CN110734512B - Preparation method of polypropylene catalyst - Google Patents
Preparation method of polypropylene catalyst Download PDFInfo
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- CN110734512B CN110734512B CN201810800963.8A CN201810800963A CN110734512B CN 110734512 B CN110734512 B CN 110734512B CN 201810800963 A CN201810800963 A CN 201810800963A CN 110734512 B CN110734512 B CN 110734512B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The invention discloses a preparation method of a polypropylene catalyst, which is a supported metallocene catalyst for preparing syndiotactic polypropylene, and comprises the following steps: adding the heat-treated carrier into a solvent for dispersion, adding alkyl aluminum, boric acid and water for reaction, adding a metallocene complex after the reaction is finished, and continuing the reaction to obtain the catalyst; the metallocene complex is represented by the general formula (1): r1(CpR2 n)(FluR3 m)MQ2Wherein Cp is cyclopentadienyl, Flu is fluorenyl, R2And R3Each independently selected from H, C1～C12M and n are integers of 0 to 4, R1Is a bridging group of a cyclopentadienyl group and a fluorenyl group, M is zirconium or hafnium, Q is halogen or C1～C6Alkyl group of (1).
Description
Technical Field
The invention relates to a preparation method of a polypropylene catalyst, in particular to a preparation method of a supported metallocene catalyst for preparing syndiotactic polypropylene.
Background
Syndiotactic polypropylene sPP was first reported in patent US 3305538, where the catalyst produced only a small amount of extracted sPP. Since Ewen JA adopted having CsSymmetric metallocene catalyst systems can then be used to prepare polypropylene of high syndiotactic degree (J.Am.chem.Soc.,1988,110, 6255-6256.). However, sPP obtained by using homogeneous metallocene catalysts has poor morphology and low bulk density, and is not suitable for the existing polypropylene industrial equipment. If the metallocene catalyst is applied to the existing polypropylene process, the metallocene catalyst is generally used after being loaded. The first and most common industrial loading method is to pre-mix the alkylaluminoxane (such as methylaluminoxane MAO) solution with the carrier for a certain period of time, then add the metallocene solution into the mixture, and filter, wash and dry to obtain the loaded metallocene catalyst (U.S. Pat. No. 4808561, 5026797).
For example, CN105555811A relates to a polypropylene preparation process and polypropylene obtained thereby. The catalyst comprises a novel metallocene compound having excellent polymerization activity. According to the present invention, by polymerizing propylene using a novel metallocene compound having excellent polymerization activity and hydrogen reactivity, physical properties of polypropylene can be easily controlled, and polypropylene having excellent physical properties can be obtained. The catalyst is used after being loaded, and alkyl aluminoxane is used as a catalyst auxiliary agent (comprising methyl aluminoxane MAO).
Because alkylaluminoxane (such as methylaluminoxane MAO) is high in cost, patent (US 5086025) uses cheap alkylaluminum (trimethylaluminum or triisobutylaluminum) to react with a silica gel carrier which is not activated by heat treatment and contains a certain amount of water (the mass fraction of the water content is 5-35%) to generate silica gel treated by aluminum alkoxide in situ. Then reacting with metallocene solution to prepare the load type metallocene catalyst. The activity of the obtained catalyst is higher than that of the supported catalyst prepared by the method of treating silica gel with MAO and then loading metallocene. However, the polymerization activity of the catalyst strongly depends on the order of addition and the rate of addition of the carrier and the aluminum alkyl, and in order to obtain a highly active catalyst, the carrier must be added to the aluminum alkyl, and the carrier used is a silica gel carrier having a specific water content, which is disadvantageous in reducing the production cost of the catalyst.
Disclosure of Invention
The invention aims to develop a preparation method of a polypropylene catalyst, and the catalyst prepared by the method is a supported metallocene catalyst for preparing syndiotactic polypropylene. The catalyst has high catalytic activity, and syndiotactic polypropylene with high molecular weight and excellent morphology can be obtained through propylene polymerization reaction catalyzed by the catalyst.
Therefore, the invention provides a preparation method of a polypropylene catalyst, which is a supported metallocene catalyst used for preparing syndiotactic polypropylene, and the preparation method comprises the following steps:
adding the heat-treated carrier into a solvent for dispersion, adding alkyl aluminum, boric acid and water for reaction, adding a metallocene complex for continuous reaction after the reaction is finished, and washing and draining after the reaction is finished to obtain the catalyst;
the metallocene complex is represented by the general formula (1): r1(CpR2 n)(FluR3 m)MQ2Wherein Cp is cyclopentadienyl, Flu is fluorenyl, R2And R3Each independently selected from H, C1～C12M and n are integers of 0 to 4, R1Is a bridging group of a cyclopentadienyl group and a fluorenyl group, M is zirconium or hafnium, Q is halogen or C1～C6Alkyl group of (1).
The preparation method of the polypropylene catalyst comprises the step of preparing the catalyst R1The structural formula of (A) is preferably-C (CH)3)2-，-C(Ph)2-，-CH2-CH2-or-Si (CH)3)2-。
In the preparation method of the polypropylene catalyst, the metallocene complex is preferably isopropylidene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride or vinyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride.
The preparation method of the polypropylene catalyst provided by the invention is characterized in that the adding amount of the metallocene complex is preferably 1g of silica gel added by (1-30) × 10-5mol of metallocene complex.
The preparation method of the polypropylene catalyst provided by the invention is characterized in that in the preparation process of the catalyst, the addition amount of each component is preferably as follows: the molar ratio of (water + boric acid)/alkyl aluminum is 0.7-0.95, SiO2The ratio of aluminum alkyl is 1g SiO2Adding (0.5-10) × 10-2mol of aluminum alkyl.
In the preparation method of the polypropylene catalyst according to the present invention, it is preferable that the boric acid is represented by general formula (2): RB (OH)2Wherein R is phenyl, C1～C6Alkyl or fluoro substituted phenyl.
In the preparation method of the polypropylene catalyst, the alkyl aluminum is preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum.
In the preparation method of the polypropylene catalyst, the carrier is preferably silica.
The preparation method of the polypropylene catalyst provided by the invention is characterized in that the specific surface area of the silicon dioxide is preferably 200m2/g～600m2The particle diameter is preferably 10 to 60 μm, and the pore volume is preferably 0.8 to 3 mL/g.
In the preparation method of the polypropylene catalyst according to the present invention, the heat treatment is further preferably: treating for 2-24 hours at 400-600 ℃ under the protection of nitrogen flow.
The preparation method of the polypropylene catalyst provided by the invention is preferably used, wherein after the carrier is subjected to heat treatment, the surface hydroxyl content of the carrier is 1-5 OH/nm2。
In the preparation method of the polypropylene catalyst, the solvent is preferably toluene, cyclohexane or n-hexane.
The preparation method of the polypropylene catalyst specifically comprises the following steps:
dispersing a carrier in a solvent, adding alkyl aluminum, boric acid and water, adding a metallocene complex after the reaction is finished, continuing the reaction, washing and draining after the reaction is finished to obtain a target catalyst system; wherein the carrier is silica having a specific surface area in the range of 200m2/g～600m2The particle size is 10-60 μm, and the pore volume is 0.8-3 mL/g. The carrier silicon dioxide is subjected to heat treatment before reaction, namely is treated for 2-24 hours at the temperature of 400-600 ℃ under the protection of nitrogen flow. The surface hydroxyl content of the obtained silica gel is (1-5) OH/nm2。
The supported metallocene catalyst system for preparing syndiotactic polypropylene has a molar ratio of (water + boric acid)/alkylaluminum of 0.7-0.95 and SiO2The ratio of aluminum alkyl is 1g SiO2Adding (0.5-10) × 10-2mol of aluminum alkyl.
The molecular formula of the metallocene complex used by the supported metallocene catalyst system of the syndiotactic polypropylene is R1(CpR2 n)(FluR3 m)MQ2. Cp is cyclopentadienyl, Flu is fluorenyl, R2And R3Are respectively selected from H, C1～C12With m and n being in the range of 0 to 4, R1A bridging group being a linked cyclopentadienyl and fluorenyl radical, characterized by-C (CH)3)2-，-C(Ph)2-，-CH2-CH2-or-Si (CH)3)2-, M is Zr or Hf, Q is halogen or C1～C6Alkyl group of (1).
The molecular formula of boric acid used by the supported metallocene catalyst system of the syndiotactic polypropylene is RB (OH)2R is C1～C6Alkyl, phenyl or fluoro substituted phenyl.
When the supported metallocene catalyst system for preparing syndiotactic polypropylene is prepared, the addition amount of the metallocene complex is 1g of silica gel added by (1-30) × 10-5mol of metallocene complex.
The invention has the following beneficial effects:
the vectors of the present invention need not be specificThe water content is limited by the use of an existing commodity as a carrier, e.g., a commodity brand of
2408D (Grace) silica gel.
The invention utilizes the carrier after heat treatment, adds alkyl aluminum and a certain amount of water and boric acid, and after the reaction with the metallocene solution, the activity of the supported catalyst obtained after the reaction is higher due to the addition of the boric acid, and syndiotactic polypropylene with high molecular weight and excellent form can be prepared.
Drawings
FIG. 1 is a flow chart of a process for preparing a polypropylene catalyst of the present invention;
FIG. 2 is a flow chart of a preparation process of example 2 of the present invention;
FIG. 3 is a flow chart of a method of preparation of example 3 of the present invention;
FIG. 4 is a flow chart of a method of preparation of example 4 of the present invention;
FIG. 5 is a flow chart of a method of preparation of example 5 of the present invention;
FIG. 6 is a flow chart of a preparation method of example 8 of the present invention.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The preparation method of the polypropylene catalyst specifically comprises the following steps:
dispersing a carrier in a solvent, adding alkyl aluminum, boric acid and water, adding a metallocene complex after the reaction is finished, continuing the reaction, washing and draining after the reaction is finished to obtain a target catalyst system; wherein the carrier is silica having a specific surface area in the range of 200m2/g～600m2The particle size is 10-60 μm, and the pore volume is 0.8-3 mL/g. CarrierThe silicon dioxide is subjected to heat treatment (activation) before reaction, i.e. under the protection of nitrogen flow, at 400-600 ℃ for 2-24 hours. The surface hydroxyl content of the obtained silica gel is (1-5) OH/nm2。
The supported metallocene catalyst system for preparing syndiotactic polypropylene has a molar ratio of (water + boric acid)/alkylaluminum of 0.7-0.95 and SiO2The ratio of aluminum alkyl is 1g SiO2Adding (0.5-10) × 10-2mol of aluminum alkyl.
The molecular formula of the metallocene complex used by the supported metallocene catalyst system of the syndiotactic polypropylene is R1(CpR2 n)(FluR3 m)MQ2. Cp is cyclopentadienyl, Flu is fluorenyl, R2And R3Are respectively selected from H, C1～C12With m and n being in the range of 0 to 4, R1A bridging group being a linked cyclopentadienyl and fluorenyl radical, characterized by-C (CH)3)2-，-C(Ph)2-，-CH2-CH2-or-Si (CH)3)2-, M is Zr or Hf, Q is halogen or C1～C6Alkyl group of (1).
The molecular formula of boric acid used by the supported metallocene catalyst system of the syndiotactic polypropylene is RB (OH)2R is C1～C6Alkyl, phenyl or fluoro substituted phenyl.
When the supported metallocene catalyst system for preparing syndiotactic polypropylene is prepared, the addition amount of the metallocene complex is 1g of silica gel added by (1-30) × 10-5mol of metallocene complex.
All syntheses and polymerizations in the following examples were carried out in the absence of water and oxygen.
Example 1
Silica gel activation (Heat treatment)
The trade mark is
2408D (Grace) silica gel, in N2Activating at 200 deg.C for 2 hr under protection, heating from 200 deg.C to 600 deg.C within 4 hr, and activating at 600 deg.CAnd (4) dissolving for 4 hours, cooling to room temperature, and filling nitrogen for storage.
Example 2
Preparation of the catalyst
3.0g of activated silica gel is added into a reaction bottle, 30mL of toluene is added, the temperature is reduced to 0 ℃, 50mL of 1M trimethylaluminum solution is slowly dropped to react for 1 hour, the temperature is reduced to-15 ℃, 0.79g of 3, 5-difluorophenylboronic acid is added, after the reaction is carried out for 1 hour, 0.63g of water is slowly dropped to react for 12 hours after the temperature is increased to 40 ℃, and 0.08g of isopropylidene (cyclopentadiene) (9-fluorenyl) zirconium dichloride solution in toluene (10mL) is slowly dropped to react. After the reaction is continued for 1h, the mixture is filtered, washed with 15mL of toluene for three times respectively, and then is dried by pumping, so that 5.2g of the supported catalyst is obtained.
Example 3
Preparation of the catalyst
The conditions were the same as in example 2 except that the metallocene catalyst was changed to 0.10g of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, i.e., 0.10g of a toluene (10mL) solution of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride. Finally, 5.3g of supported catalyst was obtained.
Example 4
Preparation of the catalyst
The conditions were the same as in example 2 except that 0.79g of 3, 5-difluorophenylboronic acid was changed to 1.06g of 2,3,4,5, 6-pentafluorophenylboronic acid. Finally, 5.3g of supported catalyst was obtained.
Example 5
Preparation of the catalyst
The conditions were the same as in example 4 except that the metallocene catalyst was changed to 0.10g of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, i.e., 0.10g of a toluene (10mL) solution of diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride. Finally, 5.3g of supported catalyst was obtained.
Example 6
Preparation of the catalyst
The conditions were the same as in example 4, except that 0.72g of water was added instead. Finally, 5.2g of the supported catalyst was obtained.
Example 7
Preparation of the catalyst
The conditions were the same as in example 5, except that 0.72g of water was added instead. Finally, 5.1g of the supported catalyst was obtained.
Example 8
Preparation of the catalyst
The conditions were the same as in example 2 except that 50mL of a 1M triethylaluminum solution was slowly added dropwise instead. Finally, 5.0g of supported catalyst was obtained.
Example 9
Preparation of the catalyst
The conditions were the same as in example 3, except that 50mL of a 1M triethylaluminum solution was slowly added dropwise instead. Finally, 5.2g of the supported catalyst was obtained.
Example 10
Preparation of the catalyst
The conditions were the same as in example 4 except that 50mL of a 1M triethylaluminum solution was slowly added dropwise instead. Finally, 5.2g of the supported catalyst was obtained.
Example 11
Preparation of the catalyst
The conditions were the same as in example 5 except that 50mL of a 1M triethylaluminum solution was slowly added dropwise instead. Finally, 5.1g of the supported catalyst was obtained.
Example 12
Preparation of the catalyst
The conditions were the same as in example 6 except that 50mL of a 1M triethylaluminum solution was slowly added dropwise instead. Finally, 5.0g of supported catalyst was obtained.
Example 13
Preparation of the catalyst
The conditions were the same as in example 7 except that 50mL of a 1M triethylaluminum solution was slowly added dropwise instead. Finally, 5.1g of the supported catalyst was obtained.
Comparative example 1
Preparation of the catalyst
3.0g of activated silica gel is added into a reaction bottle, 30mL of toluene is added, the temperature is reduced to 0 ℃, 50mL of 1M MAO toluene solution is slowly dropped into the reaction bottle for reaction for 1 hour, the temperature is reduced to-15 ℃, the temperature is increased to 40 ℃ for reaction for 12 hours, and 0.08g of isopropylidene (cyclopentadiene) (9-fluorenyl) zirconium dichloride toluene (10mL) solution is slowly dropped into the reaction bottle. After the reaction is continued for 1h, the mixture is filtered, washed with 15mL of toluene for three times respectively, and then is dried by pumping, so that 5.8g of the supported catalyst is obtained.
Examples 14 to 25
Evaluation of catalyst
The propylene polymerization was carried out in a 5L stainless steel reactor with mechanical stirring. The dried reaction vessel was replaced with propylene gas three times, 750g of liquid propylene was added, then 5mL of 1M triisobutylaluminum hexane solution was added, and a certain amount (see Table 1 for details) of the supported catalysts obtained in examples 2 to 13 and comparative example 1 was added.
The temperature was raised to 60 ℃ to start the polymerization reaction. After 1 hour, the polymerization reaction is finished, unreacted propylene is discharged, the reaction kettle is cooled to room temperature, the polymer is collected, the polymer is dried in vacuum at the temperature of 60 ℃ to constant weight, and the polymerization activity is calculated after weighing.
The kind of supported catalyst during polymerization and other reaction conditions, polymerization activity and chain structure and molecular weight of the polymer are shown in Table 1.
In Table 1, the molecular weight and molecular weight distribution of the polymer were measured on a PL GPC-220 gel chromatograph. (1, 2, 4-trichlorobenzene is used as a mobile phase, the detection temperature is 150 ℃, polystyrene standard samples are used for universal correction, K is 59.1, and alpha is 0.69). The chain structure of the polymer is formed by13C-NMR detection.
TABLE 1 results of the Supported catalysts in catalyzing propylene polymerization
As can be seen from Table 1, the polypropylene catalyst prepared by the method can realize high-activity polymerization of propylene at a certain temperature (3.2Kg/(g Cat x h) -4.7Kg/(g Cat x h)); meanwhile, the product has higher weight average molecular weight (12.9 Kg. mol)-1-20.1Kg·mol-1) And a narrower molecular weight distribution index (2.1-2.4).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of a polypropylene catalyst, which is a supported metallocene catalyst used for preparing syndiotactic polypropylene, is characterized by comprising the following steps:
adding the heat-treated carrier into a solvent for dispersion, adding alkyl aluminum, boric acid and water for reaction, adding a metallocene complex for continuous reaction after the reaction is finished, and washing and draining after the reaction is finished to obtain the catalyst; in the preparation process of the catalyst, the addition amount of each component is as follows: the molar ratio of (water + boric acid)/alkyl aluminum is 0.7-0.95, SiO2The ratio of aluminum alkyl is 1g SiO2Adding (0.5-10) × 10-2mol of aluminum alkyl;
the metallocene complex is represented by the general formula (1): r1(CpR2 n)(FluR3 m)MQ2Wherein Cp is cyclopentadienyl, Flu is fluorenyl, R2And R3Each independently selected from H, C1 ~ C12M and n are integers of 0 to 4, R1Is a bridging group of a cyclopentadienyl group and a fluorenyl group, M is zirconium or hafnium, Q is halogen or C1 ~ C6Alkyl groups of (a); the addition amount of the metallocene complex is 1g of silica gel added with (1-30) × 10-5mol of metallocene complex;
the boric acid is represented by general formula (2): RB (OH)2Wherein R is phenyl, C1 ~ C6Alkyl or fluoro substituted phenyl of (a); the carrier is silica.
2. The method for preparing polypropylene catalyst according to claim 1, wherein R is1Has the structural formula of-C (CH)3)2-、-C(Ph)2-、-CH2-CH2-or-Si (CH)3)2-。
3. The method of claim 1, wherein the metallocene complex is isopropylidene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadiene) (9-fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride or vinyl (cyclopentadiene) (9-fluorenyl) zirconium dichloride.
4. The method for preparing a polypropylene catalyst according to claim 1, wherein the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum.
5. The method for preparing a polypropylene catalyst according to claim 1, wherein the silica has a specific surface area of 200m2/g ~ 600 m2(iv)/g, particle diameter is 10 to 60 μm, and pore volume is 0.8 to 3 mL/g.
6. The method for preparing a polypropylene catalyst according to claim 1, wherein the heat treatment is: treating for 2-24 hours at 400-600 ℃ under the protection of nitrogen flow.
7. The method for preparing a polypropylene catalyst according to claim 6, wherein the surface hydroxyl group content of the carrier after the heat treatment is 1-5 OH/nm2。
8. The method for preparing a polypropylene catalyst according to claim 1, wherein the solvent is toluene, cyclohexane or n-hexane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147949A (en) * | 1988-03-29 | 1992-09-15 | Exxon Chemical Patents Inc. | Polymerization process using a silica gel supported metallocene-alumoxane catalyst |
| CN1400211A (en) * | 2001-07-27 | 2003-03-05 | 浙江大学 | Boron-aluminium-oxygen alkane, its preparation method and application |
| CN102171253A (en) * | 2008-10-02 | 2011-08-31 | 道达尔石油化学产品研究弗吕公司 | Activating supports based on perfluorinated boronic acids |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147949A (en) * | 1988-03-29 | 1992-09-15 | Exxon Chemical Patents Inc. | Polymerization process using a silica gel supported metallocene-alumoxane catalyst |
| CN1400211A (en) * | 2001-07-27 | 2003-03-05 | 浙江大学 | Boron-aluminium-oxygen alkane, its preparation method and application |
| CN102171253A (en) * | 2008-10-02 | 2011-08-31 | 道达尔石油化学产品研究弗吕公司 | Activating supports based on perfluorinated boronic acids |
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