CN115160458A - Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof - Google Patents
Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof Download PDFInfo
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- CN115160458A CN115160458A CN202210918747.XA CN202210918747A CN115160458A CN 115160458 A CN115160458 A CN 115160458A CN 202210918747 A CN202210918747 A CN 202210918747A CN 115160458 A CN115160458 A CN 115160458A
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- C08F110/02—Ethene
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Abstract
The invention relates to the technical field of catalysts, and particularly discloses a catalyst suitable for producing polyolefin with superfine particle size, which comprises a superfine carrier treated by a surfactant, wherein the particle size of the superfine carrier is 0.01-10 microns, and the superfine carrier is selected from at least one of alumina, activated carbon, clay, silica, titanium dioxide, polystyrene and calcium carbonate; a phosphinimine nickel catalyst supported on a superfine carrier; the mass percentage of the superfine carrier is 70.0-80.0%, and the mass percentage of the phosphinimine nickel catalyst is 20.0-30.0%. The invention overcomes the defects of the prior art, and the nickel phosphinimine oxide catalyst has high activity and stability for ethylene polymerization under the condition of not needing any cocatalyst, and is beneficial to the popularization of the catalyst in the application aspect of polyolefin with ultra-fine grain diameter.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly belongs to a catalyst suitable for producing polyolefin with ultra-fine particle size and a preparation method thereof.
Background
Polyolefins generally refer to a generic term for thermoplastic resins obtained by polymerizing or copolymerizing an α -olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., and certain cyclic olefins, alone.
The superfine polyethylene has wide application, and superfine polyolefin products such as superfine ultrahigh molecular weight polyethylene, superfine polyethylene wax, superfine high density polyethylene and the like are used for manufacturing products such as injection molding, extrusion molding, blow molding and the like by downstream customers.
The invention patent with the patent application number of CN201811417277.9 is characterized in that an inorganic carrier obtained after treatment by a surfactant is used as a first carrier, active magnesium chloride generated in situ on the first carrier by a magnesium-containing reagent is used as a second carrier, and a catalyst active component loaded on the second carrier is a Ziegler-Natta catalyst. Compared with the prior art, the catalyst can be used for preparing polyethylene products with high bulk density, uniform particles and average particle size of less than 200 microns, and can be used for preparing and applying middle-high density polyolefin.
However, the catalyst needs to adopt a cocatalyst when being applied to the preparation of polyolefin, which greatly limits the application of the catalyst in production, so how to develop a polyolefin catalyst without the cocatalyst becomes a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a catalyst suitable for producing polyolefin with superfine particle size and a preparation method thereof, overcomes the defects of the prior art, has high activity and stability for ethylene polymerization under the condition of not needing any cocatalyst, and is beneficial to popularization of the catalyst in the application aspect of the polyolefin with superfine particle size.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a catalyst suitable for producing polyolefin having an ultrafine particle diameter, comprising
The particle size of the superfine carrier is 0.01-10 microns, and the superfine carrier is selected from at least one of alumina, activated carbon, clay, silicon dioxide, titanium dioxide, polystyrene and calcium carbonate;
the phosphinimine nickel catalyst loaded on the superfine carrier has the following structure:
the mass percentage of the superfine carrier is 70.0-80.0%, and the mass percentage of the phosphinimine nickel catalyst is 20.0-30.0%.
Furthermore, one end of the molecular structure of the surfactant is a hydrophilic group, and the other end of the molecular structure of the surfactant is a hydrophobic group, and the surfactant is selected from one or more of fatty acid methyl ester, alkyl olefine acid methyl ester or alkyl dienoic acid methyl ester.
Further, the preparation method of the nickel phosphinimine oxide catalyst comprises the following steps:
step one, dissolving N- (2, 6-diisopropyl phenyl) benzimide chloride and diphenyl ethoxy phosphine in an organic solvent under the conditions of nitrogen protection and heating, and then carrying out reflux reaction for 12 hours;
step two, after the reaction is finished, naturally cooling to room temperature, removing the organic solvent by using a rotary evaporator, and then passing eluent through a silica gel column to obtain a bright yellow solid powdery ligand;
and step three, dissolving the ligand, sodium (3, 5-bis (trifluoromethyl) phenyl) borate and allyl nickel chloride in dichloromethane and stirring for 6 hours at room temperature under the protection of nitrogen, then filtering the reaction solution by using laponite to remove a by-product sodium chloride generated in the reaction, and pumping the filtrate to obtain a bright yellow solid product.
Further, in the first step, the molar mass ratio of the N- (2, 6-diisopropylphenyl) benzimida chloride to the diphenyl ethoxy phosphine is 1 (1-2), and the organic solvent is one of toluene, xylene, DMF or DMSO.
In the third step, the molar mass ratio of the ligand, sodium (3, 5-bis (trifluoromethyl) phenyl) borate and allyl nickel chloride is 1: (1-2).
The invention also provides a preparation method suitable for producing the superfine grain size polyolefin catalyst, which comprises the following steps:
(1) Respectively weighing a superfine carrier and a phosphinimine nickel catalyst according to the mass percentage, respectively grinding the superfine carrier and the phosphinimine nickel catalyst, and sieving for later use;
(2) Ultrasonically dispersing the superfine carrier in an organic solvent, adding a surfactant, and reacting at 20-240 ℃ to obtain a modified superfine carrier;
(3) And (3) in an organic solvent, dipping the nickel phosphinimine oxide catalyst on the superfine carrier obtained in the step (2), and reacting with the surface of the carrier to load the nickel phosphinimine oxide catalyst on the superfine carrier.
Further, the organic solvent is selected from long-chain saturated alkane, aromatic hydrocarbon or halogenated aromatic hydrocarbon of C10-C20, or a mixed solvent of the long-chain saturated alkane, the aromatic hydrocarbon and the halogenated aromatic hydrocarbon.
The invention finally protects the application of the catalyst suitable for producing the polyolefin with the ultrafine grain diameter, the catalyst is used for producing the polyethylene with the ultrafine grain diameter by olefin polymerization, and the average grain diameter of the obtained polyethylene is 10-500 mu m.
Compared with the prior art, the invention has the following implementation effects:
the catalyst suitable for producing the polyolefin with the ultrafine particle size and the preparation method thereof have high activity and stability for ethylene polymerization under the condition of not needing any cocatalyst through the phosphinimine nickel oxide catalyst, and are beneficial to popularization of the catalyst in the application aspect of the polyolefin with the ultrafine particle size.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples, and any modification is within the scope of the present invention without departing from the spirit of the present invention.
Example 1
This example discloses a catalyst suitable for producing polyolefin with ultra-fine particle size, which is characterized in that: comprises that
The particle size of the superfine carrier is 0.01-10 microns, and the superfine carrier is selected from at least one of alumina, activated carbon, clay, silicon dioxide, titanium dioxide, polystyrene and calcium carbonate; one end of the molecular structure of the surfactant is a hydrophilic group, and the other end of the molecular structure of the surfactant is a hydrophobic group, and the surfactant is selected from one or more of fatty acid methyl ester, alkyl olefine acid methyl ester or alkyl dienoic acid methyl ester.
The phosphinimine nickel catalyst loaded on the superfine carrier has the following structure:
example 2
Based on example 1, this example discloses a preparation method of a phosphinimine nickel catalyst, which comprises the following steps:
dissolving N- (2, 6-diisopropylphenyl) benzimide chloride and diphenyl ethoxy phosphine in an organic solvent according to a molar mass ratio of 1;
step two, after the reaction is finished, naturally cooling to room temperature, removing the organic solvent by using a rotary evaporator, and then passing eluent through a silica gel column to obtain a bright yellow solid powdery ligand;
and step three, dissolving the ligand, sodium (3, 5-bis (trifluoromethyl) phenyl) borate and allyl nickel chloride in dichloromethane according to a molar mass ratio of 1.
Example 3
The preparation method adopted in this example is substantially the same as that of example 2, except that: the molar mass of N- (2, 6-diisopropylphenyl) benzimida chloride and diphenylethoxyphosphine was 1.
Example 4
The preparation method adopted in this example is substantially the same as that of example 2, except that: the molar mass ratio of the ligand to the sodium (3, 5-bis (trifluoromethyl) phenyl) borate and the allylnickel chloride is 1.
Example 5
This example discloses a preparation method suitable for producing an ultrafine particle size polyolefin catalyst based on examples 1 and 2, which is characterized in that: the method comprises the following steps:
(1) Respectively weighing 20% of superfine carrier and 80% of phosphinimine nickel catalyst according to the mass percentage, respectively grinding the superfine carrier and the phosphinimine nickel catalyst, and sieving for later use;
(2) Ultrasonically dispersing the superfine carrier in an organic solvent, adding a surfactant, and reacting at 20-240 ℃ to obtain a modified superfine carrier;
(3) In an organic solvent, dipping a nickel phosphinimine oxide catalyst on the superfine carrier obtained in the step (2), and reacting with the surface of the carrier to load the nickel phosphinimine oxide catalyst on the superfine carrier;
the organic solvent is selected from C10-C20 long-chain saturated alkane, aromatic hydrocarbon or halogenated aromatic hydrocarbon, or their mixture.
Example 6
The preparation method adopted in this example is substantially the same as that of example 5, except that: the weight percentage content of the superfine carrier is 70.0 percent, and the weight percentage content of the phosphinimine nickel catalyst is 30.0 percent.
The catalyst provided by the embodiment 1 of the invention and the catalyst provided by the patent with the patent application number of CN201811417277.9 are respectively used for carrying out polyethylene catalytic polymerization experiments, and the obtained polyethylene is weighed to obtain the weight of 12mg and the weight of 10mg respectively.
Therefore, the nickel phosphinimine oxide catalyst adopted by the method can reach the level of industrial production without using a cocatalyst, and is beneficial to popularization of the catalyst in the application aspect of polyolefin with ultra-fine particle size.
The foregoing is merely exemplary and illustrative of the present inventive concept and various modifications, additions and substitutions of similar embodiments may be made to the specific embodiments described by those skilled in the art without departing from the inventive concept or exceeding the scope of the claims as defined in the accompanying claims.
Claims (8)
1. A catalyst suitable for producing polyolefin having an ultrafine particle diameter, characterized in that: comprises that
The superfine carrier is treated by a surfactant, the particle size of the superfine carrier is 0.01-10 microns, and the superfine carrier is selected from at least one of alumina, activated carbon, clay, silicon dioxide, titanium dioxide, polystyrene and calcium carbonate;
the phosphinimine nickel catalyst loaded on the superfine carrier has the following structure:
the mass percentage of the superfine carrier is 70.0-80.0%, and the mass percentage of the phosphinimine nickel catalyst is 20.0-30.0%.
2. The catalyst suitable for producing an ultra fine particle size polyolefin in accordance with claim 1, wherein: one end of the molecular structure of the surfactant is a hydrophilic group, the other end of the molecular structure of the surfactant is a hydrophobic group, and the surfactant is selected from one or more of fatty acid methyl ester, alkyl olefine acid methyl ester or alkyl dienoic acid methyl ester.
3. The catalyst suitable for producing an ultra fine particle size polyolefin in accordance with claim 1, wherein: the preparation method of the phosphinimine nickel catalyst comprises the following steps:
dissolving N- (2, 6-diisopropylphenyl) benzimide chloride and diphenyl ethoxy phosphine in an organic solvent under the conditions of nitrogen protection and heating, and then carrying out reflux reaction for 12 hours;
step two, after the reaction is finished, naturally cooling to room temperature, removing the organic solvent by using a rotary evaporator, and then passing eluent through a silica gel column to obtain a bright yellow solid powdery ligand;
and step three, dissolving the ligand, sodium (3, 5-bis (trifluoromethyl) phenyl) borate and allylnickel chloride in dichloromethane and stirring for 6 hours at room temperature under the protection of nitrogen, then filtering the reaction solution by using laponite to remove a by-product sodium chloride generated in the reaction, and pumping the filtrate to obtain a bright yellow solid product.
4. A catalyst suitable for producing an ultra fine particle size polyolefin in accordance with claim 3, wherein: in the first step, the molar mass ratio of the N- (2, 6-diisopropylphenyl) benzimidachloride to the diphenyl ethoxy phosphine is 1 (1-2), and the organic solvent is one of toluene, xylene, DMF or DMSO.
5. The catalyst suitable for producing an ultra fine particle size polyolefin according to claim 3, wherein: in the third step, the molar mass ratio of the ligand, sodium (3, 5-bis (trifluoromethyl) phenyl) borate and allyl nickel chloride is 1: (1-2).
6. A method for preparing a catalyst suitable for producing an ultra fine particle size polyolefin according to any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) Respectively weighing superfine carrier and phosphinimine nickel catalyst according to mass percentage, respectively grinding the superfine carrier and the phosphinimine nickel catalyst, and sieving for later use;
(2) Ultrasonically dispersing the superfine carrier in an organic solvent, adding a surfactant, and reacting at 20-240 ℃ to obtain a modified superfine carrier;
(3) And (3) in an organic solvent, dipping the nickel phosphinimine oxide catalyst on the superfine carrier obtained in the step (2), and reacting with the surface of the carrier to load the nickel phosphinimine oxide catalyst on the superfine carrier.
7. The method for preparing a catalyst suitable for producing an ultra fine particle size polyolefin according to claim 6, wherein: the organic solvent is selected from long-chain saturated alkane, aromatic hydrocarbon or halogenated aromatic hydrocarbon of C10-C20 or a mixed solvent thereof.
8. Use of a catalyst suitable for producing an ultra fine particle size polyolefin according to claim 1, wherein: the catalyst is used for olefin polymerization to produce polyethylene with superfine grain size, and the average grain size of the obtained polyethylene is 300-600 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210918747.XA CN115160458A (en) | 2022-08-02 | 2022-08-02 | Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof |
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| CN202210918747.XA CN115160458A (en) | 2022-08-02 | 2022-08-02 | Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof |
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| CN115160458A true CN115160458A (en) | 2022-10-11 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438593A (en) * | 2018-11-26 | 2019-03-08 | 上海化工研究院有限公司 | A kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application |
| CN109535290A (en) * | 2018-11-26 | 2019-03-29 | 上海化工研究院有限公司 | It is suitble to the catalyst and its preparation method and application of production ultra-fine grain diameter polyolefin |
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- 2022-08-02 CN CN202210918747.XA patent/CN115160458A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438593A (en) * | 2018-11-26 | 2019-03-08 | 上海化工研究院有限公司 | A kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application |
| CN109535290A (en) * | 2018-11-26 | 2019-03-29 | 上海化工研究院有限公司 | It is suitble to the catalyst and its preparation method and application of production ultra-fine grain diameter polyolefin |
Non-Patent Citations (1)
| Title |
|---|
| JIAXIN GAO ET AL.: "Sterics versus electronics:Imine/phosphine-oxide-based nickel catalysts for ethylene polymerization and copolymerization", 《JOURNAL OF CATALYSIS》, vol. 369, pages 233, XP085605974, DOI: 10.1016/j.jcat.2018.11.007 * |
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