CN116813662A - Synthesis process of titanium trichloride tetrahydrofuran compound (1:3) - Google Patents
Synthesis process of titanium trichloride tetrahydrofuran compound (1:3) Download PDFInfo
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- CN116813662A CN116813662A CN202310511047.3A CN202310511047A CN116813662A CN 116813662 A CN116813662 A CN 116813662A CN 202310511047 A CN202310511047 A CN 202310511047A CN 116813662 A CN116813662 A CN 116813662A
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- tetrahydrofuran
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- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 titanium trichloride tetrahydrofuran compound Chemical class 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 title abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 74
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- CZOJMXXOMUJZPH-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Ti+3].C1CCOC1 Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].C1CCOC1 CZOJMXXOMUJZPH-UHFFFAOYSA-K 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 11
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- SNMUMYFMLRZUFC-UHFFFAOYSA-N [AlH3].O1CCCC1 Chemical compound [AlH3].O1CCCC1 SNMUMYFMLRZUFC-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SXEBSPSTEUQPJM-UHFFFAOYSA-N oxolane;titanium Chemical compound [Ti].C1CCOC1 SXEBSPSTEUQPJM-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- QBBWRNBMWSVXBB-UHFFFAOYSA-K aluminum;oxolane;trichloride Chemical compound Cl[Al](Cl)Cl.C1CCOC1 QBBWRNBMWSVXBB-UHFFFAOYSA-K 0.000 description 1
- KSKPGAGLAZXNEO-UHFFFAOYSA-H aluminum;titanium(3+);hexachloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ti+3] KSKPGAGLAZXNEO-UHFFFAOYSA-H 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- QCAJADRKKXQEGQ-UHFFFAOYSA-J oxolane;titanium(4+);tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].C1CCOC1 QCAJADRKKXQEGQ-UHFFFAOYSA-J 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3), and particularly relates to the technical field of organic synthesis. Under the protection of argon, dry tetrahydrofuran is firstly added into a reaction container, the temperature is controlled, titanium tetrachloride is dropwise added, and after the dropwise addition is finished, the mixture is stirred at room temperature; after stirring, controlling the temperature, slowly adding zinc powder, and carrying out reflux reaction after the addition is finished; after the reaction is finished, cooling to room temperature, filtering under the protection of argon, and washing with dry tetrahydrofuran to obtain a solid vacuum-dried titanium trichloride tetrahydrofuran compound (1:3). The synthesis process is simple, and the titanium trichloride tetrahydrofuran compound (1:3) is obtained by using expensive and dangerous raw materials, namely tetrahydrofuran and titanium tetrachloride with relatively lower price and danger coefficient under the action of zinc; meanwhile, the synthesis process of the invention is simpler and is more beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3).
Background
Titanium trichloride tetrahydrofuran complex (1:3), namely titanium tetrahydrofuran chloride, is mainly used as olefin polymerization catalyst, and is widely used in petrochemical polyolefin catalysis, and the current synthesis scheme of the titanium trichloride tetrahydrofuran complex (1:3) mainly comprises the following steps:
1. titanium trichloride is directly reacted with tetrahydrofuran to generate a titanium trichloride tetrahydrofuran compound (1:3), and the method is simple and direct, but titanium trichloride and expensive and unstable titanium trichloride are not produced by manufacturers.
2. Collection of Czechoslovak Chemical Communications,2006,71,164-178, titanium tetrachloride and butyllithium are adopted to generate titanium trichloride tetrahydrofuran compound (1:3) and lithium chloride byproducts, and the lithium chloride residues in the product are removed by repeated flushing of tetrahydrofuran, but the method has the disadvantages of large solvent consumption and excessively dangerous butyllithium.
3. Chinese patent CN104226366a, using a mixture of titanium trichloride and aluminum trichloride in tetrahydrofuran to produce a titanium tetrahydrofuran complex (1:3) and an aluminum tetrahydrofuran complex, wherein the aluminum tetrahydrofuran complex is soluble in tetrahydrofuran and the titanium tetrahydrofuran complex (1:3) is insoluble in tetrahydrofuran. The aluminum trichloride tetrahydrofuran complex can be removed by means of tetrahydrofuran washing. The method is simple, but the titanium trichloride aluminum trichloride mixture is dangerous and expensive, has no suppliers in China, and is not suitable for industrial production.
4. In U.S. Pat. No. 3,182, titanium tetrachloride and titanium microparticles (100-200 mesh) are refluxed in a mixed solution of tetrahydrofuran and toluene at 100℃for 8 hours, the titanium trichloride tetrahydrofuran complex (1:3) is insoluble in tetrahydrofuran, and impurities such as titanium tetrachloride complex are removed by washing with tetrahydrofuran to obtain the titanium trichloride tetrahydrofuran complex (1:3). The method has the advantages of high price of the particulate titanium, long reaction time and high energy consumption of high-temperature reflux, and is not suitable for industrial production.
5. In U.S. Pat. No. 3,182, titanium trichloride and tetrahydrofuran are reacted for 24 hours by first forming a complex with titanium tetrachloride and tetrahydrofuran, then reducing the mixture by adding magnesium powder or aluminum powder at 50-80 ℃, the titanium trichloride and tetrahydrofuran complex (1:3) is insoluble in tetrahydrofuran, and the magnesium or aluminum complex is removed by washing with tetrahydrofuran, so that the titanium trichloride and tetrahydrofuran complex (1:3) is insoluble in tetrahydrofuran. The metal powder used in the method needs 10-200 microns, is not easy to obtain and cannot be industrially produced.
Therefore, it is urgent to find a process for synthesizing titanium trichloride tetrahydrofuran complex (1:3).
Disclosure of Invention
Therefore, the invention provides a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3) to solve the problems that the existing synthesis raw materials are expensive, the raw materials are dangerous, industrial mass production cannot be realized, and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
according to one aspect of the invention, the synthesis process of the titanium trichloride tetrahydrofuran compound (1:3) comprises the following steps:
step one, under the protection of argon, adding dry tetrahydrofuran into a reaction container, controlling the temperature, dropwise adding titanium tetrachloride, and stirring at room temperature after the dropwise adding is finished;
controlling the temperature after stirring, slowly adding zinc powder, and carrying out reflux reaction after the addition is finished;
and thirdly, cooling to room temperature after the reaction is finished, filtering under the protection of argon, and washing with dry tetrahydrofuran to obtain a solid vacuum dried titanium trichloride tetrahydrofuran compound (1:3).
Further, in the first step, the temperature is controlled to be in the range of 0-20 ℃.
Further, in the first step, the stirring time at room temperature is 4 hours.
Further, in the second step, the temperature is controlled to be 15-40 ℃.
Further, in the second step, the reflux reaction time is 8-24 hours; the reflux temperature is about 60-70 ℃ before and after the boiling point of tetrahydrofuran, and is generally about 66 ℃.
Further, in the third step, the washing times are 3-5 times.
According to another aspect of the invention, a titanium trichloride tetrahydrofuran compound (1:3) is provided, wherein the compound is prepared by the process.
The invention has the following advantages:
the synthesis process is simple, and the titanium trichloride tetrahydrofuran compound (1:3) is obtained by using expensive and dangerous raw materials, namely tetrahydrofuran and titanium tetrachloride with relatively lower price and danger coefficient under the action of zinc; meanwhile, the synthesis process of the invention is simpler and is more beneficial to industrial production.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the invention, 1-10L of excessive dry tetrahydrofuran is added into a four-mouth reaction bottle under the protection of argon, the temperature is controlled to be 0-20 ℃, titanium tetrachloride (1 eq.) is added dropwise, and after the dropwise addition is finished, the mixture is stirred for 4 hours at room temperature;
then controlling the temperature to be 15-40 ℃, slowly adding zinc powder (0.1-0.5 eq.) into the mixture, and after the addition is finished, carrying out reflux reaction for 8-24 hours at about 66 ℃, and cooling the mixture to room temperature;
filtering under the protection of argon, and washing with dry tetrahydrofuran for 3-5 times to obtain solid vacuum dried titanium trichloride tetrahydrofuran compound (1:3) with yield over 85%.
Example 1
The embodiment provides a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3):
in a 5L four-port reaction bottle, 3L of dry tetrahydrofuran is added under the protection of argon, the temperature is controlled to be 0-5 ℃,200 g of titanium tetrachloride (1 eq.) is added dropwise, the dropwise addition is finished, the stirring is carried out for 2 hours at room temperature, the temperature is controlled to be 15-20 ℃, 17.235g (0.25 eq.) of zinc powder is slowly added, after the addition is finished, the reflux is carried out for 12 hours at about 66 ℃, the temperature is restored to the room temperature, the argon is used for protection and filtration, 200-300mL of dry tetrahydrofuran is used for washing 3 times, 355.5g (yield 91%) of titanium trichloride tetrahydrofuran compound (1:3) is obtained through solid vacuum drying, the element content is analyzed through ICP-MS and element analysis, and test data are: ti (12.8%), cl (28.6%), C (38.8%), zn (0.02%), zinc content was low.
Example 2
The embodiment provides a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3):
3L of dry tetrahydrofuran is added under the protection of argon, the temperature is controlled to be 0-5 ℃,200 g of titanium tetrachloride (1 eq.) is added dropwise, the dropwise addition is finished, the stirring is carried out for 2 hours at room temperature, the temperature is controlled to be 15-20 ℃, 24.129g (0.35 eq.) of zinc powder is slowly added, after the addition is finished, the reflux is carried out for 12 hours at about 66 ℃, the temperature is restored to the room temperature, the argon is used for protection and filtration, 200-300ml of dry tetrahydrofuran is used for washing for 3 times, 371.2g (yield 95%) of titanium trichloride tetrahydrofuran compound (1:3) is obtained through solid vacuum drying, the element content is analyzed through ICP-MS and element analysis, and the test data are: ti (12.8%), cl (28.5%), C (38.7%), zn (0.3%) and zinc content were high.
Example 3
The embodiment provides a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3):
3L of dry tetrahydrofuran is added under the protection of argon, the temperature is controlled to be 0-5 ℃,200 g of titanium tetrachloride (1 eq.) is added dropwise, the dropwise addition is finished, the stirring is carried out for 2 hours at room temperature, the temperature is controlled to be 15-20 ℃, 10.341g (0.15 eq.) of zinc powder is slowly added, after the addition is finished, the reflux is carried out for 12 hours at about 66 ℃, the temperature is restored to the room temperature, the argon is used for protection and filtration, 200-300ml of dry tetrahydrofuran is used for washing 3 times, 332.1g (yield 85%) of titanium trichloride tetrahydrofuran compound (1:3) is obtained through solid vacuum drying, the element content is analyzed through ICP-MS and element analysis, and the test data are: ti (12.5%), cl (28.3%), C (38.2%), zn (0.02%), zinc content was low.
Comparative example 1
The embodiment provides a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3):
in a 5L four-port reaction bottle, 3L of dry tetrahydrofuran is added under the protection of argon, the temperature is controlled to be 0-5 ℃,200 g of titanium tetrachloride (1 eq.) is added dropwise, the dropwise addition is finished, the stirring is carried out for 2 hours at room temperature, the temperature is controlled to be 15-20 ℃, 17.235g (0.25 eq.) of zinc powder is slowly added, the reaction is carried out for 12 hours at 35-40 ℃ after the addition is finished, the reaction is restored to room temperature, the filtration is carried out under the protection of argon, 200-300mL of dry tetrahydrofuran is washed for 3 times, 159.7g (yield 41%) of titanium trichloride tetrahydrofuran compound (1:3) is obtained by solid vacuum drying, the element content is analyzed by ICP-MS and element analysis, and the test data are: ti (12.5%), cl (28.4%), C (38.7%), zn (0.8%), zinc content was high.
In comparison with example 1, the reaction temperature after the addition was lowered and the yield was lowered.
Comparative example 2
The embodiment provides a synthesis process of a titanium trichloride tetrahydrofuran compound (1:3):
in a 5L four-port reaction bottle, 3L of dry tetrahydrofuran is added under the protection of argon, the temperature is controlled to be 0-5 ℃,200 g of titanium tetrachloride (1 eq.) is added dropwise, the dropwise addition is finished, the mixture is stirred for 2 hours at room temperature, then 17.235g (0.25 eq.) of zinc powder is slowly added at 15-20 ℃, after the addition is finished, the mixture is reacted for 12 hours at 45-50 ℃, the mixture is restored to room temperature, the mixture is filtered under the protection of argon, 200-300mL of dry tetrahydrofuran is washed for 3 times, 307.7g (yield 79%) of titanium trichloride tetrahydrofuran compound (1:3) is obtained through solid vacuum drying, the content of elements is analyzed through ICP-MS and element analysis, and test data are: ti (12.7%), cl (28.4%), C (38.5%), zn (0.07%) and zinc content were low.
In comparison with example 1, the reaction temperature after the addition was lowered and the yield was lowered.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (7)
1. A process for synthesizing a titanium trichloride tetrahydrofuran complex (1:3), comprising:
step one, under the protection of argon, adding dry tetrahydrofuran into a reaction container, controlling the temperature, dropwise adding titanium tetrachloride, and stirring at room temperature after the dropwise adding is finished;
controlling the temperature after stirring, slowly adding zinc powder, and carrying out reflux reaction after the addition is finished;
and thirdly, cooling to room temperature after the reaction is finished, filtering under the protection of argon, and washing with dry tetrahydrofuran to obtain a solid vacuum dried titanium trichloride tetrahydrofuran compound (1:3).
2. The process for synthesizing a titanium trichloride tetrahydrofuran complex (1:3) as claimed in claim 1, wherein in said step one, the temperature is controlled to be in the range of 0 to 20 ℃.
3. The process for synthesizing a titanium trichloride tetrahydrofuran complex (1:3) as defined in claim 1, wherein in said step one, the stirring time at room temperature is 4 hours.
4. The process for synthesizing a titanium trichloride tetrahydrofuran complex (1:3) as claimed in claim 1, wherein in said step two, the temperature is controlled to be 15-40 ℃.
5. The process for synthesizing a titanium trichloride tetrahydrofuran complex (1:3) as claimed in claim 1, wherein in said step two, the reflux reaction time is 8-24 hours.
6. The process for synthesizing a titanium trichloride tetrahydrofuran complex (1:3) as claimed in claim 1, wherein in said step three, the number of washing is 3 to 5.
7. Titanium trichloride tetrahydrofuran complex (1:3), characterized in that said complex is prepared by the process according to any one of claims 1 to 6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1152192A (en) * | 1965-07-23 | 1969-05-14 | Sir Soc Italiana Resine Spa | Method of Preparing Catalytically Active TiCI3 |
| EP0661301A1 (en) * | 1993-12-17 | 1995-07-05 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing ethylene polymers having reduced hexane extractable content |
| US6093833A (en) * | 1999-01-14 | 2000-07-25 | Akzo Nobel N.V. | Process for producing trivalent titanium coordination complex |
| CN102030779A (en) * | 2010-11-17 | 2011-04-27 | 云南瑞亘生物科技有限公司 | Preparation method of chemiluminescence material AMPPD (4-methoxy-4-(3-phenylphosphonic)spiro[1,2-dioxetane-3,2'-adamantane]disodium salt) for immunoassay |
| CN114591455A (en) * | 2020-12-03 | 2022-06-07 | 中国石油天然气股份有限公司 | Catalyst, preparation method thereof and olefin polymerization catalyst system |
-
2023
- 2023-05-09 CN CN202310511047.3A patent/CN116813662A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1152192A (en) * | 1965-07-23 | 1969-05-14 | Sir Soc Italiana Resine Spa | Method of Preparing Catalytically Active TiCI3 |
| EP0661301A1 (en) * | 1993-12-17 | 1995-07-05 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing ethylene polymers having reduced hexane extractable content |
| US6093833A (en) * | 1999-01-14 | 2000-07-25 | Akzo Nobel N.V. | Process for producing trivalent titanium coordination complex |
| CN102030779A (en) * | 2010-11-17 | 2011-04-27 | 云南瑞亘生物科技有限公司 | Preparation method of chemiluminescence material AMPPD (4-methoxy-4-(3-phenylphosphonic)spiro[1,2-dioxetane-3,2'-adamantane]disodium salt) for immunoassay |
| CN114591455A (en) * | 2020-12-03 | 2022-06-07 | 中国石油天然气股份有限公司 | Catalyst, preparation method thereof and olefin polymerization catalyst system |
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