CN118475586A - Metal-ligand complex, catalyst composition for preparing vinyl polymer containing the same, and method for preparing vinyl polymer using the same - Google Patents

Metal-ligand complex, catalyst composition for preparing vinyl polymer containing the same, and method for preparing vinyl polymer using the same Download PDF

Info

Publication number
CN118475586A
CN118475586A CN202280086980.4A CN202280086980A CN118475586A CN 118475586 A CN118475586 A CN 118475586A CN 202280086980 A CN202280086980 A CN 202280086980A CN 118475586 A CN118475586 A CN 118475586A
Authority
CN
China
Prior art keywords
alkyl
independently
metal
ligand complex
aryl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280086980.4A
Other languages
Chinese (zh)
Inventor
申东澈
金美智
金旼志
吴娟钰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC SK Nexlene Co Pte Ltd
Original Assignee
SABIC SK Nexlene Co Pte Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020220180789A external-priority patent/KR20230101717A/en
Application filed by SABIC SK Nexlene Co Pte Ltd filed Critical SABIC SK Nexlene Co Pte Ltd
Priority claimed from PCT/IB2022/062827 external-priority patent/WO2023126844A1/en
Publication of CN118475586A publication Critical patent/CN118475586A/en
Pending legal-status Critical Current

Links

Landscapes

  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Disclosed are a metal-ligand complex, and a catalyst composition for preparing a vinyl polymer and a method for preparing a vinyl polymer using the same. The metal-ligand complex improves the tolerance of the catalyst to oxygen, moisture and other impurities by introducing specific functional groups, and remarkably improves the high-temperature activity and stability.

Description

Metal-ligand complex, catalyst composition for preparing vinyl polymer containing the same, and method for preparing vinyl polymer using the same
Technical Field
The following disclosure relates to a metal-ligand complex, a catalyst composition for preparing a vinyl polymer containing the metal-ligand complex, and a method for preparing a vinyl polymer using the metal-ligand complex.
Background
In general, in the preparation of vinyl polymers, for example copolymers of ethylene and alpha-olefins or copolymers of ethylene and olefin-dienes, use is made of so-called Ziegler-Natta catalyst systems, which generally comprise a titanium or vanadium compound main catalyst component and an alkylaluminum compound cocatalyst component.
U.S. Pat. Nos. 3594330 and 3676415 disclose improved Ziegler-Natta catalysts. However, while Ziegler-Natta catalyst systems have a very high activity for the polymerization of ethylene, they have the disadvantage that, due to the heterogeneous nature of the active sites of the catalyst, the polymers generally produced have a relatively broad molecular weight distribution, in particular copolymers of ethylene and alpha-olefins having a heterogeneous component distribution.
Thereafter, various studies have been made on metallocene catalyst systems, including metallocene compounds of group 4 transition metals of the periodic table, such as zirconium and hafnium, and methylaluminoxane as a cocatalyst. Wherein the metallocene catalyst system is a homogeneous catalyst having a single catalyst active site, and can produce polyethylene having a narrow molecular weight distribution and a uniform composition distribution, as compared with the conventional Ziegler-Natta catalyst system.
For example, european patent publication Nos. 320762 and 372632 disclose that metallocene compounds can be activated with methylaluminoxane in Cp 2TiCl2,Cp2ZrCl2,Cp2ZrMeCl,Cp2ZrMe2, ethylene (IndH 4)2ZrCl2, etc. catalysts to polymerize ethylene with high activity, thereby producing polyethylenes having a molecular weight distribution (Mw/Mn) in the range of 1.5 to 2.0.
However, it is difficult to obtain high molecular weight polymers using the above catalyst systems.
That is, it is known that when a solution polymerization method performed at a high temperature is applied, the polymerization activity rapidly decreases and the β -dehydrogenation reaction is dominant, which is not suitable for producing a high molecular weight polymer.
Meanwhile, the organometallic catalysts generally require expensive preparation costs due to the high difficulty and complexity of the preparation steps. In addition, the catalyst may be exposed to air during the preparation process or during storage and transfer, at which time the activity of the catalyst may be significantly reduced, and at worst, the catalyst may be discarded because it is not usable. Catalysts that are stable to oxygen or moisture in air must be of great advantage from the point of view of the catalyst manufacturer or the catalyst user.
Thus, there remains a need in the chemical industry for catalysts and catalyst precursors having the desired improved properties. Therefore, there is an urgent need to develop a competitive catalyst having excellent stability, high temperature activity, reactivity with higher α -olefin, and capability of preparing high molecular weight polymer.
Disclosure of Invention
Technical problem
One embodiment of the present invention aims to provide a metal-ligand complex having a specific functional group and a catalyst composition comprising the same, to alleviate the existing problems.
Another embodiment of the present invention aims to provide a preparation method for preparing a vinyl polymer using the catalyst composition according to the present invention.
Technical proposal
The present invention provides a metal-ligand complex having significantly improved high temperature activity due to improved tolerance of a catalyst to impurities such as oxygen and moisture and high temperature stability by introducing specific functional groups. In one aspect, the present invention provides a metal-ligand complex represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
M is a transition metal of group 4 of the periodic Table;
Ar 1 and Ar 2 are each independently C 6-C20 aryl, and the aryl groups described in Ar 1 and Ar 2 may be further substituted with C 1-C20 alkyl;
R 1 to R 4 are each independently C 1-C20 alkyl, C 6-C20 aryl or C 6-C20 arylc 1-C20 alkyl;
R 5 and R 6 are each independently C 1-C20 alkyl;
R 7 and R 8 are each independently halogen or C 1-C20 alkyl;
a, b, c, d, e and f are each independently integers from 0 to 4; and
M is an integer in the range of 2 to 5.
In another aspect, a catalyst composition for preparing a vinyl polymer comprises a metal-ligand complex according to the present invention and a cocatalyst.
In another aspect, a method of preparing a vinyl polymer comprises preparing a vinyl polymer by polymerizing ethylene or ethylene and an alpha-olefin in the presence of a catalyst composition for preparing a vinyl polymer according to the present invention.
Advantageous effects
The metal-ligand complex according to the present invention introduces a specific functional group so that the stability of the complex can be significantly improved, thereby promoting polymerization at high polymerization temperatures without decreasing catalytic activity.
In particular, the metal-ligand complex according to the present invention has relatively excellent tolerance to impurities such as oxygen and moisture, and can produce a high molecular weight vinyl polymer at a high polymerization temperature.
That is, in preparing a vinyl polymer, i.e., an ethylene homopolymer or a copolymer of ethylene and an α -olefin, using the catalyst composition containing the metal-ligand complex according to the present invention, an ethylene homopolymer or a copolymer of ethylene and an α -olefin having a high molecular weight and excellent catalytic activity can be effectively prepared even at a polymerization temperature of 220 ℃ or more.
This is because of the structural characteristics of the metal-ligand complex according to the present invention, and the metal-ligand complex according to the present invention has excellent impurity resistance and excellent thermal stability, so that the metal-ligand complex has excellent copolymerization reactivity with olefins and a high molecular weight ethylene-based polymer can be produced in high yield while maintaining high catalytic activity even at high temperatures.
Accordingly, the metal-ligand complex of the present invention and the catalyst composition comprising the same can be effectively used for preparing vinyl polymers having excellent physical properties.
MODE OF THE INVENTION
Hereinafter, the present invention will describe a metal-ligand complex according to the present invention, a catalyst composition for preparing a polymer of vinyl group comprising the same, and a method of preparing a polymer of vinyl group using the same, but technical terms and scientific terms used herein have the general meanings understood by those skilled in the art to which the present invention pertains unless otherwise defined, and descriptions of known functions and configurations obscuring the present invention will be omitted in the following description.
As used herein, the following terms are defined below, but are merely exemplary and are not intended to limit the invention, application or use.
As used herein, the term "substituent (substituent)", "group(s)", "group", "part" and "fragment" are used interchangeably.
As used herein, the term "C A-CB" refers to "a carbon number greater than or equal to a and less than or equal to B".
As used herein, the term "alkyl" refers to a straight or branched chain saturated monovalent hydrocarbon radical consisting of carbon and hydrogen atoms only. The alkyl group may have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 5 carbon atoms, 5 to 20 carbon atoms, 8 to 20 carbon atoms, or 8 to 15 carbon atoms, but the present invention is not limited thereto. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, methylbutyl, n-hexyl, tert-hexyl, methylpentyl, dimethylbutyl, heptyl, ethylpentyl, methylhexyl, dimethylpentyl, n-octyl, tert-octyl, dimethylhexyl, ethylhexyl, n-decyl, tert-decyl, n-dodecyl, tert-dodecyl, and the like.
As used herein, the term "aryl" refers to a monovalent organic radical derived from an aromatic hydrocarbon by removal of one hydrogen and includes single or fused ring systems wherein each ring contains suitably 4 to 7, preferably 5 or 6 ring atoms, even including the form of multiple aryl groups linked by single bonds. Specific examples of aryl groups include, but are not limited to, phenyl, naphthyl, biphenyl, fluorenyl, phenanthryl, anthracenyl, triphenyl, pyrenyl,And tetraphenyl, etc.
The term "alkylaryl (alkylaryl)" as used herein refers to an aryl group substituted with at least one alkyl group, where "alkyl" and "aryl" are as defined above. Specific examples of alkylaryl groups include, but are not limited to, tolyl and the like.
The term "arylalkyl (arylalkyl)" as used herein refers to an alkyl group substituted with at least one aryl group, wherein "alkyl" and "aryl" are as defined above. Specific examples of aralkyl groups include, but are not limited to, tolyl and the like.
The present invention relates to a metal-ligand complex having a specific functional group, and provides a metal-ligand complex represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
M is a transition metal of group 4 of the periodic Table;
Ar 1 and Ar 2 are each independently C 6-C20 aryl, and the aryl groups described in Ar 1 and Ar 2 may be further substituted with C 1-C20 alkyl;
R 1 to R 4 are each independently C 1-C20 alkyl, C 6-C20 aryl or C 6-C20 arylc 1-C20 alkyl;
R 5 and R 6 are each independently C 1-C20 alkyl;
R 7 and R 8 are each independently halogen or C 1-C20 alkyl;
a, b, c, d, e and f are each independently integers from 0 to 4; and
M is an integer in the range of 2 to 5.
The metal-ligand complex according to the exemplary embodiment introduces a specific functional group aryloxy as a leaving group to increase the tolerance of the catalyst to oxygen and moisture and other impurities, thereby allowing a firm bond to be formed between the central transition metal and the ligand. Thus, the stability of the complex can be significantly improved.
In addition, the metal-ligand complex according to the exemplary embodiment introduces an aryloxy group as a leaving group instead of a methyl group, so that the solubility in an organic solvent can be significantly improved, thereby more effectively improving the polymerization process.
Due to the above structural features, the metal-ligand complex not only has significantly improved solubility in hydrocarbon solvents, but also has higher impurity resistance and excellent thermal stability, so that the metal-ligand complex can have excellent polymerization reactivity with other substances. High catalytic activity is maintained even at high temperature, and a high molecular weight vinyl polymer can be produced in high yield. Thus, the metal-ligand complex has high commercial utility compared to known metallocene-based and non-metallocene-based single site catalysts.
Preferably, according to one exemplary embodiment, in chemical formula 1, Ar 1 and Ar 2 may each independently be C 6-C20 aryl or C 1-C20 alkyl C 6-C20 aryl; R 1 to R 4 may each independently be C 1-C20 alkyl; r 7 and R 8 may each independently be halogen or C 1-C20 alkyl; a, b, c, d, e and f may each independently be an integer ranging from 1 to 3; and m may be an integer ranging from 3 to 5, more preferably, Ar 1 and Ar 2 may each independently be C 6-C12 aryl or C 1-C20 alkyl-C 6-C12 aryl; R 1 to R 4 may each independently be C 1-C10 alkyl; r 5 and R 6 may each independently be C 1-C10 alkyl; R 7 and R 8 may each independently be halogen or C 1-C10 alkyl; a, b, c, d, e and f may each independently be an integer of 1 or 2; and m may be an integer ranging from 3 to 5.
In a specific embodiment, M can be titanium, zirconium or hafnium.
In a specific embodiment, ar 1 and Ar 2 may each independently be an aryl group that is unsubstituted or substituted with a C 1-C20 alkyl group, wherein the aryl group may be phenyl, biphenyl, naphthyl, anthracenyl, pyrenyl, phenanthrenyl, or tetracenyl.
In a particular embodiment, R 1 to R 4 may each independently be branched C 3-C10 alkyl, branched C 3-C7 alkyl or branched C 3-C4 alkyl.
For greater resistance, thermal stability and excellent catalytic activity, preferably, the metal-ligand complex according to one exemplary embodiment may be represented by the following chemical formula 2-1 or the following chemical formula 2-2:
[ chemical formula 2-1]
[ Chemical formula 2-2]
In chemical formulas 2-1 and 2-2,
M is titanium, zirconium or hafnium;
Ar 1 and Ar 2 are each independently C 6-C20 aryl or C 1-C20 alkyl C 6-C20 aryl;
R 1 to R 4 are each independently C 1-C20 alkyl;
R 5 and R 6 are each independently C 1-C20 alkyl;
x 1 and X 2 are each independently halogen;
R 'and R' are each independently hydrogen or C 1-C20 alkyl; and
M is an integer ranging from 3 to 5.
According to an exemplary embodiment, in chemical formulas 2-1 and 2-2, Ar 1 and Ar 2 may each independently be C 6-C12 aryl or C 1-C20 alkyl C 6-C12 aryl; R 1 to R 4 may each independently be C 1-C10 alkyl; r 5 and R 6 may each independently be C 1-C10 alkyl; and R' and R "may each independently be hydrogen or C 1-C10 alkyl; More preferably, the process is carried out, ar 1 and Ar 2 may be the same as each other and may be C 6-C12 aryl or C 1-C20 alkyl C 6-C12 aryl; R 1 to R 4 may be the same as each other and may be C 1-C10 alkyl; r 5 and R 6 may be the same as each other and may be C 1-C10 alkyl; R 'and R' may be the same as each other and may be hydrogen or C 1-C10 alkyl.
In a particular embodiment, R 1 to R 4 may each independently be branched C 3-C10 alkyl, branched C 3-C7 alkyl or branched C 3-C4 alkyl.
More preferably, the metal-ligand complex according to the exemplary embodiment may be represented by the following chemical formula 3-1 or the following chemical formula 3-2:
[ chemical formula 3-1]
[ Chemical formula 3-2]
In chemical formulas 3-1 and 3-2,
M is zirconium or hafnium;
ar is C 6-C12 aryl or C 1-C20 alkyl C 6-C12 aryl;
R 11 is C 1-C5 alkyl;
r 12 is C 1-C10 alkyl;
x 11 is fluorine or chlorine;
r' "is hydrogen or C 1-C10 alkyl; and
N is an integer in the range of 1 to 3.
According to an exemplary embodiment, in chemical formulas 3-1 and 3-2, ar may be a C 6-C12 aryl group or a C 8-C20 alkyl C 6-C12 aryl group; r 11 can be C 3-C5 alkyl; r 12 can be C 1-C10 alkyl; x 11 may be fluorine or chlorine; r' "can be hydrogen or C 1-C5 alkyl; and n may be an integer of 1 to 3.
In one specific example, R 11 can be a branched C 3-C4 alkyl group, specifically can be a tert-butyl group.
To further improve high temperature stability, catalytic activity and reactivity with olefins, preferably, the metal-ligand complex according to an exemplary embodiment may be represented by the following chemical formula 4-1 or the following chemical formula 4-2:
[ chemical formula 4-1]
[ Chemical formula 4-2]
In chemical formulas 4-1 and 4-2,
M is zirconium or hafnium;
R is hydrogen or C 8-C20 alkyl;
r 12 is C 1-C10 alkyl;
x 11 is fluorine or chlorine;
r' "is hydrogen or C 1-C10 alkyl; and
N is an integer in the range of 1 to 3.
In a specific embodiment, R can be hydrogen.
In one specific example, R may be a straight or branched C 8-C20 alkyl group, and specifically may be n-octyl, t-octyl, n-nonyl, t-nonyl, n-decyl, t-decyl, n-undecyl, t-undecyl, n-dodecyl, t-dodecyl, n-tridecyl, t-tridecyl, n-tetradecyl, t-tetradecyl, n-pentadecyl or t-pentadecyl.
In one particular example, R' "is hydrogen or C 1-C5 alkyl, specifically, may be hydrogen or methyl.
In particular, the metal-ligand complex according to exemplary embodiments may be a compound selected from the following structures, but is not limited to:
in the above compound, M is zirconium or hafnium.
In addition, the present invention provides a catalyst composition for preparing a vinyl polymer selected from ethylene homopolymers or copolymers of ethylene and alpha-olefins, comprising the metal-ligand complex according to the invention and a cocatalyst.
According to exemplary embodiments, the promoter may be a boron compound promoter, an aluminum compound promoter, and mixtures thereof.
According to an exemplary embodiment, the content of the cocatalyst may be 0.5 to 10000mol with respect to 1mol of the metal-ligand complex, but is not limited thereto.
The boron compound that can be used as the cocatalyst may be a boron compound disclosed in U.S. patent No.5198401, and specifically, may be a mixture of one or two or more selected from the compounds represented by the following chemical formulas a to C:
[ chemical formula A ]
B(R21)3
[ Chemical formula B ]
[R22]+[B(R21)4]-
[ Chemical formula C ]
[(R23)qZH]+[B(R21)4]-
In the chemical formulas a to C,
B is boron atom; r 21 is phenyl, and the phenyl may be further substituted with 3 to 5 substituents selected from the group consisting of a fluorine atom, a C 1-C20 alkyl group, a C 1-C20 alkyl group substituted with a fluorine atom, a C 1-C20 alkoxy group, and a C 1-C20 alkoxy group substituted with a fluorine atom; r 22 is C 5-C7 aryl, C 1-C20 alkyl C 6-C20 aryl or C 6-C20 aryl C 1-C20 alkyl, such as triphenylmethyl; z is a nitrogen or phosphorus atom; r 23 is C 1-C20 alkyl or anilino substituted with two C 1-C10 alkyl groups together with a nitrogen atom; and q is an integer of 2 or 3.
The boron-based cocatalyst may be, for example, one or more selected from tris (pentafluorophenyl) borane, tris (2, 3,5, 6-tetrafluorophenyl) borane, tris (2, 3,4, 5-tetrafluorophenyl) borane, tris (3, 4, 5-trifluorophenyl) borane, tris (2, 3, 4-trifluorophenyl) borane, bis (pentafluorophenyl) (phenyl) borane, and the like.
The boron-based promoter may be one or two or more boron compounds whose borate anions are selected from the group consisting of tetrakis (pentafluorophenyl) borate, tetrakis (2, 3,5, 6-tetrafluorophenyl) borate, tetrakis (2, 3,4, 5-tetrafluorophenyl) borate, tetrakis (3, 4, 5-trifluorophenyl) borate, tetrakis (2, 4-trifluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate and tetrakis (3, 5-bistrifluoromethylphenyl) borate.
The boron-based cocatalyst may be one or two or more boron compounds whose cation is selected from triphenylmethyl ammonium, triethylammonium, tripropylammonium, tri (N-butyl) ammonium, N, N-dimethyl ammonium, N, N-diethyl ammonium, N, N-2,4, 6-pentamethyl ammonium, diisopropylammonium, dicyclohexylammonium, triphenylphosphine, tri (methylphenyl) phosphorus and tri (dimethylphenyl) phosphorus.
Specifically, the boron-based cocatalyst may be one or two or more boron compounds whose cation is selected from triphenylmethyl ammonium, triethylammonium, tripropylammonium tri (N-butyl) ammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4, 6-pentamethylphenylammonium, diisopropylammonium, dicyclohexylammonium, triphenylphosphine, tris (methylphenyl) phosphorus and tris (dimethylphenyl) phosphorus and borate anions selected from tetrakis (pentafluorophenyl) borate, tetrakis (2, 3,5, 6-tetrafluorophenyl) borate, tetrakis (2, 3,4, 5-tetrafluorophenyl) borate, tetrakis (3, 4, 5-trifluorophenyl) borate, tetrakis (2, 4-trifluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate and tetrakis (3, 5-bistrifluoromethylphenyl) borate.
More specifically, the boron-based cocatalyst may be one or more selected from the group consisting of: triphenylmethyl amine tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-bistrifluoromethylphenyl) borate, triethylamine tetrakis (pentafluorophenyl) borate, tripropylamine tetrakis (pentafluorophenyl) borate, tri (N-butyl) amine tetrakis (3, 5-bistrifluoromethylphenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N-2,4, 6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-bistrifluoromethylphenyl) borate, diisopropylaminetetrakis (pentafluorophenyl) borate, dicyclohexylamine tetrakis (pentafluorophenyl) borate, triphenyltetrakis (pentafluorophenyl) borate, tris (methylphenyl) tetrakis (pentafluorophenyl) borate, and tris (dimethylphenyl) tetrakis (pentafluorophenyl) borate, more preferably one or two or more selected from the group consisting of triphenylmethyl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and tris (pentafluorophenyl) borane.
Examples of aluminum compounds that may be used as cocatalysts in the catalyst compositions according to exemplary embodiments of the present invention include aluminoxane compounds of the formula D or E, organoaluminum compounds of the formula F, and organoaluminum alkyl oxides or aryloxy compounds of the formula G or H:
[ chemical formula D ]
(-Al(R31)-O-)r
[ Chemical formula E ]
(R31)2Al-(-O(R31)-)s-(R31)2
[ Chemical formula F ]
(R32)tAl(E)3-t
[ Chemical formula G ]
(R33)2AlOR34
[ Chemical formula H ]
R33Al(OR34)2
In the chemical formulas D to H,
R 31 is C 1-C20 alkyl, preferably methyl or isobutyl; r and s are each independently integers from 5 to 20; r 32 and R 33 are each independently C 1-C20 alkyl; e is a hydrogen atom or a halogen atom; t is an integer from 1 to 3; r 34 is C 1-C20 alkyl or C 6-C30 aryl.
Specific examples which can be used as the aluminum compound include aluminoxane compounds such as methylaluminoxane, modified methylaluminoxane and tetraisobutyldialuminoxane; and organoaluminum compounds, such as trialkylaluminum, including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; dialkylaluminum chlorides including dimethylaluminum chloride, alkylaluminum dichloride including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride, dialkylaluminum hydrides including dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride, and alkylalkoxyaluminum hydrides including methyldimethoxyaluminum, dimethylmethoxyaluminum, ethyldiethoxyaluminum, diethylethoxyaluminum, isobutyldibutoxyaluminum, diisobutylbutoxyaluminum, hexyldimethoxyaluminum, dihexylmethoxyaluminum and dioctylmethoxyaluminum. Preferably, aluminoxane compounds, trialkylaluminum and mixtures thereof can be used as cocatalysts. Specifically, methylaluminoxane, modified methylaluminoxane, tetraisobutyl dialuminoxane is used as a starting material, the preparation method comprises the steps of preparing trimethyl aluminum, triethylaluminum and triisobutylaluminum may be used alone or in a mixture thereof. More preferably, tetraisobutyldialuminoxane, triisobutylaluminum and mixtures thereof may be used.
Preferably, in the catalyst composition according to the exemplary embodiment of the present invention, when an aluminum compound is used as a cocatalyst, a transition metal (M) in the metal-ligand complex in the cocatalyst composition: the ratio between aluminum atoms (Al), based on the molar ratio, may preferably be in the range of 1:10 to 10000.
Preferably, in the catalyst composition according to the exemplary embodiment of the present invention, when both the aluminum compound and the boron compound are used as the cocatalyst, the transition metal (M): boron atom (B) in the metal-ligand complex according to the present invention: the proportion of aluminum atoms (Al), on a molar basis, may be in the range of 1:0.1 to 200:10 to 1000, more preferably in the range of 1:0.5 to 100:25 to 5000.
Within the above range, the ratio of the metal-ligand complex and the cocatalyst according to the present invention has excellent catalytic activity for preparing vinyl polymers, and the ratio range varies depending on the reaction purity.
As another aspect of one exemplary embodiment according to the present invention, the preparation method of the vinyl polymer using the catalyst composition for preparing the vinyl polymer may be performed by contacting the metal-ligand complex, the cocatalyst and ethylene or, if necessary, the comonomer in the presence of a suitable organic solvent. In this case, the precatalyst, i.e., the metal-ligand complex, and the cocatalyst component may be injected into the reactor separately, or may be injected into the reactor by pre-mixing the components, and is not limited by the mixing conditions of the order of introduction, temperature, concentration, etc.
Preferred organic solvents for use in the preparation process may be C3-C20 hydrocarbons, specific examples of which include n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene and xylene.
Specifically, when ethylene homopolymer is prepared, ethylene alone is used as a monomer, and when a copolymer of ethylene and α -olefin is prepared, C3 to C18 α -olefin may be used as a comonomer together with ethylene. Specific examples of C3 to C18 alpha-olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and the like. In the present invention, the above-mentioned C3 to C18 alpha-olefin may be homopolymerized with ethylene or may be copolymerized with two or more kinds of olefins, and more preferably 1-ene, 1-hexene, 1-octene or 1-decene is copolymerized with ethylene.
The pressure of ethylene may be 1 to 1000atm, and more preferably 5 to 100atm. In addition, the polymerization reaction can be efficiently carried out at 80℃or more, preferably at 100℃or more, more preferably at 160℃to 250 ℃. The temperature and pressure conditions during the polymerization may be determined in consideration of the efficiency of the polymerization reaction according to the type of reaction and the type of reactor used.
In general, when the solution polymerization process is performed at the above-mentioned high temperature, it is difficult to obtain a polymer having desired physical properties because the catalyst is deformed or deteriorated with an increase in temperature, thereby decreasing the activity of the catalyst. However, when the catalyst composition of the present invention is used to prepare vinyl polymers, stable catalytic activity can be exhibited at higher polymerization temperatures.
The vinyl polymer is an ethylene homopolymer or a copolymer of ethylene and an alpha-olefin. The copolymer of ethylene and alpha-olefin contains 50% by weight or more of ethylene, preferably 60% by weight or more of ethylene, more preferably 60 to 99% by weight of ethylene.
As described above, the Linear Low Density Polyethylene (LLDPE) prepared using C4 to C10 alpha-olefins as a comonomer has a density in the range of 0.940g/cc or less and can be extended to Very Low Density Polyethylene (VLDPE) or Ultra Low Density Polyethylene (ULDPE) or olefin elastomers having a density in the range of 0.900g/cc or less. In addition, when preparing the ethylene copolymer according to the present invention, hydrogen may be used as a molecular weight regulator to regulate the molecular weight, and the weight average molecular weight (Mw) of the ethylene copolymer is generally 80000 to 500000.
Since the catalyst composition in the present invention exists in a homogeneous form in a polymerization reactor, it is preferably applied to a solution polymerization process performed at a temperature equal to or higher than the melting point of a polymer. However, as disclosed in U.S. patent No.4752597, the catalyst composition may be used in slurry polymerization or gas phase polymerization processes in the form of a heterogeneous catalyst composition obtained by supporting a pre-catalyst and a cocatalyst as a metal-ligand complex on a porous metal oxide support.
The present invention will be described in detail by the following examples, but the scope of the present invention is not limited thereto.
Unless otherwise indicated, all ligand and catalyst synthesis experiments were performed under nitrogen using standard Schlenk or glove box techniques, and the organic solvent used in the reaction was refluxed under the action of sodium metal and benzophenone to remove moisture and used after distillation immediately before use. 1 H-NMR analyses were performed on the synthesized ligands and catalysts using Bruker400 or 500MHz at room temperature.
Methyl cyclohexane and n-heptane were used as polymerization solvents, followed by passing through a container equipped withMolecular sieves and activated alumina, and sparged with high purity nitrogen to substantially remove moisture, oxygen and other catalyst poisons.
Comparative example 1 Synthesis of Pre-catalyst C1
Precatalyst C1 was prepared according to KR10-2018-0048728A and KR 10-2019-007578A using 4-tert-octylphenol and 3, 6-di-tert-butyl-9H-carbazole.
EXAMPLE 1 Synthesis of Pre-catalyst C2
The reaction was carried out in a glove box under nitrogen atmosphere. A100 mL flask was charged with pre-catalyst C1 (1.17 g,0.87 mmol) and toluene (40 mL), and 3-pentadecylphenol (0.53 g,1.74 mmol) was further added, and the mixture was stirred at room temperature for 2 hours, and then the solvent was removed. The mixture was dissolved in 50mL of n-hexane and then filtered through a filter filled with dried zeolite to remove solids. The filtered solution was dried in vacuo to give pre-catalyst C2 (1.52 g, 91%) as a white solid.
1H NMR(CDCl3)：δ8.40(s,2H),8.28(s,2H),7.53-7.00(m,14H),6.72(m,2H),6.64(m,2H),6.36(m,2H),5.89(m,2H),5.60(s,2H),4.99(m,2H),4.70(m,2H),4.12(m,2H),3.65(m,2H),2.32(m,4H),1.73(s,4H),1.59-0.81(124H).
EXAMPLE 2 Synthesis of Pre-catalyst C3
A pre-catalyst a was prepared in the same manner as in comparative example 1, except that 4-methylphenol was used instead of 4-tert-octylphenol.
1H NMR(CDCl3)：δ8.30(s,2H),8.07(s,2H),7.47-7.00(m,16H),6.27(m,2H),4.60(m,2H),3.80(m,2H),3.40(m,2H),2.34(s,6H),1.54(s,18H),1.38(s,18H),-1.50(s,6H).
Pre-catalyst C3 (white solid, 1.36g, 90%) was prepared in the same manner as in example 1 except that pre-catalyst a was used instead of pre-catalyst C1.
1H NMR(CDCl3)：δ8.36(s,2H),8.25(s,2H),7.44-7.00(m,14H),6.72(m,2H),6.60(m,2H),6.33(m,2H),5.85(m,2H),5.58(s,2H),4.94(m,2H),4.67(m,2H),4.15(m,2H),3.69(m,2H),1.56-1.26(m,52H),1.56(s,4H),1.51(s,18H),1.40(s,18H),0.90(m,6H).
EXAMPLE 3 Synthesis of Pre-catalyst C4
A pre-catalyst B was prepared in the same manner as comparative example 1 except that 4-methylphenol was used instead of 4-tert-octylphenol and 2, 7-di-tert-butyl-9H-carbazole was used instead of 3, 6-di-tert-butyl-9H-carbazole.
Pre-catalyst C4 (white solid, 0.58g, 70%) was prepared in the same manner as in example 1 except that pre-catalyst B was used instead of pre-catalyst C1.
1H NMR(CDCl3)：δ8.31(d,2H),8.25(s,2H),7.44-7.00(m,8H),6.98-6.96(m,2H),6.92-6.91(m,2H),6.75(m,4H),6.51(m,2H),5.84(m,2H),5.38(m,2H),5.23(m,2H),4.84(m,2H),4.24-4.22(m,2H),3.81-3.80(m,2H),2.32(s,6H),1.94-1.93(m,2H),1.51(m,92H),1.08(m,6H).
EXAMPLE 4 copolymerization of ethylene and 1-octene for measuring the oxygen sensitivity of the transition metal compound produced
10. Mu. Mol of the pre-catalyst C2 prepared in example 1 was exposed to air at 22.1℃and 31% humidity for about 1 hour, and the pre-catalyst C2 was dissolved in 10mL of toluene to obtain a saturated solution, and ethylene and 1-octene were copolymerized using a batch polymerization apparatus as follows:
600mL of methylcyclohexane and 50mL of 1-octene were injected into a stainless steel reactor having a capacity of 1500mL, the inside of the reactor was purged with nitrogen after sufficiently drying, and then 2mL of a 1.0M hexane solution of triisobutylaluminum was added to the reactor. Subsequently, the reactor temperature was heated to 100℃and 1mL of a saturated solution of procatalyst C2 (i.e., 1mL of toluene containing 1.0. Mu. Mol of procatalyst C2) and 40. Mu. Mol of triphenylmethyl tetrakis (pentafluorophenyl) borate were sequentially added, and ethylene was charged to the reactor to a pressure of 20bar, and then ethylene was continuously supplied for polymerization. The reaction was carried out for 5 minutes, and then the recovered reaction product was dried in a vacuum oven at 40℃for 8 hours. The polymerization results are shown in Table 1.
Example 5
Copolymerization of ethylene and 1-octene was performed in the same manner as in example 4 except that a pre-catalyst C2 (example 1) which was not exposed to air was used. The polymerization conditions and the polymerization results are shown in Table 1.
Comparative example 2
Copolymerization of ethylene and 1-octene was performed in the same manner as in example 4 except that precatalyst C1 (comparative example 1) was used instead of precatalyst C2 (example 1). The polymerization conditions and the polymerization results are shown in Table 1.
Comparative example 3
Copolymerization of ethylene and 1-octene was performed in the same manner as in example 4 except that precatalyst C1 (comparative example 1) which was not exposed to air was used instead of precatalyst C2 (example 1). The polymerization conditions and the polymerization results are shown in Table 1.
TABLE 1
Table 1 shows the observation of the temperature change (Δt) of the precatalyst C2 of example 1 and the precatalyst C1 of comparative example 1 as catalysts in the polymerization of ethylene and 1-octene, depending on whether the precatalyst is exposed to air or not. From the results, it was confirmed that the precatalyst C2 of example 1 exhibited a constant temperature change during polymerization, regardless of whether it was exposed to air or not, whereas the precatalyst C1 of comparative example 1 exhibited a significantly reduced temperature change when exposed to air.
Specifically, as can be seen from the polymerization results of table 1, since the precatalyst C2 of the present invention (example 1) has a structure in which an alkyl-substituted phenoxy leaving group, for example, pentadecyl group, is introduced, unlike the precatalyst C1 (comparative example 1) in which an alkyl-type leaving group, for example, methyl group, is introduced, the precatalyst C2 is relatively insensitive to impurities such as oxygen and moisture in the air, resulting in a decrease in activity, that is, relatively few impurities that may occur during the reaction are affected, so that the stability of the catalyst is excellent, which may be advantageous in the use in commercial factories.
As described above, it was confirmed that the tolerance of the catalyst to oxygen and moisture and other impurities, as well as the stability and activity, were significantly changed due to the structure of the polymerization catalyst.
EXAMPLES 6 TO 8 AND COMPARATIVE EXAMPLE 4 copolymerization of ethylene and 1-octene by continuous solution polymerization at high temperature
The copolymerization of ethylene and 1-octene is carried out in a temperature-controlled continuous polymerization reactor equipped with a mechanical stirrer.
The precatalysts C2, C3, C4 and C1 prepared in examples 1,2 and 3 and comparative example 1 were used as catalysts, n-heptane was used as solvent, and modified methylaluminoxane (20 wt%, nouryon) was used as cocatalyst. The catalyst amounts are shown in Table 2. Each catalyst was dissolved in toluene at a concentration of 0.2g/L and then injected, and polymerization was carried out using 1-octene as a comonomer. When polymerization is carried out with only one polymer at each reaction condition, the conversion of the reactor is estimated by the reaction conditions and the temperature gradient in the reactor. In the case of single-site catalysts, the molecular weight is controlled as a function of reactor temperature and 1-octene content. The conditions and results are shown in Table 2.
Melt Index (MI): melt Index (MI) was measured using ASTMD1238 analysis at 190℃under a load of 2.16 kg.
Density: the density was measured by astm d792 analysis method.
TABLE 2
As can be seen from the polymerization results of table 2, in examples 6,7 and 8 using the precatalyst C2 (example 1), the precatalyst C3 (example 2) and the precatalyst C4 (example 3) of the present invention as polymerization catalysts, the catalyst activity was significantly improved as compared with the existing catalyst, although the catalyst amount was reduced at 220 ℃ high temperature, as compared with comparative example 4 (comparative example 1) using the known precatalyst C1.
It is thus understood that the metal-ligand complex according to the present invention can effectively prepare a copolymer of high molecular weight ethylene and α -olefin, and has remarkably excellent catalytic activity and stability even at high temperature due to the structural characteristics of the specific functional group introduced.

Claims (11)

1. A metal-ligand complex represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
M is a transition metal of group 4 of the periodic Table;
Ar 1 and Ar 2 are each independently C 6-C20 aryl, and the aryl groups described in Ar 1 and Ar 2 may be further substituted with C 1-C20 alkyl;
R 1 to R 4 are each independently C 1-C20 alkyl, C 6-C20 aryl or C 6-C20 aryl-C 1-C20 alkyl;
R 5 and R 6 are each independently C 1-C20 alkyl;
R 7 and R 8 are each independently halogen or C 1-C20 alkyl;
a, b, c, d, e and f are each independently integers from 0 to 4; and
M is an integer in the range of 2 to 5.
2. The metal-ligand complex of claim 1, wherein
Ar 1 and Ar 2 are each independently C 6-C20 aryl or C 1-C20 alkyl C 6-C20 aryl;
R 1 to R 4 are each independently C 1-C20 alkyl;
R 7 and R 8 are each independently halogen or C 1-C20 alkyl;
a, b, c, d, e and f are each independently integers from 1 to 3; and
M is an integer ranging from 3 to 5.
3. The metal-ligand complex of claim 1, wherein the metal-ligand complex is represented by chemical formula 2-1 or chemical formula 2-2 as follows:
[ chemical formula 2-1]
[ Chemical formula 2-2]
In chemical formulas 2-1 and 2-2,
M is titanium, zirconium or hafnium;
Ar 1 and Ar 2 are each independently C 6-C20 aryl or C 1-C20 alkyl C 6-C20 aryl;
R 1 to R 4 are each independently C 1-C20 alkyl;
R 5 and R 6 are each independently C 1-C20 alkyl;
x 1 and X 2 are each independently halogen;
R 'and R' are each independently hydrogen or C 1-C20 alkyl; and
M is an integer ranging from 3 to 5.
4. A metal-ligand complex according to claim 3, wherein
Ar 1 and Ar 2 are each independently C 6-C12 or C 1-C20 alkyl C 6-C12 aryl;
R 1 to R 4 are each independently C 1-C10 alkyl;
R 5 and R 6 are each independently C 1-C10 alkyl; and
R 'and R' are each independently hydrogen or C 1-C10 alkyl.
5. The metal-ligand complex of claim 1, wherein the metal-ligand complex is formula 3-1 or formula 3-2 as shown below:
[ chemical formula 3-1]
[ Chemical formula 3-2]
In chemical formulas 3-1 and 3-2,
M is zirconium or hafnium;
ar is C 6-C12 aryl or C 1-C20 alkyl C 6-C12 aryl;
R 11 is C 1-C5 alkyl;
r 12 is C 1-C10 alkyl;
x 11 is fluorine or chlorine;
r' "is hydrogen or C 1-C10 alkyl; and
N is an integer in the range of 1 to 3.
6. The metal-ligand complex of claim 1, wherein the metal-ligand complex is formula 4-1 or formula 4-2 as shown below:
[ chemical formula 4-1]
[ Chemical formula 4-2]
In chemical formulas 4-1 and 4-2,
M is zirconium or hafnium;
R is hydrogen or C 8-C20 alkyl;
r 12 is C 1-C10 alkyl;
x 11 is fluorine or chlorine;
r' "is hydrogen or C 1-C10 alkyl; and
N is an integer in the range of 1 to 3.
7. A catalyst composition for preparing a vinyl polymer comprising:
the metal-ligand complex of any one of claims 1 to 6; and
And (3) a cocatalyst.
8. The catalyst composition of claim 7, wherein the promoter is an aluminum compound promoter, a boron compound promoter, or a mixture thereof.
9. The catalyst composition of claim 7, wherein the cocatalyst is used in an amount of 0.5 to 10000mol relative to 1mol of the metal-ligand complex.
10. A process for producing a vinyl polymer, which comprises polymerizing ethylene or ethylene and an α -olefin in the presence of the catalyst composition for producing a vinyl polymer according to claim 7 to obtain a vinyl polymer.
11. The process of claim 10, wherein the polymerization is carried out at 100 ℃ to 250 ℃.
CN202280086980.4A 2021-12-29 2022-12-28 Metal-ligand complex, catalyst composition for preparing vinyl polymer containing the same, and method for preparing vinyl polymer using the same Pending CN118475586A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2021-0190680 2021-12-29
KR10-2022-0180789 2022-12-21
KR1020220180789A KR20230101717A (en) 2021-12-29 2022-12-21 Metal-ligand complexe, catalyst composition for producing ethylene-based polymer containing the same, and method of producing ethylene-based polymer using the same
PCT/IB2022/062827 WO2023126844A1 (en) 2021-12-29 2022-12-28 Metal-ligand complex, catalyst composition for producing ethylene-based polymer containing the same, and method of producing ethylene-based polymer using the same

Publications (1)

Publication Number Publication Date
CN118475586A true CN118475586A (en) 2024-08-09

Family

ID=92157924

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280086980.4A Pending CN118475586A (en) 2021-12-29 2022-12-28 Metal-ligand complex, catalyst composition for preparing vinyl polymer containing the same, and method for preparing vinyl polymer using the same

Country Status (1)

Country Link
CN (1) CN118475586A (en)

Similar Documents

Publication Publication Date Title
US6051667A (en) Olefin polymerization using a catalyst having a bridged cyclopentadienyl-phosphole ligand
RU2374267C2 (en) Arylphenoxy catalyst system for producing homopolymer or copolymers of ethylene and alpha-olefins
US6124487A (en) Olefin polymerization catalyst having a bridged phosphole-heteroatom ligand
KR101146875B1 (en) Transition metal catalytic systems and methods for preparing ethylene homopolymers or copolymers of ethylene and olefins using the same
KR101142115B1 (en) Transition metal complexes, catalysts composition containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and -olefins using the same
KR101151606B1 (en) Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and a-olefins using the same
KR102643986B1 (en) A novel indene-based transition metal complexes, catalysts composition containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same
KR101141359B1 (en) Homogeneous catalyst system for producing ethylene homopolymer or ethylene copolymers with ?-olefins
KR20150138042A (en) NEW TRANSITION METAL COMPLEXES, CATALYST COMPOSITIONS CONTAINING THE SAME FOR OLEFIN POLYMERIZATION AND METHODS FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND α-OLEFINS USING THE SAME
KR101142122B1 (en) New transition metal catalytic systems and methods for preparing ethylene homopolymers or copolymers of ethylene and ?-olefins using the same
EP2077270B1 (en) Transition metal complexes, and catalysts compositions for preparing ethylene homopolymers or copolymers
CN118475586A (en) Metal-ligand complex, catalyst composition for preparing vinyl polymer containing the same, and method for preparing vinyl polymer using the same
KR20220094138A (en) Metal-ligand complex, catalyst composition for preparing ethylene-based polymer containing the same, and preparation method of ethylene-based polymer using the same
KR101980683B1 (en) New indene-based transition metal complexes, catalysts composition containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same
TW202330558A (en) Metal-ligand complex, catalyst composition for producing ethylene-based polymer containing the same, and method of producing ethylene-based polymer using the same
KR20210020424A (en) Novel transition metal compound and method for preparing polyethlene using the same
KR100526226B1 (en) Metallocene catalyst for producing polyethylene and polymerization method using the same
KR20130089490A (en) NEW TRANSITION METAL COMPLEX HAVING QUINOLIN-1(2H)-YL GROUP AND CATALYST COMPOSITION CONTAINING THE SAME FOR OLEFIN POLYMERIZATION, AND METHODS FOR PREPARING ETHYLENE HOMOPOLYMERS OR COPOLYMERS OF ETHYLENE AND α-OLEFINS USING THE SAME
KR20230101717A (en) Metal-ligand complexe, catalyst composition for producing ethylene-based polymer containing the same, and method of producing ethylene-based polymer using the same
CN116261572A (en) Metal-ligand complex, catalyst composition for preparing ethylene-based polymer comprising the same, and method for preparing ethylene-based polymer using the same
KR102128569B1 (en) Novel transition metal compound
KR20220101482A (en) Novel metallocene compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same
KR101889979B1 (en) new transition metal complex, catalyst composition containing the same for olefin polymerization and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same
KR20220069822A (en) Hybride supported metallocene catalyst and process for preparing polyethylene copolymer using the same
KR20180082314A (en) New transition metal complexes, catalysts composition containing the same, and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination