, kaolinite, montmorillonite, pyrophyllite, sepiolite, talc, vermiculite, and mixtures thereof.

7. The composition according to p. 1, wherein the clay is minielectro clay.

8 the Composition according to p. 1, wherein the clay is selected from the group consisting of sepiolite, bentonite and mixtures thereof.

9. The composition according to p. 1, wherein the clay is sepiolite.

10. The composition according to p. 1, wherein the clay is a bentonite.

11. The composition according to p. 1, characterized in that the compound of the Nickel represents bis(1, 5cyclooctadiene)Nickel.

12. The catalyst for polymerization of olefins, which represents a catalytic composition according Way of sepiolite, bentonite and mixtures thereof, and bis(1,5-cyclooctadiene)Nickel.

13. A method of producing polymers of olefins containing 2 to 16 carbon atoms, with the use of organic compounds of Nickel in a state with zero valence or be able to restore to a state with zero valence as a component of a catalyst, characterized in that at least one olefin containing 2 to 16 carbon atoms, result in interaction with a catalytic composition comprising at least one compound from each group of compounds: pyridine compounds, clay and organonitrogen compounds in a weight ratio of acid and Nickel 0,02 - 4 : 1 and the weight ratio of clay and Nickel 1 - 500 : 1 at a temperature of 0 to 300oC and a pressure of 10 to 10,000 psig and a reaction time from 1 min to 100 hours

14. The method according to p. 13, characterized in that the above-olefin has from 2 to 12 carbon atoms in the molecule.

15. The method according to p. 13, characterized in that the above-olefin selected from the group consisting of ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4 - methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-octene, 1-mission and mixtures thereof.

16. The method according to p. 13, characterized in that the e connection pyridine selected from the group consisting of pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,4,6-tricarboxylic acid and mixtures thereof.

18. The method according to p. 13, characterized in that the said connection pyridine selected from the group consisting of pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acid, and mixtures thereof.

19. The method according to p. 13, characterized in that the said connection pyridine is a pyridine-2-carboxylic acid.

20. The method according to p. 13, wherein said clay is selected from the group consisting of aluminosilicate clays, minielectric clays, aluminasilicate clays and mixtures thereof.

21. The method according to p. 13, wherein said clay is selected from the group consisting of attapulgite, bentonite, Gallaudet, hectorite, kaolinite, montmorillonite, pyrophyllite, sepiolite, talc, vermiculite, and mixtures thereof.

22. The method according to p. 13, characterized in that the clay is minielectro clay.

23. The method according to p. 13, wherein said clay is selected from the group consisting of sepiolite sepiolite.

25. The method according to p. 13, characterized in that the clay is a bentonite.

26. The method according to p. 13, characterized in that the said connection Nickel-represents bis(1, 5cyclooctadiene)Nickel.

27. The method according to p. 13, characterized in that ethylene is treated with a catalytic mixture, resulting from the interaction of pyridine-2-carboxylic acid, clay selected from the group consisting of sepiolite, bentonite, and mixtures thereof, and bis(1,5-cyclooctadiene)Nickel.

28. The method according to p. 13, characterized in that combine clay with a solvent, and then combine the mixture with the compound of pyridine and michelangelesque compound, and the compound obtained is subjected to interaction with at least one-olefin in the polymerization conditions.

 

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