KR20170046462A - Transition metal complexes, catalyst compositions comprising the same, and method for preparing polyolefins therewith - Google Patents
Transition metal complexes, catalyst compositions comprising the same, and method for preparing polyolefins therewith Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07F7/28—Titanium compounds
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
Abstract
Description
The present invention relates to a transition metal compound, a catalyst composition containing the same, and a process for producing a polyolefin using the same.
Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of conventional polyolefins. However, since the Ziegler-Natta catalyst has a high activity, it has a wide molecular weight distribution of the resulting polymer because it is a multi-active site catalyst, and the composition distribution of the comonomer is not uniform, thereby limiting the desired properties.
In order to overcome this limitation, a metallocene catalyst having a ligand bonded with a transition metal such as titanium, zirconium, or hafnium and a cyclopentadiene functional group has been developed and widely used.
The metallocene catalyst is a single active site catalyst, and the molecular weight distribution of the produced polymer is narrow, and molecular weight, stereoregularity, crystallinity and the like can be controlled according to the structure of the catalyst and the ligand. However, a polyolefin polymerized with a metallocene catalyst generally has a low melting point and a narrow molecular weight distribution. When such a polyolefin is applied to a product, there is a problem that it is difficult to apply the polyolefin to the field, such as productivity is remarkably decreased due to the influence of extrusion load.
In particular, in order to solve the problems of the metallocene catalyst described above, a number of metallocene compounds coordinated with a ligand compound containing a hetero atom have been proposed. However, among these attempts, only a few metallocene catalysts have been applied to commercial processes.
In particular, a large number of catalysts capable of obtaining a polymer having a high molecular weight with high reactivity to olefin monomers have been proposed. However, there are limitations in producing a polyolefin having a high molecular weight and a low density due to relatively low copolymerization activity.
The present invention is to provide a transition metal compound having a novel structure, which exhibits a high activity and an improved copolymerization activity for the polymerization reaction of an olefin monomer to enable the production of a polyolefin having a high molecular weight and a low density.
The present invention also provides a catalyst composition for olefin polymerization comprising the transition metal compound.
The present invention also provides a process for producing a polyolefin using the catalyst composition.
According to the present invention, there is provided a transition metal compound represented by the following Formula 1:
[Chemical Formula 1]
In Formula 1,
R 1 to R 7 are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;
M is a Group 4 transition metal;
Q 1 and Q 2 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
X 1 is each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;
X 2 each independently represents hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.
According to the present invention, there is provided a catalyst composition for olefin polymerization comprising the transition metal compound and a cocatalyst.
According to the present invention, there is also provided a process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for olefin polymerization.
Hereinafter, the transition metal compound, the catalyst composition and the method for producing the polyolefin according to embodiments of the present invention will be described in detail.
Prior to that, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning.
Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.
I. Transition metal compounds
According to one embodiment of the invention,
There is provided a transition metal compound represented by the following Formula 1:
[Chemical Formula 1]
In Formula 1,
R 1 to R 7 are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;
M is a Group 4 transition metal;
Q 1 and Q 2 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
X 1 is each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;
X 2 each independently represents hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.
The transition metal compound represented by Formula 1 has a structure in which ketimide ligands are linked to a derivative of cyclopentadiene having a heterocycle containing sulfur.
As a result of continuous research by the present inventors, it has been found that the transition metal compound represented by the above formula (1) has high activity when used as a catalyst for the copolymerization of ethylene with octene, hexene, butene and the like due to the influence of the cyclopentadiene derivative having a heterocycle It is possible to obtain a polyolefin having a high molecular weight and a low density.
In Formula 1, M may be a Group 4 transition metal element on the periodic table; Preferably, it may be titanium (Ti), zirconium (Zr) or hafnium (Hf).
Wherein Q 1 and Q 2 are each independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms , An arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms. Preferably, each of Q 1 and Q 2 is independently halogen or an alkyl group having 1 to 10 carbon atoms.
In Formula 1, R 1 to R 7 each independently represent hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms. Preferably, each of R 1 to R 7 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
In the above formula (1), each X 1 may independently be hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms. Preferably, each X 1 is independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms Group, a cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
In Formula 1, each of X 2 may independently be hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms. Preferably, X 2 is independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group of 3 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an arylalkyl group of 7 to 20 carbon atoms.
In the definition of the substituent, the alkyl group, the alkenyl group, and the alkynyl group may each have a linear or branched structure.
The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, and examples thereof include phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like.
The alkylaryl group means an aryl group having at least one C 1 -C 20 linear or branched alkyl group introduced therein. The arylalkyl group means a linear or branched alkyl group having at least one aryl group having 6 to 20 carbon atoms introduced therein.
The halogen means fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
According to one embodiment of the present invention, it is advantageous that each of R 1 to R 7 independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms, from the viewpoint of ease of synthesis of the transition metal compound. Each of X 1 is independently an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. In addition, it is advantageous that X 2 is each independently hydrogen or halogen.
Meanwhile, as a non-limiting example, the transition metal compound of Formula 1 may be represented by Formula 1-1, Formula 1-2, Formula 1-3, or Formula 1-4:
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
[Formula 1-4]
In the above Formulas 1-1 to 1-4,
Each Cy is a cyclohexyl group,
iPr are each an isopropyl group.
In addition to the above representative examples, the transition metal compound may have various structures within the range defined in Formula 1, and these compounds may exhibit equivalent actions and effects.
The transition metal compound can be synthesized, for example, according to Scheme 1 below:
[Scheme 1]
In Scheme 1 above,
R 1 to R 7 , M, Q 1 , Q 2 , X 1 , and X 2 are each as defined in Formula 1;
Q 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
X 3 is hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.
A more detailed synthesis method for the transition metal compound is described in the synthesis example section.
II. Catalyst composition for olefin polymerization
On the other hand, according to another embodiment of the present invention, there is provided a catalyst composition for olefin polymerization comprising the above-mentioned transition metal compound.
As described above, the transition metal compound can exhibit high activity and particularly improved copolymerization activity when used as a catalyst in the polymerization of olefin monomers, thereby enabling the provision of low density and high molecular weight polyolefins.
The catalyst composition may include a cocatalyst. The promoter is any organometallic compound capable of activating the transition metal compound, and is not particularly limited as long as it can be used in the polymerization of an olefin under the catalyst of a transition metal compound.
For example, the promoter may be at least one compound selected from the group consisting of compounds represented by the following formulas (4) to (6):
[Chemical Formula 4]
- [Al (R < 41 >) - O] c-
In the general formula (4), R 41 are the same or different from each other and each independently represents a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more ,
[Chemical Formula 5]
D ( R51 ) 3
In Formula 5, D is aluminum or boron, R 51 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 6]
[LH] + [Q (E) 4 ] -
In Formula 6,
L is a neutral Lewis base, [LH] + is a Bronsted acid, Q is boron or aluminum in a +3 type oxidation state, and E is independently at each occurrence one or more hydrogen atoms are replaced by halogen, hydrocarbyl having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with an alkoxy functional group or a phenoxy functional group.
According to one embodiment, the compound represented by Formula 4 may be an alkylaluminoxane such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane. Further, it may be a modified alkylaluminoxane (MMAO) in which two or more alkylaluminoxanes are mixed.
According to one embodiment, the compound represented by Formula 5 is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, di But are not limited to, ethyl chloro aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, Aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.
Also, according to one embodiment, the compound represented by Formula 6 may be prepared by reacting triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium (O, p-dimethylphenyl) boron, triethylammoniumtetra (p-tolyl) boron, triethylammoniumtetra (P-trifluoromethylphenyl) boron, butylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylaniliniumtetraphenyl Boron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, Trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl boron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, Aluminum triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (p- N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium Diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylpentafluorophenylaluminum, trimethylpentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethyl Triphenylcarbamoyltetraphenylboron, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarbamoniumtetra (p-trifluoromethylphenyl) boron, triphenylcarboniumtetrapentafluorophenyl Boron, and the like.
The promoter may be an organoaluminum compound, an organoboron compound, an organomagnesium compound, an organozinc compound, an organolithium compound, or a mixture thereof.
For example, the promoter is preferably an organoaluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ), Ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane), and the like. Lt; / RTI > group.
On the other hand, the content ratio of the components constituting the catalyst composition can be determined in consideration of catalytic activity. For example, the molar ratio of the transition metal compound to the cocatalyst in the catalyst composition is controlled to be 1: 1 to 1: 10,000, or 1: 1 to 1: 5,000, or 1: 1 to 1: 3,000, Lt; / RTI >
The catalyst composition may be used in a state of being supported on a carrier. The carrier may be a metal, a metal salt, a metal oxide, or the like, which is applied to a conventional supported catalyst. Non-limiting examples of the carriers include silica, silica-alumina, silica-may be magnesia or the like, Na 2 O, K 2 CO 3, BaSO 4, Mg (NO 3) 2 oxides of metals, such as carbonates, sulfates, be May contain a trichromatic component.
The components constituting the catalyst composition can be added simultaneously or in any order, in the presence or absence of suitable solvents and olefin monomers, to act as a catalyst system having activity. As a suitable solvent, hexane, heptane, toluene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone and the like can be used.
III. Process for producing polyolefin
According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the above-mentioned catalyst composition for olefin polymerization.
The polymerization reaction of the olefin monomer may be carried out in a possible conventional process applied to the polymerization of olefin monomers such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.
The polymerization of the olefin monomer may be carried out in an inert solvent. By way of non-limiting example, the inert solvent may be benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and the like.
As the olefin monomer, ethylene, alpha-olefin, cyclic olefin, or the like can be used, and a diene olefin-based monomer or triene olefin-based monomer having two or more double bonds can also be used. Specifically, the olefin monomer may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Dodecene, 1-tetradecene, 1-hexadecene, 1-aotocene, norbornene, norbornian, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, , 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like. The olefin monomers may be used singly or in combination of two or more. When the polyolefin is a copolymer of ethylene and another comonomer, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene may be used as the comonomer.
The polymerization reaction of the olefin monomer may be carried out at a temperature of 25 to 500 ° C and a pressure of 1 to 100 bar for 5 minutes to 24 hours. At this time, considering the yield of the polymerization reaction, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 120 to 160 ° C. Further, the pressure of the polymerization reaction is preferably 1 to 70 bar, more preferably 5 to 40 bar. The polymerization reaction time may be 5 minutes to 5 hours, or 5 minutes to 1 hour, or 5 minutes to 10 minutes.
The transition metal compound according to the present invention exhibits a high activity and an improved copolymerization activity in the polymerization reaction of the olefin monomer, thereby making it possible to produce a polyolefin having a high molecular weight and a low density.
Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.
Synthetic example One
[Scheme 1-1]
(15.854 g, 73.3 mmol) was dissolved in THF (180 mL) and MeMgBr (50 mL) was added at 0 < 0 & , 146.6 mmol, 2 eq.) Was slowly added dropwise. It was then slowly warmed up and stirred at room temperature for 12 hours. After confirming the disappearance of the starting material by TLC, distilled water (10 mL) was slowly added dropwise and stirred for 10 minutes. 6N HCl (180 mL) was then added and stirred for 12 hours. After TLC analysis, hexane (50 mL) was added to extract the starting material. The water layer was removed by extraction. The excess water was removed through MgSO 4 , and the solvent was removed under reduced pressure to obtain 1 , 2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophene (15.4 g, 98%).
1 H NMR (500MHz, in Benzene ): 7.83 (d, 1H), 7.71 (d, 1H), 7.35 (t, 1H), 7.20 (t, 1H), 3.33 (m, 1H), 2.09 (s, 3H ), 2.04 (s, 3H), 1.40 (d, 3H).
(ii) The 1,2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophene (14.57 g, 67.98 mmol) was dissolved in THF (230 mL) and n-BuLi (28.6 mL, 71.38 mmol, 1.05 eq.) was slowly added dropwise. It was then slowly warmed up and stirred at room temperature for 12 hours. After confirming disappearance of the starting material by NMR, TMSCl (12.9 mL, 101.97 mmol, 1.5 eq.) Was slowly added dropwise at room temperature and stirred at room temperature for 12 hours. NMR showed no starting material. The THF solvent was filtered off under reduced pressure and the reaction mixture was dissolved in hexane (150 mL). LiCl was removed by filtration and the solvent was filtered under reduced pressure to obtain trimethyl (1,2,3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl -3H-benzo [b] cyclopenta [d] thiophen-3-yl) silane.
1 H NMR (500MHz, in Benzene ): 8.00 (d, 1H), 7.87-7.84 (m, 2H), 7.73 (d, 1H), 7.37 (t, 1H), 7.32 (t, 1H), 7.25 (t (S, 3H), 2.05 (s, 3H), 1.66 (s, 3H), 1.49 3H), -0.04 (s, 9H), -0.08 (s, 9H).
3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl (1,2,3- d] thiophen-3-yl) silane (19.65 g, 68.58 mmol) was dissolved in CH 2 Cl 2 (175 mL) and then TiCl 4 (68.60 g, 68.58 mmol, 1.0 eq.) was slowly added dropwise at room temperature. The mixture was stirred at room temperature for 12 hours. Thereafter, all of CH 2 Cl 2 was removed by vacuum filtration to obtain a compound (23.0 g, 91%) represented by the above formula 2-1 as a black solid.
1 H NMR (500MHz, in Benzene ): 7.64 (d, 1H), 7.19 (d, 1H), 7.06 (t, 1H), 6.96 It, 1H), 2.24 (s, 3H), 2.10 (s, 3H) , ≪ / RTI > 1.90 (s, 3H).
(iv) The compound represented by Formula 2-1 (1.52 g, 4.14 mmol) and the ketimide ligand represented by Formula 3-1 (1.33 g, 4.14 mmol) were dissolved in toluene (20 mL) , 5.28 mmol) was slowly added dropwise. The reaction mixture was then stirred at ambient temperature for 12 hours. After confirming disappearance of the starting material by NMR, the amine salt was removed by filtration and the toluene solvent was removed by vacuum filtration. Subsequently, the solid obtained in the glovebox was washed with hexane to obtain a dark orange-colored transition metal compound (2.0 g, 75%) represented by Formula 1-1.
1 H NMR (500MHz, in Benzene ): 7.88 (d, 1H), 7.65 (d, 1H), 7.33-7.26 (m, 3H), 6.96-6.91 (m, 2H), 3.13-3.08 (m, 2H) , 2.47 (s, 3H), 2.15 (s, 3H), 2.14 (s, 3H), 1.79-0.85 (m, 20H).
Synthetic example 2
[Scheme 1-2]
The transition metal compound represented by Formula 1-2 was synthesized in the same manner as in Synthesis Example 1, except that the compound represented by Formula 3-2 of Scheme 1-2 was used instead of the compound represented by Formula 3-1. .
1 H NMR (500MHz, in Benzene ): 7.92 (d, 1H), 7.41 (d, 1H), 7.02 (m, 1H), 6.91 (t, 1H), 6.86 (t, 1H), 6.42 (m, 2H ), 2.49 (s, 3H), 2.16 (s, 3H), 2.11 (s, 3H), 1.84-1.10 (m, 20H).
Synthetic example 3
[Scheme 1-3]
The transition metal compound represented by Formula 1-3 was synthesized in the same manner as in Synthesis Example 1, except that the compound represented by Formula 3-3 of Scheme 1-3 was used instead of the compound represented by Formula 3-1. .
1 H NMR (500MHz, in Benzene ): 7.74 (d, 1H), 7.42-7.35 (m, 3H), 7.09-7.06 (m, 3H), 7.01-6.97 (m, 2H), 3.11-2.99 (m, 2H), 2.31 (s, 3H), 2.04 (s, 3H), 1.74 (s, 3H), 1.53-0.80 (m, 20H).
Synthetic example 4
[Scheme 1-4]
The transition metal compound represented by Formula 1-4 was synthesized in the same manner as in Synthesis Example 1, except that the compound represented by Formula 3-4 of Scheme 1-4 was added instead of the compound represented by Formula 3-1. .
1 H NMR (500MHz, in Benzene ): 7.86 (d, 1H), 7.38 (d, 1H), 7.14 (t, 1H), 7.01 (t, 1H), 6.54 (m, 1H), 6.48 (t, 2H ), 2.41 (s, 3H), 2.12 (s, 3H), 2.07 (s, 3H), 1.28-1.17 (dd, 6H), 0.65-0.62 (m, 6H).
Synthetic example 5
[Scheme 1-5]
The transition metal compound represented by Formula 1-F was synthesized by the method of Synthesis Example 1, except that the compound represented by Formula 2-F of Scheme 1-5 was added instead of the compound represented by Formula 2-1. .
1 H NMR (500MHz, in Benzene ): 6.89-6.80 (m, 3H), 3.47-3.35 (m, 1H), 2.37 (s, 15H), 2.20-1.86 (m, 7H), 1.70-0.86 (m, 14H).
Example One
A 2 L autoclave reactor was charged with 1 L of hexane and 350 mL of 1-octene, then the temperature of the reactor was preheated to 150 DEG C and ethylene was saturated at 35 bar. 1 micromole (based on Ti) of the transition metal compound of the formula 1-1 according to Synthesis Example 1, 10 equivalents of N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate and scavenger with triisobutylaluminum (TIBAL, 1.0 M solution in hexane, Aldrich) was charged into the reactor and then injected into the reactor. The copolymerization reaction proceeded for 8 minutes while continuously injecting ethylene to maintain the pressure in the reactor at 35 bar. The reaction heat was removed through a cooling coil inside the reactor to keep the polymerization temperature at a constant level.
After the completion of the reaction, the remaining ethylene gas was removed and the polymer solution was added to an excess amount of ethanol to induce precipitation of the polymer. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 DEG C for over 12 hours.
Example 2
A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of the formula 1-2 according to Synthesis Example 2 was used instead of the transition metal compound of Synthesis Example 1.
Example 3
A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of Formula 1-3 according to Synthesis Example 3 was used instead of the transition metal compound of Synthesis Example 1.
Example 4
A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of Formula 1-4 according to Synthesis Example 4 was used instead of the transition metal compound of Synthesis Example 1.
Comparative Example One
A polymer was obtained in the same manner as in Example 1, except that the transition metal compound of the formula 1-F according to Synthesis Example 5 was used instead of the transition metal compound of the above Synthesis Example 1.
Test Example
The physical properties of the polymers according to Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 1.
1) The yield was measured by the ratio of the weight (g) of the produced polymer.
2) The melt index (MI) of the polymer was measured according to ASTM D-1238 (condition E, 190 캜, 2.16 kg load).
3) The density (g / cc) of the polymer was measured using a 180 ° C press mold with a sample treated with an antioxidant (1000 ppm). The sample was made into a sheet having a thickness of 3 mm and a radius of 2 cm. (Mettler) scales.
4) The glass transition temperature (T c ) and melting temperature (T m ) of the polymer were measured using differential scanning calorimetry (DSC 2920, TA instrument). Specifically, the polymer was heated to 220 캜, maintained at that temperature for 5 minutes, cooled again to 20 캜, and then increased in temperature. At this time, the temperature rising rate and the falling rate were adjusted to 10 ° C / min, respectively.
Referring to Table 1 above, it was confirmed that the polymer according to Examples was a low density polyolefin having a molecular weight equivalent to that of the polymer of Comparative Example 1.
Claims (7)
[Chemical Formula 1]
In Formula 1,
R 1 to R 7 are each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;
M is a Group 4 transition metal;
Q 1 and Q 2 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;
X 1 is each independently hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms;
X 2 each independently represents hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a heterohydrocarbyl group having 1 to 20 carbon atoms.
M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
Wherein Q 1 and Q 2 are each independently halogen or an alkyl group having 1 to 10 carbon atoms.
Each of R 1 to R 7 and X 1 is independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group of 3 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an arylalkyl group of 7 to 20 carbon atoms;
X 2 is independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
Each of R 1 to R 7 is independently hydrogen or an alkyl group having 1 to 10 carbon atoms;
Each X 1 is independently an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms;
And X < 2 > are each independently hydrogen or halogen.
The compound represented by the formula (1) is a transition metal compound represented by the following formula (1-1), (1-2), (1-3)
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
[Formula 1-4]
In the above Formulas 1-1 to 1-4,
Each Cy is a cyclohexyl group,
iPr are each an isopropyl group.
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| WO2019132687A1 (en) | 2017-12-25 | 2019-07-04 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and thiophene fused cyclopentadienyl ligands |
| WO2019203676A1 (en) | 2018-04-16 | 2019-10-24 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and indole fused cyclopentadienyl ligands |
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| WO2019132687A1 (en) | 2017-12-25 | 2019-07-04 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and thiophene fused cyclopentadienyl ligands |
| WO2019129502A1 (en) | 2017-12-25 | 2019-07-04 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and thiophene fused cyclopentadienyl ligands |
| CN111527095A (en) * | 2017-12-25 | 2020-08-11 | 阿朗新科荷兰有限公司 | Metal complexes comprising amidine and thiophene fused cyclopentadienyl ligands |
| JP2021507938A (en) * | 2017-12-25 | 2021-02-25 | アランセオ・ネザーランズ・ベー・フェー | Metal complex containing amidine and thiophene condensed cyclopentadienyl ligand |
| US11578148B2 (en) | 2017-12-25 | 2023-02-14 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and thiophene fused cyclopentadienyl ligands |
| WO2019203676A1 (en) | 2018-04-16 | 2019-10-24 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and indole fused cyclopentadienyl ligands |
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| CN111989336A (en) * | 2018-04-16 | 2020-11-24 | 阿朗新科荷兰有限公司 | Metal complexes comprising amidine and indole fused cyclopentadienyl ligands |
| JP2021521225A (en) * | 2018-04-16 | 2021-08-26 | アランセオ・ネザーランズ・ベー・フェー | Metal complex containing cyclopentadienyl ligand fused with amidine and indole |
| US11560394B2 (en) | 2018-04-16 | 2023-01-24 | Arlanxeo Netherlands B.V. | Metal complex comprising amidine and indole fused cyclopentadienyl ligands |
| CN111989336B (en) * | 2018-04-16 | 2023-07-07 | 阿朗新科荷兰有限公司 | Metal complexes comprising amidine and indole fused cyclopentadienyl ligands |
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