CN113201086A - Catalyst system of polyolefin blend and application - Google Patents
Catalyst system of polyolefin blend and application Download PDFInfo
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- CN113201086A CN113201086A CN202110461301.4A CN202110461301A CN113201086A CN 113201086 A CN113201086 A CN 113201086A CN 202110461301 A CN202110461301 A CN 202110461301A CN 113201086 A CN113201086 A CN 113201086A
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- catalyst
- transition metal
- complex
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- nano carrier
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a catalyst system of a polyolefin blend and application thereof, wherein the catalyst system comprises a main catalyst, a cocatalyst, a reference catalyst and a complex; the main catalyst consists of a nano carrier and a transition metal catalyst loaded on the nano carrier, wherein the mass percent of the nano carrier is 60-80%, and the mass percent of the transition metal catalyst is 20-40%; the cocatalyst is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum; the reference catalyst employs Cp2ZrCl2(ii) a The complex adopts high-activity alpha-diimine nickel. Overcomes the defects of the prior art, improves the copolymerization activity of a catalytic system, effectively improves the molecular weight of the obtained polyolefin, simultaneously improves the elasticity of the polyolefin at normal temperature, and greatly improves the quality of polyethylene products。
Description
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a catalyst system of a polyolefin blend and application thereof.
Background
Polyolefin products obtained by homopolymerization or copolymerization of ethylene and alpha-olefin (butene, hexene, octene and the like) are one of the most important synthetic polymers, and are widely applied to life and production, such as food packaging, agricultural film mulching films and vehicle materials. Although the supply and demand of the polyolefin market in China are generally stable in recent years, the low-end product has surplus capacity, and the high-end product has low self-sufficient rate, so that the external dependence of the high-end product (high added value) reaches 80%. With the improvement of the living standard of people in China and the continuous change of consumption structures, the demand of high-grade products is rapidly increased, and the traditional polyolefin industry faces severe supply and demand contradictions. The traditional polyolefin industry needs to accelerate transformation and upgrade of industrial structure and research and development of high-end products, so as to reduce the external dependence of China on high-end brand products, ensure the sustainable development of the polyolefin industry, and further promote the development of social economy and improvement of the living standard of people
Olefin polymerization catalysts are the core of polyolefin polymerization technology, and there are two main aspects in summary from the development of olefin polymerization catalysts: (1) the development of a polyolefin resin catalyst capable of producing a polyolefin resin having a specific property or a more excellent property, such as a metallocene catalyst, a non-metallocene late transition metal catalyst, etc.; (2) for the production of general polyolefin resin, on the basis of further improving the performance of the catalyst, the preparation process of the catalyst is simplified, the cost of the catalyst is reduced, and an environment-friendly technology is developed to improve the benefit and enhance the competitiveness. Before the 80 s in the 20 th century, the research on polyethylene catalysts focuses on pursuing catalyst efficiency, and through the efforts of nearly 30 years, the catalytic efficiency of the polyethylene catalysts is improved, the production process of polyolefin is simplified, and the energy consumption and material consumption are reduced.
The polyethylene prepared by the existing polyethylene catalyst has the problem of insufficient tensile strength, influences the quality of polyethylene products and hinders the high-end upgrading of the industry.
Disclosure of Invention
The invention aims to provide a catalyst system of polyolefin blend and application thereof, overcomes the defects of the prior art, improves the copolymerization activity of the catalyst system, effectively improves the molecular weight of the obtained polyolefin, simultaneously improves the elasticity of the polyolefin at normal temperature, and greatly improves the quality of polyethylene products.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a catalyst system and application of polyolefin blend comprises a main catalyst, a cocatalyst, a reference catalyst and a complex;
the main catalyst consists of a nano carrier and a transition metal catalyst loaded on the nano carrier, wherein the mass percent of the nano carrier is 60-80%, and the mass percent of the transition metal catalyst is 20-40%;
the cocatalyst is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum;
the reference catalyst employs Cp2ZrCl2；
The complex adopts high-activity alpha-nickel diimine;
the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: (1-10): (0.2-2): (2-6).
Further, the catalyst comprises a main catalyst, a cocatalyst, a reference catalyst and a complex;
the main catalyst consists of a nano carrier and a transition metal catalyst loaded on the nano carrier, wherein the mass percent of the nano carrier is 70%, and the mass percent of the transition metal catalyst is 30%;
the cocatalyst is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum;
the reference catalyst employs Cp2ZrCl2；
The complex adopts high-activity alpha-nickel diimine;
the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: 5: 1: 3.
further, the nano-carrier is composed of silicate and reactive magnesium chloride, and the weight ratio of the silicate to the reactive magnesium chloride is (1-10): 1.
Further, the transition metal catalyst is selected from at least one of a ziegler-natta catalyst, a metallocene catalyst, a non-metallocene pre-transition metal catalyst, or a post-transition metal catalyst.
Further, the pro-oxidant is activated by heating and microwave irradiation prior to mixing.
Further, a reducing agent can be added into the complex before use to mix the complex to prepare a reducing catalyst with a certain concentration.
The invention also protects the application of the catalyst system of the polyolefin blend, in an olefin polymerization reactor, ethylene, alpha-olefin comonomer and the catalyst system are added for polymerization reaction to produce polyethylene, and the addition amount of the catalyst system is 5-10% of the total mass of the ethylene.
Compared with the prior art, the invention has the following beneficial effects:
according to the catalyst system and the application of the polyolefin blend, the copolymerization activity of the catalyst system is improved through the matching of the main catalyst, the cocatalyst and the reference catalyst, the molecular weight of the obtained polyolefin is effectively improved, the branching degree of the polyolefin is reduced through the reduced complex, and the elasticity of the polyolefin at normal temperature is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example discloses a catalyst system for polyolefin blends, which is characterized by: comprises a main catalyst, an auxiliary catalyst, a reference catalyst and a complex;
the main catalyst consists of a nano carrier and a transition metal catalyst loaded on the nano carrier, wherein the mass percent of the nano carrier is 60%, and the mass percent of the transition metal catalyst is 40%;
the cocatalyst is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum;
the reference catalyst employs Cp2ZrCl2；
The complex adopts high-activity alpha-nickel diimine;
the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: 1: 0.2: 2.
wherein the nano-carrier consists of silicate and reactive magnesium chloride, and the weight ratio of the silicate to the reactive magnesium chloride is 1:1.
Wherein the transition metal catalyst is selected from at least one of Ziegler-Natta catalyst, metallocene catalyst, non-metallocene pre-transition metal catalyst or post-transition metal catalyst.
Wherein the pro-oxidant is activated by heating and microwave irradiation prior to mixing.
Wherein, the complex can be added with a reducing agent before use to be mixed to prepare a reducing catalyst with a certain concentration, and the reducing agent adopts cobaltocene.
Example 2
This example is essentially the same as example 1 with respect to catalyst system composition and ratio, except that: the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: 5: 1: 3.
example 3
This example is essentially the same as example 1 with respect to catalyst system composition and ratio, except that: the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: 10: 2: 6.
comparative example 1
This comparative example is essentially the same as the catalyst system of example 1 in composition and ratio, except that: the mass percent of the nano carrier is 70 percent, and the mass percent of the transition metal catalyst is 30 percent.
Comparative example 2
This comparative example is essentially the same as the catalyst system of example 1 in composition and ratio, except that: the mass percent of the nano carrier is 80 percent, and the mass percent of the transition metal catalyst is 20 percent
Comparative example 3
This comparative example is essentially the same as the catalyst system of example 1 in composition and ratio, except that: the nano-carrier consists of silicate and reactive magnesium chloride in a weight ratio of 5: 1.
Comparative example 4
This comparative example is essentially the same as the catalyst system of example 1 in composition and ratio, except that: the nano-carrier consists of silicate and reactive magnesium chloride in a weight ratio of 10: 1.
Comparative example 5
This comparative example is essentially the same as the catalyst system of example 1 in composition and ratio, except that: the pro-oxidant is not heated and microwave irradiated prior to mixing.
Comparative example 6
This comparative example is essentially the same as the catalyst system of example 1 in composition and ratio, except that: the complex is not reduced prior to use.
And (3) performance detection:
in an olefin polymerization reactor, ethylene, an alpha-olefin comonomer and the catalyst systems prepared in examples 1 to 3 and comparative examples 1 to 6 were added to carry out polymerization reaction to produce polyethylene, wherein the addition amount of the catalyst system was 5% of the total mass of ethylene, and the obtained polyethylene products were tested according to the following test methods:
1. polymer Melt Index (MI): measured according to GB/T3682-2000;
2. and (3) activity calculation: the catalyst activity (mass of polyolefin prepared)/(mass of catalyst solid component) g/g;
3. resin tensile bending stress: measured according to GB/T1040.2-2006;
4. resin flexural strength and flexural modulus: measured according to GB/T9341-2008;
5. impact strength of the simply supported beam: measured according to GB/T1043.1-2008.
The specific detection results are shown in table 1;
TABLE 1 Performance test results
The addition amount of the catalyst system prepared in the proportion of example 1 is adjusted to 7% and 10% of the total mass of ethylene, and the performance test is performed, and the specific detection results are shown in table 2:
TABLE 2 Performance test results for different addition ratios
The results in tables 1 and 2 show that the catalyst system obtained by the method of the embodiment of the invention can effectively improve the copolymerization activity of the catalyst system, improve the performance of the polyethylene product, improve the elasticity of the polyethylene product at normal temperature, and facilitate the upgrading of the product.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. A catalyst system for polyolefin blends characterized by: comprises a main catalyst, an auxiliary catalyst, a reference catalyst and a complex;
the main catalyst consists of a nano carrier and a transition metal catalyst loaded on the nano carrier, wherein the mass percent of the nano carrier is 60-80%, and the mass percent of the transition metal catalyst is 20-40%;
the cocatalyst is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum;
the reference catalyst employs Cp2ZrCl2；
The complex adopts high-activity alpha-nickel diimine;
the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: (1-10): (0.2-2): (2-6).
2. Catalyst system for polyolefin blends according to claim 1, characterized in that: comprises a main catalyst, an auxiliary catalyst, a reference catalyst and a complex;
the main catalyst consists of a nano carrier and a transition metal catalyst loaded on the nano carrier, wherein the mass percent of the nano carrier is 60%, and the mass percent of the transition metal catalyst is 40%;
the cocatalyst is selected from one or more of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum;
the reference catalyst employs Cp2ZrCl2；
The complex adopts high-activity alpha-nickel diimine;
the molar ratio of the main catalyst to the cocatalyst to the reference catalyst to the complex is as follows: 100: 5: 1: 3.
3. catalyst system for polyolefin blends according to claim 1, characterized in that: the nano-carrier consists of silicate and reactive magnesium chloride, and the weight ratio of the silicate to the reactive magnesium chloride is (1-10): 1.
4. Catalyst system for polyolefin blends according to claim 1, characterized in that: the transition metal catalyst is selected from at least one of Ziegler-Natta catalyst, metallocene catalyst, non-metallocene pre-transition metal catalyst or post-transition metal catalyst.
5. Catalyst system for polyolefin blends according to claim 1, characterized in that: the pro-oxidant is activated by heating and microwave irradiation prior to mixing.
6. Catalyst system for polyolefin blends according to claim 1, characterized in that: the complex can be added with a reducing agent before use to be mixed to prepare a reducing catalyst with a certain concentration.
7. Use of a catalyst system for polyolefin blends according to any of claims 1 to 6, characterized in that: in an olefin polymerization reactor, ethylene, an alpha-olefin comonomer and a catalyst system are added for polymerization reaction to produce polyethylene, wherein the addition amount of the catalyst system is 5-10% of the total mass of the ethylene.
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| CN202110461301.4A CN113201086A (en) | 2021-04-27 | 2021-04-27 | Catalyst system of polyolefin blend and application |
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Citations (6)
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| US20070255022A1 (en) * | 2006-04-28 | 2007-11-01 | Fina Technology, Inc. | Fluorinated transition metal catalysts and formation thereof |
| CN102887967A (en) * | 2012-10-17 | 2013-01-23 | 上海化工研究院 | Composite catalyst for producing polyethylene with wide molecular weight distribution as well as production method and application thereof |
| CN103450381A (en) * | 2013-05-30 | 2013-12-18 | 上海化工研究院 | Nano-carrier catalyst for producing reinforced polyethylene as well as preparation method and application of catalyst |
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| CN107022040A (en) * | 2017-03-29 | 2017-08-08 | 上海化工研究院有限公司 | Produce carried catalyst of wear-resisting anti-static polyolefin and its preparation method and application |
| CN107903344A (en) * | 2017-11-02 | 2018-04-13 | 上海化工研究院有限公司 | Produce catalyst of polyalkene diaphragm PP Pipe Compound and its preparation method and application |
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2021
- 2021-04-27 CN CN202110461301.4A patent/CN113201086A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070255022A1 (en) * | 2006-04-28 | 2007-11-01 | Fina Technology, Inc. | Fluorinated transition metal catalysts and formation thereof |
| CN102887967A (en) * | 2012-10-17 | 2013-01-23 | 上海化工研究院 | Composite catalyst for producing polyethylene with wide molecular weight distribution as well as production method and application thereof |
| CN103450381A (en) * | 2013-05-30 | 2013-12-18 | 上海化工研究院 | Nano-carrier catalyst for producing reinforced polyethylene as well as preparation method and application of catalyst |
| CN104558295A (en) * | 2015-02-09 | 2015-04-29 | 上海化工研究院 | Carrier catalyst for producing wear-resistant flame-retardant polyethylene as well as preparation method and application of carrier catalyst |
| CN107022040A (en) * | 2017-03-29 | 2017-08-08 | 上海化工研究院有限公司 | Produce carried catalyst of wear-resisting anti-static polyolefin and its preparation method and application |
| CN107903344A (en) * | 2017-11-02 | 2018-04-13 | 上海化工研究院有限公司 | Produce catalyst of polyalkene diaphragm PP Pipe Compound and its preparation method and application |
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