WO2021221283A1 - Composé de chrome et son procédé de production - Google Patents

Composé de chrome et son procédé de production Download PDF

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Publication number
WO2021221283A1
WO2021221283A1 PCT/KR2021/002240 KR2021002240W WO2021221283A1 WO 2021221283 A1 WO2021221283 A1 WO 2021221283A1 KR 2021002240 W KR2021002240 W KR 2021002240W WO 2021221283 A1 WO2021221283 A1 WO 2021221283A1
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formula
crcl
chromium compound
compound
chromium
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PCT/KR2021/002240
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English (en)
Korean (ko)
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이분열
이동근
백준원
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아주대학교 산학협력단
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Publication of WO2021221283A1 publication Critical patent/WO2021221283A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table

Definitions

  • the present invention relates to a chromium compound and a method for preparing the same.
  • CrCl 3 ⁇ 3 (THF is tetrahydrofuran) is a material frequently used as a starting material in the preparation of organometallic chromium compounds and chromium coordination compounds.
  • CrCl 3 ⁇ 3 (THF) is a basic compound with high commercial utility, such as being used in ethylene oligomerization catalysis by reacting with a bisphosphine ligand.
  • THF adduct of crystalline high purity CrCl 3 having a single structure can be synthesized by an easy method, it can be usefully utilized for the synthesis of various types of organometallic and coordinated chromium compounds, including ethylene oligomerized chromium catalyst.
  • CrCl 3 ⁇ 3 THF can be used to solve various problems encountered when attempting synthesis.
  • Another object of the present invention is to provide a chromium compound capable of preparing a catalyst precursor for ethylene oligomerization with high purity and increasing the catalytic activity of ethylene oligomerization.
  • Another object of the present invention is to provide a method for producing a chromium compound having excellent processability and economy.
  • One aspect of the present invention is a chromium compound.
  • the chromium compound is represented by the following formula (1):
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 are each independently halogen
  • R 1 , R 2 , R 3 , R 4 are each independently one or more oxygen-containing heteroalicyclic rings, wherein the oxygen is directly linked to chromium (Cr)).
  • the chromium compound represented by Formula 1 may be a compound represented by Formula 1-1 below.
  • Another aspect of the present invention is a method for preparing a chromium compound of formula (1).
  • the method for preparing the chromium compound of Formula 1 is prepared by heat-treating CrX 1 X 2 X 3 .6 (H 2 O) (in this case, X 1 , X 2 , and X 3 are each independently halogen) under vacuum under reduced pressure. Step 1 to obtain a product (first step),
  • Y 1 , Y 2 , Y 3 are each independently monovalent to a filtrate obtained by adding a solvent having at least one oxygen-containing heteroalicyclic ring to the first product and filtering it) an organic group, and X is a halogen) and reacting to obtain a second product (second step);
  • the CrX 1 X 2 X 3 ⁇ 6 (H 2 O) is CrCl 3 ⁇ 6 (H 2 O)
  • the solvent having at least one oxygen-containing heteroalicyclic ring is tetrahydrofuran
  • the Y 1 Y 2 Y 3 SiX may be (CH 3 ) 3 SiCl.
  • H 2 O in the first step At least one of CrX 1 X 2 X 3 ⁇ 6 (H 2 O) 30% by weight to 40% by weight may be removed.
  • the Y 1 Y 2 Y 3 SiX in the second step is a molar ratio of 1:4 to 1:7 compared to CrX 1 X 2 X 3 .6 (H 2 O) in the first step ( CrX 1 X 2 X 3 ⁇ 6 (H 2 O): Y 1 Y 2 Y 3 SiX) may be added.
  • CH 2 Cl 2 may be used as a solvent for recrystallization in the third step.
  • the present invention provides a chromium compound that can be prepared with high purity by a simple manufacturing method.
  • the present invention provides a chromium compound capable of preparing a catalyst precursor for ethylene oligomerization with high purity and increasing the catalytic activity of ethylene oligomerization.
  • the present invention provides a method for producing a chromium compound having excellent processability and economy.
  • Example 1 is an X-ray crystallography analysis result of the chromium compound ([CrCl 2 (THF) 2 ( ⁇ 2 -Cl)] 2 ) prepared in Example 1.
  • FIG. 1 is an X-ray crystallography analysis result of the chromium compound ([CrCl 2 (THF) 2 ( ⁇ 2 -Cl)] 2 ) prepared in Example 1.
  • FIG. 1 is an X-ray crystallography analysis result of the chromium compound ([CrCl 2 (THF) 2 ( ⁇ 2 -Cl)] 2 ) prepared in Example 1.
  • FIG. 2 is an X-ray crystal analyzer analysis result of [CrCl 2 (NCCH 3 ) 4 ] + [B(C 6 F 5 ) 4 ] - prepared from the chromium compound of Example 1.
  • FIG. 2 is an X-ray crystal analyzer analysis result of [CrCl 2 (NCCH 3 ) 4 ] + [B(C 6 F 5 ) 4 ] - prepared from the chromium compound of Example 1.
  • the present invention provides a chromium compound that can be prepared with high purity by a simple manufacturing method, can prepare a catalyst precursor for ethylene oligomerization with high purity, and can increase the catalytic activity of ethylene oligomerization through this.
  • the chromium compound of an embodiment of the present invention is a chromium coordination compound having a chromium trivalent cation, and is represented by the following formula (1):
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 are each independently halogen
  • R 1 , R 2 , R 3 , R 4 are each independently one or more oxygen-containing heteroalicyclic rings, wherein the oxygen is directly linked to chromium (Cr)).
  • the 'halogen' may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • the halogen may be chlorine.
  • the 'at least one oxygen-containing heteroalicyclic ring' may be a functional group containing at least one oxygen among elements constituting the heteroalicyclic ring.
  • the at least one oxygen-containing heteroalicyclic ring is a heteroalicyclic ring having 2 to 10 carbon atoms, in which case carbon and oxygen are connected in the heteroalicyclic ring, and specifically, it may be tetrahydrofurfuryl.
  • the 'directly connected' means that no other element is bonded between oxygen and chromium.
  • the chromium compound of Formula 1 is a chromium trivalent compound CrX 3 (X is halogen) formed by two units having a structure in which two oxygen-containing heteroalicyclic rings are coordinated sharing a halogen ligand including halogen X 3 and X 4 with each other. It is a compound in the dinuclear form.
  • a chromium divalent compound that is, a compound in which two THF (tetrahydrofuran) molecules are coordinated to CrCl 2 (ie, CrCl 2 (THF) 2 ) is commonly used. However, it is extremely rare to use one in which two THF molecules are coordinated to the chromium trivalent compound CrCl 3 (ie, CrCl 3 (THF) 2 ).
  • the present invention provides a compound of Formula 1 having a single (discrete) structure and purified through recrystallization having a single composition in the form of a dinuclear of high purity.
  • CrCl 3 containing three THF molecules ie, CrCl 3 ⁇ 3 (THF)
  • THF THF
  • CrCl 3 ⁇ 3 (THF) does not have an example in which high-purity purification through recrystallization is implemented, and the manufacturing method is also difficult.
  • the compound of Formula 1 can be prepared with high purity by the preparation method described in detail below, and thus has high processability and economical efficiency.
  • the compound of Formula 1 can prepare a catalyst precursor for ethylene oligomerization described in detail below with high purity, thereby increasing ethylene oligomerization catalyst activity.
  • the compound of Formula 1 may be used to prepare a catalyst precursor for oligomerization to provide a method for preparing ethylene oligomers having high catalytic activity for ethylene oligomerization.
  • the compound of Formula 1 may be the compound of Formula 1-1 ([CrCl 2 (THF) 2 ( ⁇ 2 -Cl)] 2 ):
  • Y 1 Y 2 Y 3 SiX (in this case, Y 1 , Y 2 , Y 3 are each independently monovalent to a filtrate obtained by adding a solvent having at least one oxygen-containing heteroalicyclic ring to the first product and filtering it) an organic group and X is a halogen) is added and reacted to obtain a second product (second step),
  • the first step is to obtain a first product by heat-treating CrX 1 X 2 X 3 ⁇ 6 (H 2 O) under vacuum under reduced pressure.
  • the first step is to remove HX 1 (or HX 2 or HX 3 ) together with some H 2 O contained in CrX 1 X 2 X 3 ⁇ 6 (H 2 O) through heat treatment under vacuum reduced pressure.
  • HX 1 or HX 2 or HX 3 ) as well as H 2 O from CrX 1 X 2 X 3 ⁇ 6 (H 2 O) were also removed.
  • the first step it is possible to easily perform the second step and the third step reaction carried out later, and it is possible to prepare the chromium compound of Formula 1 with high purity.
  • the first step may make it possible to prepare the chromium compound of Formula 1 with high purity from the crystalline form of CrX 1 X 2 X 3 .6 (H 2 O).
  • the heat treatment under vacuum reduced pressure may be performed at a temperature containing CrX 1 X 2 X 3 ⁇ 6 (H 2 O) from 40°C to 100°C.
  • the heat treatment under vacuum reduced pressure is a primary heat treatment performed at 40°C to 50°C; Secondary heat treatment raising the temperature from 40°C to 50°C to 100°C; And it may be carried out by step-by-step heat treatment including a tertiary heat treatment performed at 100 °C.
  • the desired effect of the first step of the present invention may be well performed.
  • the primary heat treatment may be performed for 1 hour to 2 hours. Secondary heat treatment may be performed for 30 minutes to 2 hours. The tertiary heat treatment may be performed for 3 to 5 hours. In the above time range, the desired effect of the first step of the present invention may be well performed.
  • the first product prepared through the first step may be reduced by 30% to 40% by weight compared to CrX 1 X 2 X 3 .6 (H 2 O), which is the first reactant used in weight conversion. That is, not only H 2 O removed through the first step, but also HX 1 (or HX 2 or HX 3 ) may be 30% to 40% by weight of CrX 1 X 2 X 3 .6 (H 2 O). .
  • HX 1 or HX 2 or HX 3
  • H 2 O the desired effect of the first step can be obtained, and there is no additional heat treatment, so that economic efficiency and fairness can be improved.
  • CrX 1 X 2 X 3 ⁇ 6 (H 2 O) may be CrCl 3 ⁇ 6 (H 2 O). If CrX 1 X 2 X 3 ⁇ 6(H 2 O) is CrCl 3 ⁇ 6(H 2 O), the first product prepared from the first step is to be deduced as CrCl 2 (OH)(H 2 O) 2 and the removed components may be H 2 O and HCl.
  • a solvent containing one or more heteroalicyclic rings is added to CrX 1 X 2 X 3 .6 (H 2 O) in a method similar to the second step detailed below, and Y 1 Y 2 Y 3 SiX (In this case, Y 1 , Y 2 , and Y 3 are each independently a monovalent organic group, and X is a halogen) is known.
  • Y 1 , Y 2 , and Y 3 SiX is known.
  • the following Reaction Scheme 2 may be used. .
  • Y 1 Y 2 Y 3 SiX (in this case, Y 1 , Y 2 , Y 3 is each independently a monovalent organic group, X is a halogen) is added and reacted to obtain a second product.
  • the monovalent organic group may be an alkyl group having 1 to 30 carbon atoms.
  • the second step is the OH ligand contained in the first product in the removal of H 2 O that remains without being removed from after the first step of CrX 1 X 2 X 3 ⁇ 6 (H 2 O) and the first stage halogen
  • This is a step of reacting Y 1 Y 2 Y 3 SiX to convert to a ligand.
  • H 2 O remaining in the first product is removed by adding and reacting a solvent containing at least one heteroalicyclic ring to the first product of the first step.
  • This reaction is an exothermic reaction, and it is preferable to add a solvent containing a heteroalicyclic ring at a low temperature, for example, -30°C to 0°C, followed by addition of Y 1 Y 2 Y 3 SiX.
  • the solvent containing one or more heteroalicyclic rings may be tetrahydrofuran.
  • Filtration is to remove a small amount of insoluble by-products and the like produced in the first step. Filtration may be carried out in a conventional manner.
  • Y 1 Y 2 Y 3 SiX is taken for the first step 1 CrX 1 X 2 X 3 ⁇ 6 (H 2 O) over the molar ratio (CrX 1 X 2 X 3 ⁇ 6 (H 2 O): Y 1 Y 2 Y 3 SiX) in a molar ratio of 1:4 to 1:7, preferably 1:5 to 1:6.
  • the compound of Formula 1 to be obtained by the present invention can be prepared with high purity.
  • the reaction after adding Y 1 Y 2 Y 3 SiX to the filtrate may be performed at room temperature, for example, 20° C. to 30° C.
  • Y 1 Y 2 Y 3 SiX may be (CH 3 ) 3 SiCl.
  • the second product may be a compound of Formula 1-1.
  • the third step is a step of obtaining the compound of Formula 1 with high purity by recrystallizing the reaction solution containing the second product prepared in the second step.
  • the compound of Formula 1 may be recrystallized by methods commonly known to those skilled in the art.
  • the recrystallization solvent is not particularly limited, but CH 2 Cl 2 may be used as a solvent for dissolving the compound of formula (1).
  • Crystalline CrCl 3 .6(H 2 O) (10.0 g, 37.5 mmol) was placed in a flask and stirred at 40° C. for 1 hour using a vacuum pump of the shrink line to form crystalline CrCl 3 .6 (H 2 O)
  • the volatile components in the inside were removed.
  • the temperature in the flask was slowly increased to 100° C. over 1 hour, and the volatile components were removed through a vacuum line while maintaining 100° C. for 4 hours.
  • the crystalline form of CrCl 3 ⁇ 6 (H 2 O) was transformed into a powder form.
  • the color of CrCl 3 ⁇ 6 (H 2 O) in the crystalline form changed from dark green to light green to light purple through light gray.
  • the removed volatile components were acidic water containing water and HCl.
  • the volatile component was confirmed by measuring the mass (6.39 g) of the remaining chromium compound that was removed to 36% by weight relative to the mass of CrCl 3 ⁇ 6 (H 2 O) put into the flask. It was confirmed that the maximum value of volatile components that can be removed converges to the level of 36 wt% through the insignificant mass change even after treatment at 100 °C for a longer period of time. Through this, it was deduced that the chromium compound remaining after removal of the volatile component was CrCl 2 (OH)(H 2 O) 2 .
  • THF (36 mL) cooled at -30°C was added to the pale purple fine powder obtained in the first step. As heat was generated, the chromium compound was dissolved in THF to form a dark-purple solution. Some insoluble by-products were removed by filtration using Celite.
  • the resulting solid powder was obtained by filtration, and the obtained solid powder was successively washed with THF (10 mL) and hexane (10 ml) to obtain a non-reactant (CH 3 ) 3 SiCl and a by-product (CH 3 ) 3 SiOSi(CH 3 ) 3 and HCl were completely washed away. Residual solvent was completely removed using vacuum tubing to give a light purple solid powder (6.60 g).
  • the powder obtained in the second step was recrystallized using CH 2 Cl 2 to obtain a chromium compound.
  • the powder (4.12 g) obtained in the second step was dissolved in CH 2 Cl 2 (15.5 mL), put in a vial, and put into a larger container containing methylcyclohexane.
  • CH 2 Cl 2 in the vial evaporates slowly and dissolves into the methylcyclohexane layer in the larger container.
  • the chromium compound was removed, the chromium compound was precipitated as dark purple crystals, which were washed to obtain a chromium compound (2.28 g, yield: 55%).
  • FIG. 1 A single crystal of the chromium compound was taken and the structure of the chromium compound was analyzed through an X-ray crystal analyzer. The results are shown in FIG. 1 .
  • the compound of Formula 1-1 [CrCl 2 (THF) 2 ( ⁇ 2 -Cl)] 2 ) was prepared.
  • the compound of Formula 1-1 has a crystalline single structure with high purity.
  • Example 1 The compound prepared in Example 1 was evaluated as follows.
  • Example 1 the recrystallisation method similar to that obtained above in [CrCl 2 (NCCH 3) 4 ] + [B (C 6 F 5) 4] described in the step 3 in-crystalline when recrystallized by treating the compound The compound precipitated.
  • the obtained crystalline compound was analyzed for the structure of the chromium compound through an X-ray crystal analyzer. The results are shown in FIG. 2 .

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Abstract

L'invention concerne un composé de chrome représenté par la formule chimique 1, et son procédé de production.
PCT/KR2021/002240 2020-04-29 2021-02-23 Composé de chrome et son procédé de production WO2021221283A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100882891B1 (ko) * 2005-05-27 2009-02-10 롬 앤드 하아스 컴패니 촉매 조성물, 그의 제조 방법 및 에틸렌계 불포화단량체로부터 중합체를 제조하기 위한 그의 용도
WO2011108772A1 (fr) * 2010-03-03 2011-09-09 에스케이이노베이션 주식회사 Catalyseur d'oligomérisation d'éthylène hautement actif et hautement sélectif, et procédé de préparation d'hexène ou d'octène utilisant ce catalyseur

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3268129A2 (fr) * 2015-03-13 2018-01-17 Dow Global Technologies LLC Procédé d'oligomérisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100882891B1 (ko) * 2005-05-27 2009-02-10 롬 앤드 하아스 컴패니 촉매 조성물, 그의 제조 방법 및 에틸렌계 불포화단량체로부터 중합체를 제조하기 위한 그의 용도
WO2011108772A1 (fr) * 2010-03-03 2011-09-09 에스케이이노베이션 주식회사 Catalyseur d'oligomérisation d'éthylène hautement actif et hautement sélectif, et procédé de préparation d'hexène ou d'octène utilisant ce catalyseur

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LEE DONG GEUN, BAEK JUN WON, LEE JUNG HYUN, LEE HYUN JU, SEO YEONG HYUN, LEE JUNSEONG, LEE CHONG GU, LEE BUN YEOUL: "Replacement of the Common Chromium Source CrCl3(thf)3 with Well-Defined [CrCl2(μ-Cl)(thf)2]2", MOLECULES, vol. 26, no. 4, 22 February 2021 (2021-02-22), XP055867104, DOI: 10.3390/molecules26041167 *
SOBOTA PIOTR, JOLANTA EJFLER, SLAWOMIR SZAFERT, KRZYSZTOF SZCZEGOT, WANDA SAWKA-DOBROWOLSKA: "New Intermediates for the Synthesis of Olefin Polymerization Catalysts: the Complexes [M&CI),Cl,(thf thf = tetrahydrofuran); Crystal Structures and Properties t", JOURNAL OF THE CHEMICAL SOCIETY. DALTON TRANSACTIONS, vol. 15, 31 December 1993 (1993-12-31), pages 2353 - 2357, XP055867109, DOI: 10.1039/DT9930002353 *
WANG JUAN-JUAN, AN DONG-LI, ZHU HONG-PING: " [(NHC)CrCl(µ-Cl)(THF)] 2 and (NHC) 2 CrCl 2 (NHC = 1,3- Diisopropyl-4,5-dimethylimidazole-2-ylidene): Syntheses, Structures, and Polymerization Activities", CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, vol. 29, no. 6, 30 June 2010 (2010-06-30), pages 933 - 939, XP055867116 *
WERNER DANIEL, ANWANDER REINER: "Unveiling the Takai Olefination Reagent via Tris( tert -butoxy)siloxy Variants", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 140, no. 43, 31 October 2018 (2018-10-31), pages 14334 - 14341, XP055867107, ISSN: 0002-7863, DOI: 10.1021/jacs.8b08739 *

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