CN114702616B - Method for preparing olefin copolymer by utilizing microbubbles - Google Patents

Method for preparing olefin copolymer by utilizing microbubbles Download PDF

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CN114702616B
CN114702616B CN202210430074.3A CN202210430074A CN114702616B CN 114702616 B CN114702616 B CN 114702616B CN 202210430074 A CN202210430074 A CN 202210430074A CN 114702616 B CN114702616 B CN 114702616B
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olefin copolymer
comonomer
microbubbles
molecular weight
weight distribution
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CN114702616A (en
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历伟
严翔
叶姝瑶
王靖岱
帅云
黄正梁
阳永荣
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Zhejiang University ZJU
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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
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • 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

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Abstract

The invention discloses a method for preparing an olefin copolymer by utilizing microbubbles, which is characterized in that the olefin copolymer with adjustable molecular weight distribution and density is prepared by introducing olefin monomers and/or comonomers and/or microbubbles of inert gases into a polymerization system. The method has simple process, the olefin copolymer prepared by the method has the characteristics of adjustable molecular weight distribution and density, strong comonomer insertion capability and the like, flexibly meets various product requirements, improves the utilization rate of the comonomer, solves the problem of reduced comonomer insertion capability in the later stage of polymerization, and improves the processing performance and the service performance of the product to a certain extent.

Description

Method for preparing olefin copolymer by utilizing microbubbles
Technical Field
The present invention relates to a method for preparing an olefin copolymer, and more particularly, to a method for preparing an olefin copolymer having an adjustable molecular weight distribution and density by introducing microbubbles of an olefin monomer and/or a comonomer and/or an inert gas into a polymerization system.
Background
Polyolefin materials are the most widely used and most productive polymer materials at present, and generally refer to resin materials obtained by homo-or copolymerization of ethylene, propylene, alpha-olefin and certain cycloolefins. With the increase of the alpha-olefin content in olefin copolymers, the property of materials is changed from polyolefin plastics to polyolefin elastomers (POE), and the materials have been widely used in the fields of automobiles, shoe materials, wires, cables, packages, seals and the like.
The molecular weight and molecular weight distribution of the polymer are important factors affecting the mechanical properties and processability of the polymer, and the preparation of a polymer having a broad or bimodal molecular weight distribution can effectively improve the processability of the polymer, which has been widely studied in the field of polyolefin resins. Compared with a polymer with narrow molecular weight distribution, the polymer with broad or bimodal molecular weight distribution not only maintains the excellent mechanical property of the high molecular weight part, but also has the unique processing property of the small molecular weight part, so that the mechanical property and the processing property are well balanced. Chinese patent CN201610041319.8 provides a method for directly synthesizing a bimodal molecular weight distribution cycloolefin copolymer using a single reactor and a double active center composite catalyst, and the molecular weight distribution of the cycloolefin copolymer obtained by the method is between 15 and 35, and the cycloolefin copolymer has both excellent mechanical properties of the high molecular weight portion and excellent processability of the low molecular weight portion. Meanwhile, the method avoids the defect that the copolymer prepared by a non-metallocene single-site catalyst is easy to cause gel because of too high molecular weight, and solves the problems that the cycloolefin copolymer prepared by a metallocene catalyst system is relatively narrow in molecular weight distribution and poor in processability. Chinese patent CN201810361306.8 provides a process for preparing a bimodal polyolefin elastomer using a single catalyst system in a single reactor using a bimetallic complex as the main catalyst, the molecular weight distribution of the resulting polymer product being between 4 and 10. The patent mentioned above all starts from the point of catalyst design, and the preparation of polymer with bimodal molecular weight distribution, the synthesis of catalyst has complicated process, and the problem of mutual interference of active components exists.
In addition, in the copolymerization of an olefin monomer with an α -olefin, the copolymerization efficiency of the α -olefin is generally not sufficiently high. In order to increase the alpha-olefin content of the copolymer, a special catalyst with a limited geometry is required, or a large amount of alpha-olefin is required to be added, so that the production cost is increased, the utilization rate of the alpha-olefin is reduced, and the recovery load is increased. In addition, in the later stage of the polymerization reaction, the insertion capability of the comonomer is reduced, so that the random sequence distribution content in the copolymer is less, and the production process and the product quality are affected. The presently disclosed patent addresses the above problems primarily by synthesizing novel catalyst systems. Chinese patent CN201610030967.3 provides a ziegler-natta type vanadium-based catalyst system for olefin polymerization comprising a vanadium compound main catalyst, an organoaluminum compound cocatalyst and a compound modifier comprising a carbon-halogen bond. The vanadium-based catalyst system has high catalytic activity, can reduce the catalyst dosage, and can improve the copolymerization efficiency of alpha-olefin or diene, the utilization rate of alpha-olefin or diene and the random sequence distribution content in the copolymer in the copolymerization of ethylene and alpha-olefin, ethylene and diene or ethylene and alpha-olefin and/or diene, and the comonomer insertion rate is obviously improved. Chinese patent CN202110468624.6 provides a new catalyst system for ethylene/α -olefin copolymerization which fine-adjusts the electronic properties and steric hindrance of the catalyst ligand substituents, and has the advantages of high catalytic activity, high molecular weight and high comonomer insertion rate. The synthesis catalyst has complex process and high requirement on synthesis conditions, and is not beneficial to industrial production. However, the presently disclosed patent does not address the above-mentioned problems from the standpoint of chemical reaction engineering.
In view of the above, the present inventors have studied to solve the problems exposed in the related art, such as difficulty in balancing processability and usability of olefin copolymers, low comonomer insertion ability in polymers, low comonomer utilization, lowered comonomer insertion ability in the late stage of polymerization, etc., and have desired to provide a method for producing olefin copolymers using microbubbles which effectively solves the above problems.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, it is an object of the present invention to provide a method for producing an olefin copolymer using microbubbles. In recent years, microbubbles have played an important role in the fields of water treatment, drug release, metallurgy, and the like. As the size of the bubbles decreases, the mass transfer efficiency of the bubbles increases, the rising speed decreases, the residence time increases, and the burst energy increases. By virtue of the above advantages of microbubbles, the present invention prepares olefin copolymers with adjustable molecular weight distribution and density by introducing microbubbles of olefin monomers and/or comonomers and/or inert gases into the polymerization system. The method has simple process, the olefin copolymer prepared by the method has the characteristics of adjustable molecular weight distribution and density, strong comonomer insertion capability and the like, flexibly meets various product requirements, improves the utilization rate of the comonomer, solves the problem of reduced comonomer insertion capability in the later stage of polymerization, and improves the processing performance and the service performance of the product to a certain extent.
It is another object of the present invention to provide an olefin copolymer having an adjustable molecular weight distribution and density, which is produced according to the method.
According to one aspect of the present invention, there is provided a process for producing an olefin copolymer using microbubbles, wherein an olefin monomer, a comonomer, a procatalyst, a cocatalyst and/or an inert gas are subjected to polymerization reaction in a solvent, wherein the apparatus for carrying out the polymerization reaction has a microbubble generator through which at least one of the olefin monomer, the comonomer and the inert gas participates in the reaction in the form of microbubbles.
In the method of the present invention, the molecular weight distribution and density of the olefin copolymer are adjusted by changing the gas type of the microbubbles or adjusting the ratio of each gas of the microbubbles, and the molecular weight distribution of the olefin copolymer prepared is 2 to 80, and the density is 0.86 to 0.97g/cm 3 。
The molecular weight distribution and density of the olefin copolymer and the microbubble adjustment means have the following correspondence, and the corresponding microbubble adjustment means can be selected according to the required olefin copolymer:
when only the olefin monomer is selected to participate in the polymerization reaction in the form of microbubbles, the catalyst can be used for preparing a catalyst having a molecular weight distribution of 2 to 10 and a density of 0.90 to 0.97g/cm 3 An olefin copolymer of (a);
when only the comonomer is selected to participate in the polymerization reaction in the form of microbubbles, the polymer can be prepared with a molecular weight distribution of 2 to 20 and a density of 0.86 to 0.90g/cm 3 An olefin copolymer of (a);
when only inert gas is selected to assist the polymerization reaction in the form of micro bubbles, an olefin copolymer with a molecular weight distribution of 20-80 can be prepared;
when the olefin monomer and the comonomer are selected to participate in the polymerization reaction together in the form of microbubbles, the catalyst can prepare a catalyst with molecular weight distribution of 2-10 and density of 0.86-0.97 g/cm 3 An olefin copolymer of (a);
when olefin monomers and inert gases are selected to participate in polymerization reaction together in the form of microbubbles, olefin copolymers with molecular weight distribution of 10-80 can be prepared;
co-participation of selected comonomer and inert gas in the form of microbubbles in polymerizationIn the reaction, the molecular weight distribution is 20 to 80 and the density is 0.86 to 0.90g/cm 3 An olefin copolymer of (a);
when olefin monomer, comonomer and inert gas are selected to participate in polymerization reaction together in the form of micro bubbles, the catalyst can prepare the catalyst with molecular weight distribution of 2-80 and density of 0.86-0.97 g/cm 3 An olefin copolymer of (a) and (b).
When the olefin monomer participates in the polymerization reaction in the form of microbubbles, the mass transfer coefficient of the olefin monomer in the solvent increases, the dissolution rate increases, and the polymerization activity increases. In addition, because of the violent disturbance action of the micro bubbles on the solvent, the back mixing action of the solvent is enhanced, so that the raw material gas is uniformly mixed in the solvent, the influence of dead zones in the reactor on the performance of the polymerization product is improved, and the olefin copolymer with narrower molecular weight distribution is generated.
When the comonomer participates in the polymerization reaction in the form of microbubbles, the mass transfer coefficient of the comonomer in the solvent is increased, the dissolution rate is increased, the comonomer content is enriched, so that the utilization rate of the comonomer is improved, the insertion capability of the comonomer in the product is improved, the problem that the insertion capability of the comonomer is reduced in the later stage of the polymerization reaction is effectively solved, and the density range of the copolymerization product is adjusted. In addition, comonomer microbubbles have a severe disturbance effect on the solvent, the back mixing effect of the solvent is enhanced, and the raw material gas is uniformly mixed in the solvent to generate the olefin copolymer with narrower molecular weight distribution.
When the inert gas assists the polymerization reaction in the form of microbubbles, the large amount of inert microbubbles reduces the concentration of the feed gas, forming a plurality of feed gas enrichment regions and feed gas depletion regions in the reactor. The heterogeneous distribution of the raw material gas in the solvent and the concentration difference of each region lead to the broadening of the molecular weight distribution of the polymerization product, and the olefin copolymer with wider molecular weight distribution is generated, so that the performance of the polymerization product is improved to a certain extent.
When the olefin monomer and the comonomer participate in the polymerization reaction together in the form of microbubbles, the molecular weight distribution of the generated polymerization product is narrower, but the density of the polymerization product can be flexibly adjusted according to the content difference of the olefin monomer and the comonomer. When the comonomer content is a majority, the density of the polymerization product is smaller, and when the olefin monomer content is a majority, the density of the polymerization product is greater.
When the olefin monomer and the inert gas participate in the polymerization reaction together in the form of microbubbles, the resulting polymerization product has a wide and narrow molecular weight distribution according to the difference in the contents of the olefin monomer and the inert gas. When the olefin monomer content is a large part, the molecular weight distribution of the polymerization product tends to be narrow, and when the inert gas content is a large part, the molecular weight distribution of the polymerization product tends to be broad, and the mixed micro-bubble form can satisfy the requirements of high catalyst polymerization activity and broad molecular weight distribution of the product.
When the comonomer and the inert gas participate in the polymerization reaction together in the form of microbubbles, the resulting polymerization product will have different molecular weight distribution and density depending on the difference in the content of the comonomer and the inert gas. When the comonomer content is a large part, the density of the polymerization product is small, and when the inert gas content is a large part, the molecular weight distribution of the polymerization product is broad.
When the olefin monomer, the comonomer and the inert gas are co-participated in the polymerization reaction in the form of microbubbles, the resulting polymerization product has an adjustable molecular weight distribution and density range according to the difference in the contents of the olefin monomer, the comonomer and the inert gas.
In the preferred embodiment of the present invention, the desired olefin copolymer is obtained by merely changing the gas type of the microbubbles or adjusting the ratio of each gas of the microbubbles without changing the apparatus of the polymerization reaction and other reaction conditions.
In the process of the present invention, the olefin monomer is preferably one or more of ethylene, propylene, butene, butadiene, pentene.
In the process of the present invention, the comonomer is one or more of C3 to C20 alpha olefins, preferably one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene.
In the process of the present invention, the inert gas is a gas which is poorly soluble or insoluble in a solvent, and which does not affect the polymerization reaction, preferably one or more of nitrogen, argon, propane, butane.
In the process of the present invention, the solvent is an organic solvent, preferably toluene, ethylbenzene, benzene, n-hexane, cyclohexane, n-heptane, cyclopentane, C 4 ～C 18 One or more of normal paraffins, isoparaffins and naphthenes.
In the method of the invention, the main catalyst is selected from one or more of Ziegler Natta catalyst, FI catalyst, rare earth amino complex, post-transition metal catalyst, phillips catalyst, pre-transition metal catalyst and metallocene catalyst, and the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, n-butyllithium, triisobutylaluminum, trimethylaluminum, trifluorophenylboron, tributylammonium tetra (pentafluorophenyl) aluminum, trifluoroborane and tetrapentafluorobenzeneborate.
In the method of the invention, the microbubble generator is one or more of microporous materials, micro-channels, micro-nozzles, ultrasonic generators, venturi tubes and aeration heads, preferably one or more of ceramic membranes, SPG membranes, metal sintering porous media, polycarbonate membranes and polystyrene membranes, and the aperture ratio of the microporous materials is 10-80%. The diameter of the microbubbles generated by the microbubble generator was 10 -6 ～10 -2 m, the volume fraction of the micro-bubbles in the solvent in the reaction system is 10% -90%.
According to one embodiment of the invention, the polymerization temperature is-50 to 230 ℃ and the polymerization pressure is 0.1 to 20MPa.
According to another aspect of the present invention, there is provided an olefin copolymer having an adjustable molecular weight distribution and density, the olefin copolymer having a molecular weight distribution of 2 to 80 and a density of 0.86 to 0.97g/cm, prepared according to the method 3 。
Compared with the prior art, the invention utilizes the introduction of the olefin monomer and/or comonomer and/or the micro-bubble of inert gas in the polymerization system, thereby effectively solving the technical problems that the processability and the service performance of the olefin copolymer are difficult to balance, the comonomer insertion capability of the polymer is low, the comonomer utilization rate is low, the comonomer insertion capability is reduced in the later period of the polymerization reaction and the like which are exposed in the prior art. The polymerization method has simple process and improves the processing property and the service property of the product to a certain extent.
According to another aspect of the present invention, there is also provided an olefin copolymer prepared according to the above method. The olefin copolymer prepared by the invention has the advantages of adjustable molecular weight distribution and density, strong comonomer insertion capability and the like.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples. The following examples are only illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used in the examples were conventional products commercially available without the manufacturer's knowledge.
Characterization method of olefin copolymer structure and performance:
(1) Weight average molecular weight and molecular weight distribution: determined by high Wen Shentou gel chromatography HT-GPC.
(2) Density: measured according to the method of GB/1033-1986.
(3) Comonomer insertion rate: according to 13 C-NMR was measured and calculated.
Example 1
In this example, ziegler-Natta catalyst was used as the main catalyst, triethylaluminum as the co-catalyst, cyclopentane as the solvent, and 1-butene as the comonomer. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst, cocatalyst and comonomer into the reaction vessel and is dispersed in the solvent by means of a stirrer. And then introducing ethylene microbubbles by using a microbubble generator, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and polymerizing for 1h to obtain the olefin copolymer A. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer A prepared in this example are shown in Table 1.
Example 2
In this example, ziegler-Natta catalyst was used as the main catalyst, triethylaluminum as the co-catalyst, cyclopentane as the solvent, and 1-butene as the comonomer. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst and cocatalyst into the reaction vessel and is dispersed in the solvent by means of a stirrer. The microbubble generator is utilized to introduce the microbubbles of the 1-butene, and the air inlet pipe is utilized to introduce the ethylene (the air inlet pipe is commonly used in the prior art and is not provided with the microbubble generator, and the following steps are carried out), so that the system is polymerized at 120 ℃ and 1.0MPa, and the olefin copolymer B is obtained after polymerization for 1 h. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer B prepared in this example are shown in Table 1.
Example 3
In this example, ziegler-Natta catalyst is used as the main catalyst, triethylaluminum as the cocatalyst, cyclopentane as the solvent, 1-butene as the comonomer, and nitrogen as the inert gas. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst, cocatalyst and comonomer into the reaction vessel and is dispersed in the solvent by means of a stirrer. And introducing nitrogen microbubbles by using a microbubble generator, and introducing ethylene by using an air inlet pipe, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and polymerizing for 1h to obtain the olefin copolymer C. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer C prepared in this example are shown in Table 1.
Example 4
In this example, ziegler-Natta catalyst was used as the main catalyst, triethylaluminum as the co-catalyst, cyclopentane as the solvent, and 1-butene as the comonomer. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst and cocatalyst into the reaction vessel and is dispersed in the solvent by means of a stirrer. And introducing microbubbles of ethylene and 1-butene (the air inflow ratio of the ethylene to the 1-butene is 1:1) by utilizing a microbubble generator, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and polymerizing for 1h to obtain the olefin copolymer D. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer D prepared in this example are shown in Table 1.
Example 5
In this example, ziegler-Natta catalyst is used as the main catalyst, triethylaluminum as the cocatalyst, cyclopentane as the solvent, 1-butene as the comonomer, and nitrogen as the inert gas. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst, cocatalyst and comonomer into the reaction vessel and is dispersed in the solvent by means of a stirrer. And introducing microbubbles of ethylene and nitrogen by using a microbubble generator (the air inflow ratio of the ethylene to the nitrogen is 3:1), so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and polymerizing for 1h to obtain the olefin copolymer E. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer E prepared in this example are shown in Table 1.
Example 6
In this example, ziegler-Natta catalyst is used as the main catalyst, triethylaluminum as the cocatalyst, cyclopentane as the solvent, 1-butene as the comonomer, and nitrogen as the inert gas. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst and cocatalyst into the reaction vessel and is dispersed in the solvent by means of a stirrer. And (3) introducing microbubbles of 1-butene and nitrogen by using a microbubble generator (the air inflow ratio of the 1-butene to the nitrogen is 3:1), and introducing ethylene by using an air inlet pipe, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and polymerizing for 1h to obtain the olefin copolymer F. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer F prepared in this example are shown in Table 1.
Example 7
In the embodiment, ziegler-Natta catalyst is used as a main catalyst, triethylaluminum is used as a cocatalyst, cyclopentane is used as a solvent, 1-butene is used as a comonomer, and nitrogen is used as inert gas. The microbubble generator consists of four microporous aeration heads and is symmetrically distributed at the bottom of the reaction kettle. The microporous material is ceramic, and the diameter of micropores is 50 μm.
First, the feed solvent carries the procatalyst and cocatalyst into the reaction vessel and is dispersed in the solvent by means of a stirrer. And introducing microbubbles of ethylene, 1-butene and nitrogen (the air inflow ratio of the ethylene, the 1-butene and the nitrogen is 2:2:1) by using a microbubble generator, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and polymerizing for 1h to obtain the olefin copolymer G. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer G prepared in this example are shown in Table 1.
Comparative example 1
In this example, ziegler-Natta catalyst was used as the main catalyst, triethylaluminum as the co-catalyst, cyclopentane as the solvent, and 1-butene as the comonomer.
First, the feed solvent carries the procatalyst, cocatalyst and comonomer into the reaction vessel and is dispersed in the solvent by means of a stirrer. Ethylene is introduced from an air inlet pipe, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and the olefin copolymer H is obtained after polymerization for 1H. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer H prepared in this example are shown in Table 1.
Comparative example 2
In this example, ziegler-Natta catalyst is used as the main catalyst, triethylaluminum as the cocatalyst, cyclopentane as the solvent, 1-butene as the comonomer, and nitrogen as the inert gas.
First, the feed solvent carries the procatalyst, cocatalyst and comonomer into the reaction vessel and is dispersed in the solvent by means of a stirrer. Ethylene and nitrogen are introduced from an air inlet pipe, so that the system is subjected to polymerization reaction at 120 ℃ and 1.0MPa, and the olefin copolymer I is obtained after polymerization for 1 h. Discharging after the reaction is finished, and calculating the activity of the product.
The results of the characterization and performance test of the olefin copolymer I prepared in this example are shown in Table 1.
The results of the performance tests on the olefin copolymer products prepared in examples 1 to 7 and comparative example 1 are as follows:
TABLE 1
Figure BDA0003609853550000081
From the results of characterization of the olefin copolymers prepared in examples 1 to 7 and comparative examples 1 and 2, it is understood that the olefin copolymer A prepared in example 1 has the narrowest molecular weight distribution and the highest activity, the comonomer insertion capability and the minimum density of the olefin copolymer B are the strongest, and the molecular weight distribution of the olefin copolymer C is the widest. By introducing microbubbles of olefin monomer and/or comonomer and/or inert gas into the polymerization system, olefin copolymers A, B, C, D, E, F and G have a more adjustable molecular weight distribution and density than olefin copolymer H, I of comparative examples 1 and 2, affecting comonomer insertion capability in the polymer to some extent, by varying the microbubbles introduced.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (5)

1. A method for preparing an olefin copolymer by utilizing microbubbles is characterized in that an olefin monomer, a comonomer, a main catalyst, a cocatalyst and inert gas are subjected to polymerization reaction in a solvent, wherein a device for carrying out the polymerization reaction is provided with a microbubble generator, the olefin monomer is ethylene, the comonomer is 1-butene, the inert gas is indissolvable or insoluble in the solvent, and the inert gas does not participate in the polymerization reaction; the diameter of the micro-bubbles generated by the micro-bubble generator is 10 -6 ~10 - 2 m, wherein the micro-bubbles account for 10% -90% of the volume fraction of the solvent in the reaction system;
according to the molecular weight distribution and density required by the target olefin copolymer, in the preparation process, the required olefin copolymer is obtained by changing the gas types of the microbubbles according to the corresponding relation;
the corresponding relation is as follows:
a) When an olefin monomer and inert gas are selected to participate in polymerization reaction together in the form of microbubbles, an olefin copolymer with molecular weight distribution of 10-80 can be prepared;
b) When the comonomer and the inert gas are selected to participate in the polymerization reaction together in the form of microbubbles, the polymer can be prepared with molecular weight distribution of 20-80 and density of 0.86-0.90 g/cm 3 An olefin copolymer of (a);
c) The olefin monomer, comonomer and inert gas are selected to be co-referenced in the form of microbubblesCan prepare a polymer having a molecular weight distribution of 2 to 80 and a density of 0.86 to 0.97g/cm 3 An olefin copolymer of (a);
in the preparation process, according to the corresponding relation, the device and other reaction conditions of the polymerization reaction are not changed, and the needed olefin copolymer is obtained only by changing the gas types of the microbubbles.
2. The method of claim 1, wherein the solvent is one or more of toluene, ethylbenzene, benzene, n-hexane, cyclohexane, n-heptane, cyclopentane.
3. The process according to claim 1, wherein the main catalyst is selected from one or more of Ziegler Natta catalyst, FI catalyst, phillips catalyst, and the cocatalyst is selected from one or more of methylaluminoxane, triethylaluminum, n-butyllithium, triisobutylaluminum, trimethylaluminum, trifluoroborane.
4. The method of claim 1, wherein the microbubble generator is one or more of an ultrasonic wave generator, a venturi tube, and an aerator.
5. The method according to any one of claims 1 to 4, wherein the polymerization temperature is-50 to 230 ℃ and the polymerization pressure is 0.1 to 20mpa.
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