CN113527561B - Molybdenum-based catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity and application method thereof - Google Patents
Molybdenum-based catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity and application method thereof Download PDFInfo
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- CN113527561B CN113527561B CN202110993721.7A CN202110993721A CN113527561B CN 113527561 B CN113527561 B CN 113527561B CN 202110993721 A CN202110993721 A CN 202110993721A CN 113527561 B CN113527561 B CN 113527561B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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Abstract
The invention relates to a molybdenum catalyst, in particular to a molybdenum catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity and an application method thereof.The catalyst consists of a bridged binuclear molybdenum compound and aryloxy dialkyl aluminum, wherein the mass ratio of the bridged binuclear molybdenum compound to the aryloxy dialkyl aluminum is 1: 4-1: 30; the molecular formula of the bridged binuclear molybdenum compound is [ Cl ]2(OR)2Mo(μ‑OR)2Mo(OR)2Cl2]Wherein R is methyl or ethyl; the molecular formula of the aryloxy dialkyl aluminum is AlR'2OAr, wherein R' is ethyl or isobutyl and Ar is aryl. The catalyst is used for catalyzing butadiene polymerization in heptane, hexane, solvent oil, hydrogenated gasoline or toluene to prepare high vinyl polybutadiene, the content of 1, 2-structural units of the product can reach more than 80%, and the activity can reach 600kg PB/mol Mo.
Description
Technical Field
The invention relates to a molybdenum catalyst, in particular to a molybdenum catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity and an application method thereof.
Background
Molybdenum pentachloride can react with alcohol to prepare polybutadiene catalyst containing alkoxy molybdenum. The currently disclosed alkoxy-containing molybdenum-based polybutadiene main catalyst has the molecular formula of Mo (OR) Cl4(Nishoudu, Tang Dynasty, a novel polybutadiene [ J ]]Journal of chemical industry, 1983,34(1):84-89.) or Mo (OR)2Cl3Etc. (Yangyiwei, Tang Ming. study of preparation of 1, 2-polybutadiene Using molybdenum-based Ziegler-Natta initiator [ J)]Polymers reported, 1990,000(004): 198. ang. 204.) these catalysts usually require substitution with long carbon chain alcohols such as octanol and molybdenum pentachloride, otherwise the activity is low ([1 ])]General description of 1, 2-polybutadiene Synthesis with molybdenum-based catalyst from Von oriole, Yangyiwei and Tang Ming]The university of Qingdao science and technology, Nature science edition, 1989(2): 111-.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a molybdenum catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity, which has low production cost, high atom economy and little pollution; the invention also provides an application method of the composition.
The molybdenum-based catalyst for catalyzing butadiene high-1, 2-selectivity polymerization comprises a bridged binuclear molybdenum compound and aryloxy dialkyl aluminum, wherein the mass ratio of the bridged binuclear molybdenum compound to the aryloxy dialkyl aluminum is 1: 4-1: 30;
the structural formula of the bridged binuclear molybdenum compound is as follows:
wherein R is a small sterically hindered alkylmethyl group (CH)3) Or ethyl (CH)2CH3)。R＝CH3When the bridged binuclear molybdenum compound is named as a complex 1, R is CH2CH3When so, the bridged binuclear molybdenum compound is named as a complex 2.
The molecular formula of the bridged binuclear molybdenum compound is [ Cl2(OR)2Mo(μ-OR)2Mo(OR)2Cl2]。
The structural formula of the aryloxy dialkyl aluminum is as follows:
wherein R' is ethyl (Et) or isobutyl (i-Bu), Ar is aryl; the aryl group includes but is not limited to phenyl, 1-naphthyl, 2-naphthyl, o-methylphenyl, m-methylphenyl, p-methylphenyl; preferably, the aryl group is m-methylphenyl.
The molecular formula of the aryloxy dialkyl aluminum is AlR'2OAr。
Preferably, the amount ratio of the bridged binuclear molybdenum compound to the aryloxydialkyl aluminum substance is 1:5 to 1: 15.
The reaction equation for preparing the bridged binuclear molybdenum compound is as follows:
MoCl5+ROH→[Cl2(OR)2Mo(μ-OR)2Mo(OR)2Cl2]+HCl。
the preparation method of the bridged binuclear molybdenum compound comprises the following steps:
under the anhydrous and oxygen-free atmosphere, adding molybdenum pentachloride into ROH under low-temperature stirring, heating and stirring for reaction, removing most of liquid, and freezing and crystallizing to obtain the bridged binuclear molybdenum compound.
The low-temperature stirring temperature is-85 to-65 ℃.
The temperature of the heating stirring reaction is-20 to 0 ℃, and the reaction time is 1 to 2 hours.
Preferably, the preparation method of the bridged binuclear molybdenum compound comprises the following specific steps:
under the anhydrous and oxygen-free atmosphere, a certain amount of molybdenum pentachloride (slowly added into ROH under the condition of stirring at-78 ℃, then slowly increased to-10 ℃, continuously stirred for 1 hour, and continuously discharged generated hydrogen chloride gas), then most of liquid is dried in a spinning mode at the temperature of below 50 ℃, the residual concentrated solution is frozen for more than 24 hours at the temperature of-18 ℃, and dark crystals are separated out at low temperature, wherein the crystals are target products.
The application method of the molybdenum-based catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity comprises the following steps:
under the anhydrous and oxygen-free conditions, adding the molybdenum catalyst for catalyzing butadiene to polymerize in a high 1, 2-selectivity mode, stirring for 1-480 minutes at 20-80 ℃, adding ethanol to terminate the reaction, and drying to obtain the rubber-like high vinyl polybutadiene.
The volume portion of the butadiene in the polymerization solution is 10-25%.
The mass ratio of the butadiene to the molybdenum atoms in the catalyst is 1: 500-1: 2000.
The solvent is heptane, hexane, solvent oil, hydrogenated gasoline or toluene.
The rubber-like high vinyl polybutadiene has a number average molecular weight of 10-40 ten thousand, a molecular weight distribution index PDI of 2.0-4.5, a 1, 2-structure content of 70-93% and an activity of 600kg PB/mol Mo.
Compared with the prior art, the invention has the following beneficial effects:
the molybdenum catalyst for catalyzing butadiene high-1, 2-selectivity polymerization, which is composed of the bridged binuclear molybdenum compound and the aryloxy dialkyl aluminum, does not need to use large steric hindrance substrates such as octanol and the like, adopts short carbon chain alcohols such as methanol and ethanol and the like, and has the advantages of low cost, high atom economy and less pollution. In addition, the previously reported catalysts are all mononuclear, and the molybdenum polybutadiene catalyst taking the bridged binuclear molybdenum compound as the catalyst component is not reported.
The catalyst of the invention catalyzes butadiene to polymerize and prepare high vinyl polybutadiene in heptane, hexane, solvent naphtha, hydrogenated gasoline or toluene, the content of 1, 2-structural units of the product can reach more than 80 percent, and the activity can reach 600kg PB/mol Mo.
Drawings
FIG. 1 is the crystal structure of complex 1.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials used in the examples are all commercially available raw materials.
Example 1
Preparation of Complex 1:
molybdenum pentachloride (1g, 3.65mmol) was slowly added to 10mL of methanol at-78 deg.C with stirring under a dry nitrogen argon atmosphere. Then, slowly raising the temperature to-10 ℃, gradually changing the color of the solution from brown yellow to green, discharging a large amount of hydrogen chloride gas in the reaction process, and concentrating the solution to 2mL under the protection of inert gas. The solution was then frozen at-18 ℃ for more than 24 hours and crystallized. The crystals were brown needles sensitive to air. The yield was about 55%. Elemental analysis has a molecular formula of C3H9Cl2MoO3：C,13.80；H,3.32；Cl,27.31；Mo,36.75；O,18.42。
The reaction equation is as follows:
MoCl5+CH3OH→[Cl2(OCH3)2Mo(μ-OCH3)2Mo(OCH3)2Cl2]+HCl。
diffraction analysis of the single crystal of the product confirms that the obtained product is the complex 1, and the crystal structure is shown in figure 1.
Example 2
Preparation of Complex 2:
molybdenum pentachloride (2g, 3.65mmol) was slowly added to 10mL of ethanol at-50 deg.C with stirring under a dry nitrogen argon atmosphere. Then, slowly raising the temperature to-10 ℃, gradually changing the color of the solution from brown yellow to green, and discharging a large amount of hydrogen chloride gas in the reaction process. The solution was frozen at 0 ℃ for 24 hours or more to precipitate crystals. The solution was concentrated to 2mL under inert gas. The solution was then frozen at-18 ℃ for more than 24 hours and crystallized. The yield was about 60%. Elemental analysis has a molecular formula of C6H15Cl2MoO3：C,23.91；H,5.01；Cl,23.55；Mo,31.61；O,15.92。
The reaction equation is as follows:
MoCl5+CH2CH3OH→[Cl2(OCH2CH3)2Mo(μ-OCH2CH3)2Mo(OCH2CH3)2Cl2]+HCl。
application example 1
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.78mmol of m-methylphenoxydiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.1mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, whereby 3.9g of a rubbery high vinyl polybutadiene was obtained, the yield was 92.9%, the product 1, 2-structure content was 82% by infrared analysis, the product molecular weight was about 20 ten thousand by GPC analysis, and the PDI was 2.3.
Application example 2
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.78mmol of m-methylphenoxydiethylaluminum and 0.078mmol of complex 2 (previously dissolved in 0.1mL of toluene), stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, and the product was dried to give 3.75g of rubbery high-vinyl polybutadiene, a yield of 89.3%, a product 1, 2-structure content of 84% by infrared analysis, a product molecular weight of about 23 ten thousand by GPC analysis, and a PDI of 2.1.
Application example 3
To 100mL of a butadiene-n-hexane solution (0.12g/mL) were added 4.3mmol of m-methylphenoxydiisobutylaluminum and 0.43mmol of complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and 2mL of ethanol was added to terminate the reaction, and the product was dried to give 11.6g of rubbery high vinyl polybutadiene, a yield of 96.7%, a content of 1, 2-structure of 83% by infrared analysis, a molecular weight of the product of about 17 ten thousand by GPC analysis, and PDI of 2.2.
Application example 4
To 30mL of a toluene solution of butadiene (0.22g/mL) were added 1.2mmol of m-methylphenoxydiethylaluminum and 0.12mmol of complex 1 (previously dissolved in 0.2mL of toluene), the mixture was stirred at 120 ℃ for 0.5 hour, 2mL of ethanol was added to terminate the reaction, and the product was dried to give 5.2g of a rubbery high vinyl polybutadiene, a yield of 78.7%, a content of 1, 2-structures of the product was 76% by infrared analysis, a molecular weight of the product was 19 ten thousand by GPC analysis, and PDI was 3.6.
Application example 5
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 1.2mmol of m-methylphenoxydiisobutylaluminum and 0.12mmol of complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 20 ℃ for 8 hours, and then 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, thereby obtaining 2.1g of a rubbery high vinyl polybutadiene with a yield of 50.0%, a product 1, 2-structure content of 93% was analyzed by infrared, a product molecular weight of about 29 ten thousand was analyzed by GPC, and PDI was 3.2.
Application example 6
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.78mmol of phenoxydiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and then 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, whereby 3.7g of a rubbery high vinyl polybutadiene was obtained, the yield was 88.1%, the product 1, 2-structure content was 80% by infrared analysis, the product molecular weight was 20 ten thousand by GPC analysis, and the PDI was 2.5.
Application example 7
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.78mmol of 1-naphthoxydiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, whereby 3.8g of a rubbery high vinyl polybutadiene was obtained with a yield of 90%, and the product had a 1, 2-structure content of 82% as determined by infrared analysis and a molecular weight of about 21 ten thousand as determined by GPC analysis, and had a PDI of 2.3.
Application example 8
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.78mmol of 2-naphthoxydiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, whereby 3.5g of a rubbery high vinyl polybutadiene was obtained, the yield was 83.3%, the content of 1, 2-structures was 86% by infrared analysis, and the molecular weight of the product was about 24 ten thousand by GPC analysis, and the PDI was 2.6.
Application example 9
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.78mmol of o-methylphenoxydiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, to obtain 2.5g of a rubbery high vinyl polybutadiene, giving a yield of 59.5%, and as a result, the infrared analysis showed that the content of 1, 2-structures was 80%, and as a result, the GPC analysis showed that the molecular weight of the product was about 23 ten thousand, and the PDI was 4.5.
Application example 10
To 30mL of a heptane solution of butadiene (0.14g/mL) were added 0.78mmol of o-methylphenoxydiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.2mL of toluene), stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, and the product was dried to give 3.7g of a rubbery high vinyl polybutadiene, with a yield of 88.1%, a 1, 2-structure content of 84% by infrared analysis, a molecular weight of the product by GPC analysis of about 20 ten thousand, and a PDI of 2.4.
Application example 11
To 30mL of a hydrogenated gasoline of butadiene (0.14g/mL) were added 0.78mmol of o-methylphenoxydiisobutylaluminum and 0.078mmol of Complex 1 (previously dissolved in 0.2mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, thereby drying the product and obtaining 3.7g of rubbery high-vinyl polybutadiene, giving a yield of 88.1%, and as a result of infrared analysis, the content of 1, 2-structures was 82%, and as a result of GPC analysis, the molecular weight of the product was about 20 ten thousand, and the PDI was 2.4.
Application example 12
To 30mL of butadiene in 120# solvent oil (0.14g/mL) was added 0.78mmol of o-methylphenoxydiodiisobutylaluminum and 0.078mmol of complex 1 (previously dissolved in 0.2mL of toluene), stirred at 60 ℃ for 4 hours, and 0.5mL of ethanol was added to terminate the reaction, and the product was dried to give 3.8g of rubbery high vinyl polybutadiene, yield 90.4%, product 1, 2-structure content 79% by infrared analysis, molecular weight of the product 23 ten thousand by GPC analysis, and PDI 3.1.
Application example 13
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 2.34mmol of m-methylphenoxydiethylaluminum and 0.078mmol of complex 2 (previously dissolved in 0.1mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and then 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, thereby obtaining 2.9g of a rubbery high vinyl polybutadiene, showing a yield of 69.0%, 90% of a 1, 2-structure content of the product by infrared analysis, about 23 ten thousand of the molecular weight of the product by GPC analysis, and 2.1 as PDI.
Application example 14
To 30mL of a butadiene-n-hexane solution (0.14g/mL) were added 0.312mmol of m-methylphenoxydiethylaluminum and 0.078mmol of complex 2 (previously dissolved in 0.1mL of toluene), and the mixture was stirred at 60 ℃ for 4 hours, and then 0.5mL of ethanol was added to terminate the reaction, thereby drying the product, thereby obtaining 2.6g of a rubbery high vinyl polybutadiene, showing a yield of 61.9%, a 1, 2-structure content of 76% as a product by infrared analysis, a molecular weight of the product by GPC analysis of about 26 ten thousand, and a PDI of 3.7.
Claims (10)
1. A molybdenum-based catalyst for catalyzing butadiene to polymerize with high 1, 2-selectivity is characterized in that: the catalyst consists of a bridged binuclear molybdenum compound and aryloxy dialkyl aluminum, wherein the mass ratio of the bridged binuclear molybdenum compound to the aryloxy dialkyl aluminum is 1: 4-1: 30;
the structural formula of the bridged binuclear molybdenum compound is as follows:
wherein R is methyl or ethyl;
the structural formula of the aryloxy dialkyl aluminum is as follows:
wherein R' is ethyl or isobutyl, and Ar is aryl.
2. The molybdenum-based catalyst for catalyzing the polymerization of butadiene with high 1, 2-selectivity according to claim 1, wherein: the ratio of the amount of the bridged binuclear molybdenum compound to the amount of the aryloxydialkyl aluminum compound is 1:5 to 1: 15.
3. The molybdenum-based catalyst for catalyzing the polymerization of butadiene with high 1, 2-selectivity according to claim 1, wherein: the aryl group comprises phenyl, 1-naphthyl, 2-naphthyl, o-methylphenyl, m-methylphenyl and p-methylphenyl.
4. The molybdenum-based catalyst for catalyzing the polymerization of butadiene with high 1, 2-selectivity according to claim 3, wherein: the aryl is m-methylphenyl.
5. The molybdenum-based catalyst for catalyzing the polymerization of butadiene with high 1, 2-selectivity according to claim 1, wherein: the preparation method of the bridged binuclear molybdenum compound comprises the following steps:
under the anhydrous and oxygen-free atmosphere, adding molybdenum pentachloride into ROH under low-temperature stirring, heating and stirring for reaction, removing most of liquid, and freezing and crystallizing to obtain the bridged binuclear molybdenum compound.
6. The molybdenum-based catalyst for catalyzing the polymerization of butadiene with high 1, 2-selectivity according to claim 5, wherein: the low-temperature stirring temperature is-85 to-65 ℃.
7. The molybdenum-based catalyst for catalyzing the polymerization of butadiene with high 1, 2-selectivity according to claim 5, wherein: the temperature of the heating stirring reaction is-20 to 0 ℃, and the reaction time is 1 to 2 hours.
8. A method for using the molybdenum-based catalyst of any one of claims 1 to 7 for catalyzing the 1, 2-selective polymerization of butadiene, wherein: the method comprises the following steps:
under the anhydrous and oxygen-free conditions, adding the molybdenum catalyst for catalyzing butadiene to polymerize in a high 1, 2-selectivity mode, stirring for 1-480 minutes at 20-80 ℃, adding ethanol to terminate the reaction, and drying to obtain the rubber-like high vinyl polybutadiene.
9. The method of application according to claim 8, characterized in that: the mass ratio of the butadiene to the molybdenum atoms in the catalyst is 1: 500-1: 2000.
10. The application method according to claim 8, characterized in that: the rubber-like high vinyl polybutadiene has a number average molecular weight of 10-40 ten thousand, a molecular weight distribution index PDI of 2.0-4.5, and a 1, 2-structure content of 70-93%.
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