CN119409719A - A method for synthesizing methylaluminoxane from polyol and modifying methylaluminoxane - Google Patents
A method for synthesizing methylaluminoxane from polyol and modifying methylaluminoxane Download PDFInfo
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- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229920005862 polyol Polymers 0.000 title claims abstract description 18
- 150000003077 polyols Chemical class 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 23
- -1 polyol compound Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 30
- 229910052782 aluminium Inorganic materials 0.000 description 24
- 238000007334 copolymerization reaction Methods 0.000 description 22
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- CWEHKOAQFGHCFQ-UHFFFAOYSA-N methylalumane Chemical class [AlH2]C CWEHKOAQFGHCFQ-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SVOZEWXYCOBNAY-UHFFFAOYSA-M bromo(dioctyl)alumane Chemical compound [Br-].CCCCCCCC[Al+]CCCCCCCC SVOZEWXYCOBNAY-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QRQUTSPLBBZERR-UHFFFAOYSA-M dioctylalumanylium;chloride Chemical compound CCCCCCCC[Al](Cl)CCCCCCCC QRQUTSPLBBZERR-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
- C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
Abstract
本发明适用于精细化工合成技术领域，提供了一种多元醇合成甲基铝氧烷及改性甲基铝氧烷的方法，包括以下步骤：步骤一、多元醇化合物在溶剂中与三甲基铝在一定温度下反应，制备得到甲基铝氧烷前驱体；步骤二、将步骤一所得的甲基铝氧烷前驱体在一定温度下热解，得到甲基铝氧烷；步骤三、将步骤二得到的甲基铝氧烷与长链烷基铝进行混合，加热，然后用溶剂稀释到一定浓度，得到改性甲基铝氧烷。本发明能够有效避免现有反应需要高温高压、无法较大规模生产的缺点，更加有利于实现工业上大规模生产要求。The present invention is applicable to the technical field of fine chemical synthesis, and provides a method for synthesizing methylaluminoxane and modified methylaluminoxane from polyols, comprising the following steps: step 1, reacting a polyol compound with trimethylaluminum in a solvent at a certain temperature to prepare a methylaluminoxane precursor; step 2, pyrolyzing the methylaluminoxane precursor obtained in step 1 at a certain temperature to obtain methylaluminoxane; step 3, mixing the methylaluminoxane obtained in step 2 with a long-chain alkyl aluminum, heating, and then diluting with a solvent to a certain concentration to obtain modified methylaluminoxane. The present invention can effectively avoid the disadvantages of the existing reaction requiring high temperature and high pressure and being unable to be produced on a large scale, and is more conducive to achieving industrial large-scale production requirements.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to methylaluminoxane and a method for modifying methylaluminoxane.
Background
Methylaluminoxane (MAO for short) is an important cocatalyst for metallocene catalyst systems and has very important applications in the field of olefin polymerization. The methylaluminoxane has a cage-shaped structure which can effectively disperse negative charges to form a non-coordination charge balance body of a metallocene cation active center, and the methylaluminoxane has unique performance in olefin polymerization. The use of methylaluminoxane type cocatalysts can greatly improve the activity of the catalyst.
The synthesis method of methylaluminoxane is basically divided into two types. One is a hydrolysis method, which can be summarized as a direct hydrolysis process and an indirect hydrolysis process according to different feeding modes of water participating in the reaction. The direct hydrolysis process includes static mixer process, atomized water process, falling film process, T-reactor process, ice block process, ultrasonic dispersion process, etc. and the indirect water process is to prepare MAO through reaction of trimethyl aluminum and inorganic salt crystal hydrate. The direct water process adopts a mode of adding water into trimethylaluminum toluene solution, so that higher reaction yield can be obtained, but the process has high requirements on equipment quality due to extremely high danger of the reaction of trimethylaluminum and water. The indirect water process has lower reaction yield of the target product MAO due to the limitation of the feeding process. The other is non-hydrolysis method, which mainly adopts trimethylaluminum to react with carbon dioxide, alcohol, aldehydes and organic acid compounds, and then MAO is obtained through pyrolysis. Some of the methods reported at present for preparing methylaluminoxane by using oxygen source reagents such as carbon dioxide, benzoic acid and the like generally need to be carried out under the condition of high temperature and high pressure, and certain risks exist, and all the methods are not suitable for carrying out the large-scale production of the methylaluminoxane. The polyol is an organic compound having a plurality of hydroxyl groups, and the raw materials are readily available. From the aspect of atomic economy, the polyol molecules with the same mass can provide more oxygen atoms, so that the MAO prepared from the polyol has the atomic economy advantage, in addition, the reaction speed is gradually reduced due to the multistage gradual reaction of the alkyl aluminum and the hydroxyl groups of the polyol, the reaction is milder, and the polyallylalkyl aluminum complex generated by the reaction of the alkyl aluminum and the polyol has milder pyrolysis conditions due to the synergistic effect of a plurality of aluminum alkoxide groups. For this purpose we propose a method for synthesizing methylaluminoxane and modified methylaluminoxane from polyalcohol.
Disclosure of Invention
The invention aims to provide a method for synthesizing methylaluminoxane and modified methylaluminoxane by using polyalcohol, which aims to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A method for synthesizing methylaluminoxane and modified methylaluminoxane by using polyalcohol, which comprises the following steps:
Step one, a polyol compound reacts with trimethylaluminum in a solvent at a certain temperature to prepare a methylaluminoxane precursor;
Pyrolyzing the methylaluminoxane precursor obtained in the step one at a certain temperature to obtain methylaluminoxane;
And step three, mixing the methylaluminoxane obtained in the step two with long-chain alkyl aluminum, heating, and diluting to a certain concentration by using a solvent to obtain the modified methylaluminoxane.
Further, in the first step, the molar ratio of the trimethylaluminum to the polyol is 3:1-5:1.
Further, in the first step, the temperature of the reaction of the polyol and the trimethylaluminum is 0-80 ℃.
Further, in the second step, the pyrolysis temperature of the methylaluminoxane precursor is 80-200 ℃.
Further, in the third step, the temperature of the reaction of the methylaluminoxane and the long-chain alkyl aluminum is 60-180 ℃.
Further, the molar ratio of the trimethylaluminum to the long-chain alkyl aluminum is 10:1-1:1.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts polyalcohol as oxygen source reagent to synthesize methyl aluminoxane and modified methyl aluminoxane. By adopting the polyol mode, the reaction is easy to quantify, the reaction condition is mild, and high-pressure operation is not needed. The method has higher economic advantage, can effectively avoid the defect that the prior reaction cannot be produced in a large scale, and is more beneficial to realizing the industrial large-scale production requirement.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
The method for synthesizing methylaluminoxane and modified methylaluminoxane by using polyalcohol provided by one embodiment of the invention comprises the following steps:
Step one, a polyol compound reacts with trimethylaluminum in a solvent at a certain temperature to prepare a methylaluminoxane precursor;
Pyrolyzing the methylaluminoxane precursor obtained in the step one at a certain temperature to obtain methylaluminoxane;
And step three, mixing the methylaluminoxane obtained in the step two with long-chain alkyl aluminum, heating, and diluting to a certain concentration by using a solvent to obtain the modified methylaluminoxane.
In the embodiment of the invention, the methylaluminoxane can be prepared, and the modified methylaluminoxane can also be further prepared. The resulting methylaluminoxane or modified methylaluminoxane can be used as a cocatalyst for limiting the copolymerization of ethylene and alpha-olefin catalyzed by the geometric catalyst to test the activity of the catalyst.
The polymerization evaluation used a2 liter polymerization reactor with 5. Mu. Mol of [ tetramethyl cyclopentadienyl-dimethyl silicon bridge-t-butylamino ] zirconium as the main catalyst, 2ml of the prepared MMAO solution (modified methylaluminoxane solution), 250 ml of octene, 1000 ml of hexane, a polymerization pressure of 3MPa, a polymerization temperature of 140℃and a polymerization time of 15 minutes.
As a preferred embodiment of the present invention, in the first step, the polyol compound means an organic compound having a plurality of hydroxyl groups, such as ethylene glycol, glycerol, pentaerythritol, etc., preferably glycerol.
In the first step, the organic solvent may be a single organic solvent or a mixture of a plurality of organic solvents, and the organic solvent may be alkanes, aromatics, and heptane and Isopar E are preferred. The medium may comprise one or more alkanes and aromatic hydrocarbons. Heptane and toluene are preferred organic solvents in the examples of the present invention.
As a preferred embodiment of the present invention, in the first step, the molar ratio of trimethylaluminum to polyol is 3:1-5:1. More preferred conditions are 3:1.
As a preferred embodiment of the present invention, in the first step, the temperature at which the polyhydric alcohol is reacted with trimethylaluminum is 0 to 80 ℃. More preferred conditions are 20-40 ℃.
As a preferred embodiment of the present invention, in the second step, the pyrolysis temperature of the methylaluminoxane precursor is 80 to 200 ℃. More preferred conditions are 100-150 ℃.
As a preferred embodiment of the present invention, in the third step, the reaction temperature of the methylaluminoxane and the long chain alkyl aluminum is 60 to 180 ℃. More preferred conditions are 80-100 ℃.
As a preferred embodiment of the invention, the molar ratio of trimethylaluminum to long-chain alkylaluminum is 10:1-1:1. More preferred conditions are 5:1 to 3:1.
As a preferred embodiment of the present invention, in the third step, the long chain alkyl aluminum may be some common alkyl aluminum reagents with a chain carbon number of 4 or more, including but not limited to triisobutyl aluminum, tributyl aluminum, tri-n-octyl aluminum, triisooctyl aluminum, di-n-octyl aluminum chloride, di-n-octyl aluminum bromide, etc. In practical operation, a single variety of long-chain alkyl aluminum reagent can be selected, and a mixture of several long-chain alkyl aluminum reagents can be selected. Triisobutylaluminum and tri-n-octylaluminum are preferred.
Example 1 methylaluminoxane and modified methylaluminoxane were prepared and used as co-catalyst for copolymerization comprising the steps of:
(1) Into a 100 ml flask was charged trimethylaluminum (14.4 g, 0.2 mol), 100 ml heptane. Glycerol (6.13 g, 0.066 mol) was slowly added at 20℃and the resulting solution was stirred at 20℃for 20 hours to produce a methylaluminoxane precursor in a molar ratio of trimethylaluminum to glycerol of 3:1. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 120 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining the methylaluminoxane heptane solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Heptane was added to the solution to an aluminum concentration of about 7%. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane solution prepared in (2) was added a certain amount of tri-n-octylaluminum (molar ratio of trimethylaluminum to tri-n-octylaluminum is 5:1), and the resulting mixture was heated and stirred at 90℃for 5 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 2.5X10- 7 g polymer/mol catalyst/hr.
Example 2 preparation of methylaluminoxane and modified methylaluminoxane as cocatalyst for copolymerization comprising the steps of:
(1) Into a 100 ml flask was charged trimethylaluminum (14.4 g, 0.2 mol), 100 ml heptane. Glycerol (6.13 g, 0.066 mol) was slowly added at 40 ℃ (molar ratio of trimethylaluminum to glycerol 3:1). The resulting solution was stirred at 50 ℃ for 12 hours to produce a methylaluminoxane precursor. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 120 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining the methylaluminoxane heptane solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Heptane was added to the solution to an aluminum concentration of about 7%. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane solution prepared in (2) was added a certain amount of tri-n-octylaluminum (molar ratio of trimethylaluminum to tri-n-octylaluminum is 5:1), and the resulting mixture was heated and stirred at 100℃for 5 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 2.4X10- 9 g polymer/mol catalyst/hr.
Example 3 preparation of methylaluminoxane and modified methylaluminoxane as cocatalyst for copolymerization comprising the steps of:
(1) Into a 100 ml flask was charged trimethylaluminum (14.4 g, 0.2 mol), 100 ml heptane. Ethylene glycol (6.2 g, 0.1 mol) (molar ratio of trimethylaluminum to ethylene glycol 2:1) was slowly added at 20℃and the resulting solution was stirred at 60℃for 12 hours to prepare a methylaluminoxane precursor. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 150 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining the methylaluminoxane toluene solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Toluene was added to give an aluminum concentration of about 7% in the solution. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane solution prepared in (2) was added 3.5 g of triisobutylaluminum (molar ratio of trimethylaluminum to triisobutylaluminum is 3:1), and the resulting mixture was heated and stirred at 100℃for 6 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 1.9X10- 8 g polymer/mol catalyst/hr.
Example 4 preparation of methylaluminoxane and modified methylaluminoxane as cocatalyst for copolymerization comprising the steps of:
(1) Into a 100 ml flask was charged trimethylaluminum (14.4 g, 0.2 mol), 100 ml heptane. The solution obtained by slowly adding (6.13 g, 0.066 mol) at 20℃and the molar ratio of trimethylaluminum to polyaluminum glycerol acetate was 3:1 was stirred at 30℃for 12 hours to prepare a methylaluminoxane precursor. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 140 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining the methylaluminoxane heptane solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Heptane was added to the solution to an aluminum concentration of about 7%. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane solution prepared in (2) was added a certain amount of tri-n-octylaluminum (molar ratio of trimethylaluminum to tri-n-octylaluminum: 5:1), and the resulting mixture was heated and stirred at 100℃for 5 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 2.3X10- 9 g polymer/mol catalyst/hr.
Example 5 preparation of methylaluminoxane and modified methylaluminoxane as cocatalyst for copolymerization comprising the steps of:
(1) Into a 100 ml flask was charged trimethylaluminum (14.4 g, 0.2 mol), 100 ml heptane. Pentaerythritol (6.8 g, 0.05 mol) was slowly added at 20℃and the resulting solution was stirred at 20℃for 12 hours to give a methylaluminoxane precursor. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 140 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining the methylaluminoxane toluene solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Toluene was added to give an aluminum concentration of about 7% in the solution. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane solution prepared in (2) was added a certain amount of tri-n-octylaluminum (molar ratio of trimethylaluminum to tri-n-octylaluminum: 5:1), and the resulting mixture was heated and stirred at 100℃for 5 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 1.7X10- 9 g polymer/mol catalyst/hr.
Example 6 preparation of methylaluminoxane and modified methylaluminoxane as cocatalyst for copolymerization comprising the steps of:
(1) Into a 100 ml flask was charged 14.4 g of trimethylaluminum, 100 ml of heptane. 14.4 g of glycerol was slowly added at 20℃and the resulting solution (molar ratio of trimethylaluminum to glycerol 10:1) was stirred at 20℃for 12 hours to produce a methylaluminoxane precursor. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 140 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining the methylaluminoxane heptane solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Heptane was added to the solution to an aluminum concentration of about 7%. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane solution prepared in (2) was added a certain amount of tri-n-octylaluminum (molar ratio of trimethylaluminum to tri-n-octylaluminum: 5:1), and the resulting mixture was heated and stirred at 100℃for 5 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 2.1X10- 9 g polymer/mol catalyst/hr.
Example 7 preparation of methylaluminoxane and modified methylaluminoxane as cocatalyst for copolymerization comprising the steps of:
(1) Into a 100ml flask was charged 14.4 g of trimethylaluminum, 100ml of Isopar E solution. 14.4 g of glycerol was slowly added at 20℃and the resulting solution (molar ratio of trimethylaluminum to glycerol 10:1) was stirred at 20℃for 12 hours to produce a methylaluminoxane precursor. Nuclear magnetic resonance hydrogen spectrum shows that aluminum alkoxide complex is generated.
(2) The methylaluminoxane precursor prepared in (1) was heated to 150 ℃ and stirred overnight, releasing the generated gas, and nuclear magnetic resonance hydrogen spectrum showed that the aluminum alkoxide compound had been converted to MAO. Obtaining methylaluminoxane Isopar E solution. Since there is no loss of alkyl aluminum in this process, the yield of methylaluminoxane can be considered to be 100%. Heptane was added to the solution to an aluminum concentration of about 7%. The solution obtained in this step can be used for the copolymerization of ethylene and octene.
(3) To the methylaluminoxane Isopar E solution prepared in (2) was added a certain amount of tri-n-octylaluminum (molar ratio of trimethylaluminum to tri-n-octylaluminum: 5:1), and the resulting mixture was heated and stirred at 100℃for 5 hours to obtain a transparent modified methylaluminum solution. The MMAO obtained was used for copolymerization of ethylene and octene, and the activity was 1.9X10- 9 g polymer/mol catalyst/hr.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent.
Claims (6)
1. A method for synthesizing methylaluminoxane and modified methylaluminoxane by using polyalcohol, which is characterized by comprising the following steps:
Step one, a polyol compound reacts with trimethylaluminum in a solvent at a certain temperature to prepare a methylaluminoxane precursor;
Pyrolyzing the methylaluminoxane precursor obtained in the step one at a certain temperature to obtain methylaluminoxane;
And step three, mixing the methylaluminoxane obtained in the step two with long-chain alkyl aluminum, heating, and diluting to a certain concentration by using a solvent to obtain the modified methylaluminoxane.
2. The method for synthesizing methylaluminoxane and modified methylaluminoxane from a polyol according to claim 1, wherein in the first step, the molar ratio of trimethylaluminum to the polyol is 5:1 to 10:1.
3. The method for synthesizing methylaluminoxane and modified methylaluminoxane from a polyhydric alcohol according to claim 1, wherein in said step one, the temperature of the reaction of the polyhydric alcohol with trimethylaluminum is 0 to 100 ℃.
4. The method for synthesizing methylaluminoxane and modified methylaluminoxane from a polyhydric alcohol according to claim 1, wherein in the second step, the pyrolysis temperature of the methylaluminoxane precursor is 80 to 250 ℃.
5. The method for synthesizing methylaluminoxane and modified methylaluminoxane from a polyhydric alcohol according to claim 1, wherein in the third step, the reaction temperature of methylaluminoxane and long chain alkyl aluminum is 50 ℃ to 180 ℃.
6. The method for synthesizing methylaluminoxane and modified methylaluminoxane from a polyhydric alcohol according to claim 1, wherein the molar ratio of trimethylaluminum to long chain alkylaluminum is 10:1-1:1.
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