BG60319A - Catalyst for ethylene polymerization and method for its preparation - Google Patents

Abstract

The catalyst has the formula wherein r1, r2, r3, r6, r7, r8 are independently alkyl groups containing from 1 to 15 carbon atoms, aryl groups of 6 to 15 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, arylalkyl groups of 7 to 20 carbon atoms, R4 and R5 independently of one another are alkyl groups of 1 to 15 carbon atoms, aryl groups of 6 to 15 carbon atoms, alkylaryl groups of 7 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atom, -c (O) OR ', where r' is a hydrocarbon substituent of 1 to 15 carbon atoms, -SO 3 m, where is a hydrocarbon substituent of 1 to 15 carbon atoms, is a bivalent hydrocarbon radical, for example, alkanediyl, alkenediyl, cycloalkanediyl, bicycloalkanediyl, cycloalkenediyl, bicycloalkenediyl, arendiyl , arylalkanediyl, alkylaryndiyl, 1 to 20 carbon atoms, 1,1'-ferrocidialyl radical, mono or disubstituted 1,1'-ferrocidadienyl radical, wherein the substituents are - C (O) OR 'or SO3' have the indicated meanings. The catalyst is obtained by reacting ni (o) compounds with bisketoylides and tertiary phosphines in a medium of polar or non-polar solvents or mixtures thereof at a temperature of from -20 to 800 ° C.

Description

Technical field.

The invention relates to a catalyst for the polymerization of ethylene, to the production of polyethylene, and to a process for the preparation of the catalyst.

BACKGROUND OF THE INVENTION

Nickel complexes containing chelate-linked α-ketoylid ligands are known to be active catalysts for the oligomerization of ethylene to linear α-alkenes [1,2]. In the presence of acceptor additives, these organo-nickel compounds are converted into ethylene polymerization catalysts, increasing their catalytic activity [3]. The nickel-catalysts described in the literature [6,7] also polymerize ethylene to polyethylene of different molecular weights, but are obtained in situ at the beginning of the polymerization reaction. All the nickelide catalysts described in the literature can also be used to copolymerize ethylene with different comonomers to obtain linear low-density polyethylene [LLDPE] or low-density functionalized polyethylene [FLLDPE] [4,5].

SUMMARY OF THE INVENTION

The ethylene polymerization catalyst according to the invention has the following general chemical formula

N1 N ⁹ X 1 h * %% ^C A in which R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , R _J independently are alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms, alkylaryl groups containing from 7 to 20 carbon atoms, R ₄ and R _s independently of one another are H, alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms atom; alkylaryl groups containing from 7 to 20 carbon atoms; arylalkyl groups containing from 7 to 20 carbon atoms, -C (O) OR ', where R' is a hydrocarbon substituent containing from 1 to 15 carbon atoms -SO ₃ M, where M is Li, Na, K, NH ₄ + , NR ₄ +, wherein R is a hydrocarbon substituent containing from 1 to 15 carbon atoms.

-R- is a bivalent hydrocarbon radical, for example alkanediyl, alkenediyl, cycloalkanediyl, bicycloalkanediyl, cycloalkenediyl, bicycloalkenediyl, Arendiyl, arylalkanediyl, alkyllarendenyl, containing from 1 to 20 carbon atoms, 1-, cyclohexenene, 1-, a ferrocendyl radical, where -C (O) OR '(R' is defined as above) or SO ₃ M (M is defined as above) are used as substitutes.

The ethylene polymerization catalyst according to the invention is prepared by reacting Ni (O) compounds with bisα-ketoylides and tertiary phosphines in a medium of polar or non-polar solvents or mixtures thereof at -20 ° C to 80 ° C. Bis-1,5cyclooctadienickel (O), bisborbornadienickel (O), tetrakistriphenylphosphinickel (O) are used as Ni (O) compounds. Compounds of the general formula o are used as bis-α ketoylides

wherein R ₄ and R ₃ independently of one another are H, alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms, alkylaryl groups containing from 7 to 20 carbon atoms, arylalkyl groups, containing from 7 to 20 carbon atoms, -C (O) OR ', where R' is a hydrocarbon substituent containing from 1 to 15 carbon atoms, -SO ₃ M, where M is Li, Na, K, NH 1, NR " ₄ , wherein R " is a hydrocarbon substituent containing from 1 to 15 carbon atoms.

-R- is a bivalent hydrocarbon radical, for example alkanediyl, alkenediyl, cycloalkanediyl, bicycloalkanediyl, cycloalkenediyl, bicycloalkenediyl, areenedyl, arylalkanediyl, alkylarendiyl, containing from 1 to 20 carbon atoms, 1-methyl-di-ester, 1-methyl-di-ester, 1-methyladenene, 1- -ferocentenedyl radical, where C (O) OR '(R' is defined as above) or SO ₃ M (M is defined as above) are used as substitutes. Compounds of general formula are used as tertiary phosphines

P (R, R ₂ R ₃₎ wherein RpRj and R ₃ independently of one another are alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms, alkylaryl groups containing from 7 to 20 carbon atoms, arylalkyl groups containing from 7 to 20 carbon atoms.

Ethers containing from 3 to 20 carbon atoms, ketones containing from 3 to 15 carbon atoms, esters containing from 2 to 15 carbon atoms, tetrahydrofuran, dioxane, pyridine are used as polar solvents for the synthesis of the catalyst according to the invention.

Benzene, alkyl aromatic hydrocarbons containing from 7 to 20 carbon atoms, attachments containing from 5 to 20 carbon atoms are used as non-polar solvents for the synthesis of the catalyst according to the invention.

The ethylene polymerization catalyst according to the invention catalyzes the polymerization of ethylene in solution or suspension in the presence of acceptor additives at a catalyst concentration of 1.10 ³ to 1 mol / ί, ethylene pressure of 1 to 150 at, temperature of 10 to 150 ° C, reaction time from 1 min to 24 h in medium of polar or non-polar solvents or mixtures thereof.

As acceptor additives in the polymerization of ethylene with the catalyst for ethylene polymerization according to the invention, compounds are used that bind the phosphine ligand more tightly than the nickel atom of the catalyst or convert the phosphine ligand into a less coordinating ligand. Typical examples of acceptor additives are amino oxides, organic hydroperoxides, hydrogen peroxide, metal complexes of group VIII of the periodic system, for example bis-1,5cyclooctadienickel (O), tetrakis (ethylene) - μ-chloro nickel (I), bis (ethyl is n) a cetyl l is a tonatorodium (I), bis (acetonitrile) palladium (II) · The acceptor additives in the polymerization of ethylene with the catalyst for the polymerization of ethylene according to the invention are present in the reaction mixture in an amount of 0.1 to 10 mol per 1 mol catalyst.

The polar solvents used as the polymerization medium of ethylene according to the invention are alcohols containing from 1 to 15 carbon atoms or aqueous solutions thereof with an alcohol concentration of 70 to 99% by weight. diols containing 2 to 15 carbon atoms, ethers containing 3 to 15 carbon atoms, esters containing 2 to 15 carbon atoms, ketones containing 3 to 10 carbon atoms, carboxylic amides containing 2 to 15 carbon atoms , nitriles containing from 2 to 10 carbon atoms, tetrahydrofuran, dioxane.

The non-polar solvents used as the polymerization medium of ethylene according to the invention are benzene, alkyl aromatic hydrocarbons containing from 7 to 20 carbon atoms, alkanes containing from 5 to 20 carbon atoms. The resulting polymer with the ethylene polymerization catalyst according to the invention is isolated from the reaction medium by precipitation, filtration, solvent evaporation, centrifugation. *

The residual catalyst may be removed from the polymer by washing with polar solvents such as methanol, ethanol, acetone, dimethylformamide, acetonitrile, or aqueous mineral acids at a concentration of 1 to 60%.

The advantages of the catalyst according to the invention are its high activity, its inertness to polar solvents, and the ability to produce copolymers of ethylene with linear α-alkenes formed in situ during the polymerization reaction.

The invention is illustrated by the following examples.

Examples 1-8.

The catalysts, the preparation of which is illustrated by these examples, are described by the general chemical formula shown above, and the specific meanings of the substituents are

¥ ^: H-!

Example 9-25.

Examples 9 - 25 illustrate the application of catalysts 1 - | in the reaction, the polymeric acid is ethylene.

In a metal autoclave (250 Xia *) equipped with a mechanical stirrer, a thermometer and a maintenance device

100 mg of solvent blue is ethylene with stirred ice to reach the appropriate temperature. The reaction was then solubilized in MB m < t > then the resulting polymer was isolated, pressurized, and ethylene flow logged, 10 - 200 mg of the appropriate catalyst was charged in argon medium, 5 - 300 mg of the corresponding accept was washed with methanol until removal of the reaction. catalyst and dried at 504? / 1 mm Nd dr constant weight.

Catalytic properties of catasmatrum I

Table 2

Experience Cat. Sokat. 4 • p 0 9 F 0 • N I J 9. 1 Rh-1 TOOOOA 50 26 7 14 52 5.0 2.1 12 « 0.968 10. 1 It is not TOOOOA 50 28 47 15 48 12.0 4.5 128 0.965 11. 1 It is not heptane 50 30 36 5 48 8.0 2.8 125 0.943 12. 2 Rh-2 TOOOOA 50 91 26 23 50 2.9 0.6 129 0.949 13. 2 It is not TOOOOA 50 30 35 5 50 2.5 1.0 126 0.944 14. 3 It is not TOOOOA 90 29 10 27 . ί 90 1.8 0.9 130 O.? 4 | IS. 4 JBi-i TOOOOA 90 29 0 47 90 29.6 I.4 »41 6.944 16. 4 It is not TOOOOA 96 20 It ' 46 10.6 6.6 fit 0 999 17. 4 It is not TOOOOA 50 19 13 5 50 3.5 2.2 128 0.960 16. S It is not TOOOOA 90 29 30 17 50 2.7 1.9 130 0.471 19. 6 Pd TOOOOA 90 28 9 29 90 2.9 1.1 130 0.969 20. 6 It is not 90 17 at ♦ 69 10.9 7.9 i27 0-0¾ 21. 6 It is not TOOOOA '' With 50 it fin 22. 6 It is not C ^ OJ 50 10 w 7 J '▼ * tJw 22. % »Ί / ' 'Ww _f M · 4μ ί * τ; 7 Μ. r and impression ¹ r jrl • M W t * JL— as. 6 It is not TOOOOA 100 ίο Ж0 149 ο. «Ο It is not TOOOOA - - • 9 89 - 29.2 B * II * CICCA * Aug 90 w - ·! J * k- too 100 1 * C-- J 0.966

gBAD ORIGINAL Λ

listed in Table 1.

To a solution of 4.10 ³ mol bis-1,5-cyclooctadienyl (O) is added a solution or suspension of

2.10 ³ mol of the corresponding illide and 4.10 ³ inol triphenyphosphine in 100-150 cm @ -1 of toluene. The reaction mixture was stirred for 18 h at room temperature, 1 h at 50 ° C, and after cooling, 120-200 cm ^{3 of} hexane was added. The separated crystals were filtered (Examples 3-7), washed with a 10-20 cm ³ mixture of (1: 2) toluene-hexane and dried for 6 h at 50 ° C and 0.1 mm Hg.

In the cases of Examples 1,2 and 8, the reaction mixture was filtered without the addition of hexane. The separated crystals were washed with 10 cm ^{3 of} toluene and dried for 10 h at 50 ° C and 0.1 mm Hg.

Table 1

Catalyst Data 1-8.

Experience No Cat. No R 4 R 5 R Elemental analysis Yield% Found Calculated sd Sun. SD Sun. 1. 1 n H 1,4-C H 6 4 73.93 4.79 74.33 5.03 51.7 2. 2 Ph Ph 1,3-C H 6 4 76.91 5.18 76.43 5.06 54.4 3. 3 Ph Ph (-CH ₂ -I _e 75.82 5.38 76.19 5.74 60.4 4. 4 COCH 2 9 CO CH 2 9 "" A 71.29 4.99 71.00 5.26 68.0 5. 5 COCH 2 9 COCH 2 9 (“CH -) 2 9 71.93 5.89 71.55 5.61 49.8 b. 6 Ph Ph 5,6-NBEN ⁴ 76.29 5.05 76.41 5.28 63.2 7. 7 CH 9 CH 9 l, l-Fc ^b 71.63 5.44 71.41 5.29 36.5 8. 8 SO Na 9 SO Na 9 X ¹ *, 63.85 4.62 64.42 4.23 62.7

^a 5,6-bicyclo (2,2,1] hept-2-endo - ^b 1 D -ferotsendiil5

A - type of solvent; B is the volume of the solvent, cm '; C-amount of catalyst, mg, D-amount of acceptor additive, mg; E-pressure of C ₂ H ₄ , at; F-reaction temperature, ° C; G-yield of PE, d; H-catalyst productivity, kg PE / g Ni-h; I-temp. melting point of PE, ° C; J-relative density of PE; Sokat. Acceptance supplement.

Rh-Ι - μ -Rh ₂ Cl ₂ (C ₂ H ₄ ) ₄ ; Rh-2 - μ -Rh ₂ Cl ₂ (COD) ₂ ; Ni - Ni (COD) ₂ ; Pd - PdCl, (CH ₃ CN) ₂ ; COD-cis, cis-1,5-cyclooctadiene α-88% aqueous methanol; b, c-comparative literature data - lit. [3,6].

Claims (13)

An ethylene catalyst of the general formula for polymerisation of 5 1,1'-Ferocen-diyl radical, where -C (O) OR '<R' is defined as above) or SO ₃ M (M is defined as above) as substituents. 2. A process for the preparation of a catalyst Ιθ for the polymerization of ethylene according to claim 1, characterized in that the Ni (O) compounds are reacted with bis-ketoylides and tertiary phosphines in a slf medium in which R ₍ , R ₂ , R ₃ , R ₆ , R ₇ and R _g independently of each other alkyl and alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms, alkylaryl groups containing from 7 to 20 carbon atoms, arylalkyl groups containing from 7 to 20 carbon atoms, R ₄ and R ₃ independently of one another are H, alkyl groups containing from 1 to 15 carbon atoms ma, aryl groups containing from 6 to 15 carbon atoms, alkylaryl groups containing from 7 to 20 carbon atoms, arylalkyl groups containing from 7 to 20 carbon atoms, -C (O) OR ', where R' is a hydrocarbon substituent, containing from 1 to 15 carbon atoms, -S0 ₃ M, where M is Li, Na, K, NH 1, NR _{4 '} having R' being a hydrocarbon substituent containing from 1 to 15 carbon atoms; -R- is a bivalent hydrocarbon radical , for example alkanediyls, alkenediyls, cycloalkanediyls, bicycloalkanediyls, cycloalkenediyls, bicycloalkenediyls, areenedyls, arylalkanediyls, alkylarendiyls, sodpolar or non-polar solvents or mixtures thereof at -20 ° C to 80 ° C. Process according to claim 2, characterized in that bis-1,5-cyclooctadienyl (O), bisborbornadienyl (O), tetrakistri- (Ni) compounds are used as Ni (O) compounds. 2θ phenylphosphinickel (O). A process according to claim 2, characterized in that as bis-α-ketoylides compounds of the general formula are used wherein R ₄ and R _{s are} independently H, alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms, alkylaryl groups containing from 7 to 20 carbon atoms, 35 arylalkyl groups containing from 7 to 20 carbon atoms, -C (O) OR ', where R' is a hydrocarbon substituent containing from 1 to 15 carbon atoms, -SO ₃ M, where M is Li, Na, K, NH * ₄ , NR / *, wherein R 'is a hydrocarbon substituent containing from 1 to 15 carbon atoms; -R- is a bivalent hydrocarbon radical, for example alkanediyl, alkenediyl, cycloalkanediyl, bicycloalkanediyl, cycloalkenediyl, bicycloalkenediyl, areenedyl, arylalkanediyl, alkyllarendenyl containing from 1 to 20 carbon atoms, 1,1 'or dienol, 1' or -indolene, 1,1'-disodium , A 1 '-ferocenzyl radical, where C (O) OR' (R * is defined as above) or SO ₃ M (M is defined as above) are used as substitutes. 5. A method according to claim 2, characterized in that compounds of the general formula are used as tertiary phosphines P (R, R ₂ R ₃ ) in which R _t , R j and R ₃ independently of one another are alkyl groups containing from 1 to 15 carbon atoms, aryl groups containing from 6 to 15 carbon atoms, alkyl aryl groups containing from 7 to 20 carbon atoms, arylalkyl groups containing 7 to 20 carbon atoms. A process according to claim 2, characterized in that ethers containing from 3 to 20 carbon atoms, ketones containing from 3 to 15 carbon atoms, esters containing from 2 to 15 carbon atoms, tetrahydrofuran, are used as polar solvents. dioxane, pyridine. 7. The process according to claim 2, wherein benzene, alkyl aromatic hydrocarbons containing from 7 to 20 carbon atoms, alkanes containing from 5 to 20 carbon atoms are used as non-polar solvents. A method according to claim 2, characterized in that the catalyst is isolated from the reaction mixture by dissolving, precipitation, filtration, centrifugation, evaporation of the solvent. Ethylene polymerization method, characterized in that the ethylene polymerizes in the presence of a catalyst according to claim 1 and acceptor additives at a catalyst concentration of 1.10 ' ⁵ to 1 mol / 1, a concentration of acceptor additives of 1.10 * to 10 mol / 1, ethylene pressure from 1 to 150 at, temperature from 10 to 150 ° C, reaction time from 1 min to 24 h in medium of polar or non-polar solvents or mixtures thereof. A method according to claim 9, characterized in that amino oxides, organic hydroperoxides, hydrogen peroxide, metal complexes of group VIII of the periodic system, for example bis-1,5-cyclooctadienyl (0), tetrakis (are used as acceptor additives). ethylene) - μ-dichlorodinikel (1), bis (ethylene) acetylacetonate-rhodium (I), bis (acetonitrile) palladium (II). 11. A method according to claim 9, characterized in that alcohols containing from 1 to 15 carbon atoms or aqueous solutions thereof with an alcohol concentration of from 70 to about 99% by weight are used as polar solvents; diols containing from 2 to 15 carbon atoms, ethers containing from 3 to 15 carbon atoms, esters containing from 2 to 15 carbon atoms, ketones containing from 3 to 10 carbon atoms, carboxylic amides containing from 2 to 15 carbon atoms, nitriles containing from 2 to 10, carbon atoms, tetrahydrofuran, dioxane. A process according to claim 9, characterized in that benzene, alkyl aromatic hydrocarbons containing from 7 to 20 carbon atoms, alkanes containing from 5 to 20 carbon atoms are used as non-polar solvents. Method for isolating the resulting polymer according to claim 9, characterized in that the polymer is isolated from the reaction mixture by precipitation with polar solvents according to claim 11, filtration, washing, centrifugation and evaporation of the solvent.