CN115043964A - Inert liquid assisted olefin polymerization method - Google Patents
Inert liquid assisted olefin polymerization method Download PDFInfo
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- CN115043964A CN115043964A CN202210879187.1A CN202210879187A CN115043964A CN 115043964 A CN115043964 A CN 115043964A CN 202210879187 A CN202210879187 A CN 202210879187A CN 115043964 A CN115043964 A CN 115043964A
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- 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
Abstract
The invention discloses an inert liquid assisted olefin polymerization method. The method of the invention adds inert liquid which does not chemically react with any substance in a polymerization reaction system into a slurry reaction kettle, so that the inert liquid collides with polymer particles in a droplet form, and after the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover the inert liquid and a reaction solvent, and finally, a dry olefin polymerization product is obtained, and the polymerization product has the characteristic of low entanglement.
Description
Technical Field
The present invention relates to an inert liquid assisted olefin polymerization process. More particularly, the present invention relates to the control of the condensed state structure of a polymer product by introducing an inert liquid into an olefin slurry polymerization such that the inert liquid and a reaction solvent rich in the reaction raw materials form a micromixing flow field which alternately contacts with active particles.
Background
Polyolefin materials are one of the most used high molecular materials at present, and the condensed structure of the materials is a key factor influencing the mechanical property and the processing property. In olefin polymerization, the growth process of molecular chains influences the condensed structure of the polymerization product. At industrial reaction temperature, the chain growth rate is far greater than the chain crystallization rate, so that the primary chain segment cannot be crystallized in time, and the molecular chain is subjected to intra-chain overlapping, so that a large amount of chain entanglement exists in a polymerization product. For olefin polymers with higher molecular weight, in the process of processing and melting, chain entanglement limits the diffusion and creeping behavior of molecular chains, so that the melt viscosity is increased rapidly, a large number of defects exist in products easily, and the advantage of mechanical strength of a high molecular weight part cannot be exerted.
US 7671159B 2 discloses a method for preparing low-entanglement ultrahigh molecular weight polyethylene by dilute solution-low temperature homogeneous polymerization, wherein the polymerization under low temperature can ensure that the chain crystallization rate is greater than the chain growth rate, and effectively inhibit the formation of chain entanglement. However, the temperature condition of the polymerization method is too low, and the industrial application value is not high. CN202011295674.0 discloses a polymerization method and apparatus for preparing super-high molecular weight disentangled polyethylene, wherein nitrogen gas passes through a nano-micro-bubble generator and enters a reactor in the form of nano-micro-bubbles to intermittently collide catalyst particles, so as to create an inert gas (nitrogen gas)/ethylene monomer "alternating and alternating" micro-mixed flow field around the active center, so that the chain growth rate is less than the chain crystallization rate, and the molecular chain disentanglement of nascent state super-high molecular weight polyethylene is realized. However, bubbles rise continuously in a liquid phase system until the bubbles disappear, and inert gas needs to be continuously introduced and discharged, so that the problem of entrainment of gas and liquid is easily caused, and the recovery of ethylene raw material gas is difficult.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art and to provide an inert liquid assisted olefin polymerization process.
In the process of the present invention, an inert liquid sparingly soluble and/or immiscible with a reaction solvent is introduced into a slurry polymerization reaction system to collide with polymer particles in the form of droplets, and a polymerization product is obtained after the slurry polymerization reaction is completed. In the process of the present invention, the resulting polymer slurry is fed to a post-treatment section to recover inert liquid and reaction solvent, and finally a dry olefin polymerization product is obtained.
In the method of the present invention, the inert liquid does not chemically react with any substance in the reaction system;
in the process of the present invention, the mass of the dissolved portion of the inert liquid in the reaction solvent is less than 10% by weight of the amount of the inert liquid added.
In the process of the present invention, the volume of inert liquid in the slurry polymerization system is less than 10% of the total liquid volume.
In the process of the invention, the inert liquid has the formula (C) y1 H y2 O y3 X y4 Si y5 P y6 ) n Y1 is 1-15, y2 is 0-31, y3 is 0-47, y4 is 0-37, and y4>0 (when y2 is 0), y5 is 0-32, y6 is 0-33, and n is 1-1000. X is one of F, Cl and Br. Preferably, the inert liquid is (C) 4 H 7 F 3 OSi) n, n being 10-1000, or (CF) 2 O) n, n is 10-3000.
In the method of the present invention, the inert liquid droplet size ranges from 0.1 μm to 10 mm.
In the process of the invention, the collision frequency of the inert liquid droplets with the polymer particles is from 5 to 500 Hz.
In the process of the present invention, the procatalyst of the slurry polymerization reaction system is selected from the group consisting of ziegler-natta catalyst, metallocene catalyst, transition metal catalyst, inorganic chromium catalyst and organic chromium catalyst; the cocatalyst is selected from alkyl aluminum or alkyl aluminoxane.
In the process of the present invention, the reaction temperature of the slurry polymerization is in the range of-10 to 160 deg.C, preferably 68 to 85 deg.C.
In the process of the present invention, the pressure of the slurry polymerization is 0.1 to 10MPa, preferably 0.5 to 1 MPa.
In the method of the present invention, the reaction monomer of the slurry polymerization reaction system is one or more of alpha-olefins having 2 to 10 carbon atoms, preferably ethylene.
In the process of the present invention, the reaction solvent of the slurry polymerization reaction system is selected from alkanes having less than 15 carbon atoms, preferably isopentane, n-hexane and n-heptane.
The slurry polymerization reaction system can be a homopolymer system or a copolymerization system, and the comonomer is alpha-olefin which is different from the reaction monomer and has carbon number more than 3, preferably 1-butene, 1-hexene and 1-octene. When the comonomer addition is 0, the polymerized product is an olefin homopolymer.
The molecular weight of the polymer obtained by the polymerization of the method of the invention is 10-10000kg/mol, and the initial storage modulus at 160 ℃ is 0.06-1.8MPa, preferably 0.1-0.3 MPa. When y4 is not 0, the X content of the polymer surface is 0.01-10% by mass. When y5 is not 0, the Si content of the polymer surface is 0.01 to 10% by mass. When y6 is not 0, the P content of the polymer surface is 0.01-10% by mass.
Compared with the prior art, the invention has the advantages that:
the invention adds the inert liquid into the olefin slurry polymerization, so that the inert liquid is dispersed in a system in a droplet form and is in intermittent contact with polymer particles, the growing active chain is frequently switched between a reaction state and a dormant state, the time is gained for the crystallization of a primary chain segment, and the final polymerization product has the characteristic of low entanglement. Meanwhile, the inert liquid can be continuously present in the system, and the action time is long. In addition, the inert liquid remains partially on the polymer surface after the separation operation, and the selection of a specific inert liquid can improve the surface properties of the olefin polymer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The following methods were used to test the structure or properties of the polymers produced in the examples:
high temperature gel permeation chromatography is used to test the molecular weight of the polymer and its distribution index.
A rotational rheometer was used to measure the shear storage modulus (160 ℃ C.) of the polymer. The smaller the initial storage modulus, the lower the degree of chain entanglement.
An X-ray energy spectrometer is used for analyzing the mass content of the F element on the surface of the olefin polymer.
In each example and each comparative example, the amounts of the catalyst, the cocatalyst, the solvent n-heptane and the reaction monomer ethylene were all the same.
Example 1
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, isopentane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n being 10-100, n having an average value of 20.
Isopentane and an inert liquid were fed into the reactor, wherein the volume of the inert liquid was 2% of the total liquid volume, and a slurry polymerization was carried out at a temperature of 40 ℃ and a pressure of 0.3MPa, the average size of droplets of the inert liquid was 150 μm, and the collision frequency of the droplets with the polymer particles was 220 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained. The results of the related characterization and performance tests of the obtained product are shown in table 1.
Example 2
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, normal hexane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n is 200-400, and the average value of n is 250.
N-hexane and an inert liquid were fed into the reactor, wherein the volume of the inert liquid was 2% of the total liquid volume, and a slurry polymerization was carried out at a temperature of 80 ℃ and a pressure of 0.8MPa, the average size of the droplets of the inert liquid was 560 μm, and the collision frequency of the droplets with the polymer particles was 110 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained.
Example 3
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n is 500-700, and the average value of n is 580.
Into the reactor were fed n-heptane and an inert liquid, the volume of which was 2% of the total liquid volume, and the slurry polymerization was carried out at a temperature of 130 ℃ and a pressure of 2MPa, the average size of the droplets of the inert liquid being 1.4mm, and the collision frequency of the droplets with the polymer particles being 65 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained.
Example 4
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n is 800-.
Into the reactor were fed n-heptane and an inert liquid, wherein the volume of the inert liquid was 0.5% of the total liquid volume, and the slurry polymerization was carried out at a temperature of 160 ℃ and a pressure of 6MPa, the average size of the droplets of the inert liquid was 5.5mm, and the collision frequency of the droplets with the polymer particles was 8 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained.
Example 5
This example uses MgCl 2 Supported TiCl 4 As a catalyst, toTriethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (CF) 2 O) n, n is 10-500, and the average value of n is 200.
Into the reactor were fed n-heptane and an inert liquid, wherein the volume of the inert liquid was 4% of the total liquid volume, and the slurry polymerization was carried out at a temperature of 70 ℃ and a pressure of 0.6MPa, the average size of the droplets of the inert liquid was 350 μm, and the collision frequency of the droplets with the polymer particles was 160 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally a dry olefin polymerization product is obtained.
Example 6
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n being 10-100, n having an average value of 20.
Into the reactor were fed n-heptane and an inert liquid, wherein the volume of the inert liquid was 6% of the total liquid volume, and the slurry polymerization was carried out at a temperature of 70 ℃ and a pressure of 0.6MPa, the average size of the droplets of the inert liquid was 380 μm, and the collision frequency of the droplets with the polymer particles was 270 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained.
Example 7
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n being 10-100, n having an average value of 20.
Into the reactor were fed n-heptane and an inert liquid, wherein the volume of the inert liquid was 8% of the total liquid volume, and the slurry polymerization was carried out at a temperature of 70 ℃ and a pressure of 0.6MPa, the average size of the droplets of the inert liquid was 430 μm, and the collision frequency of the droplets with the polymer particles was 340 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained.
Example 8
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer. The inert liquid is (C) 4 H 7 F 3 OSi) n, n being 10-100, n having an average value of 20.
Into the reactor were fed n-heptane and an inert liquid, wherein the volume of the inert liquid was 4% of the total liquid volume, and the slurry polymerization was carried out at a temperature of 70 ℃ and a pressure of 0.6MPa, the average size of the droplets of the inert liquid was 500 μm, and the collision frequency of the droplets with the polymer particles was 450 Hz. After the reaction is finished, the obtained polymer slurry enters a post-treatment working section to recover inert liquid and reaction solvent, and finally, a dry olefin polymerization product is obtained.
Comparative example 1
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, normal hexane is used as a solvent, and ethylene is used as a reaction monomer.
N-hexane (the volume of the n-hexane used in comparative example 1 is the sum of the volumes of the n-hexane and the inert liquid used in example 2) was charged into a reactor to conduct slurry polymerization at a temperature of 80 ℃ and a pressure of 0.8 MPa.
Comparative example 2
This example uses MgCl 2 Supported TiCl 4 As a catalyst, triethyl aluminum is used as a cocatalyst, n-heptane is used as a solvent, and ethylene is used as a reaction monomer.
N-heptane (the volume of n-heptane used in comparative example 2 was the sum of the volumes of n-heptane and the inert liquid used in example 5) was charged into the reactor to conduct slurry polymerization at 70 ℃ and a pressure of 0.6 MPa.
The results of the characterization and performance testing of the products obtained in the examples and comparative examples are shown in table 1.
TABLE 1 test results of polyethylene products finally obtained in examples 1 to 8 and comparative examples 1 to 2
As can be seen from examples 1 to 8 and comparative examples 1 to 2, the addition of the inert liquid is effective in reducing the initial storage modulus of the polymerization product, i.e., in reducing the degree of chain entanglement of the polymerization product.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. An inert liquid assisted olefin polymerization process comprising the steps of:
introducing inert liquid which is slightly soluble and/or insoluble with a reaction solvent into a slurry polymerization reaction system, so that the inert liquid collides with polymer particles in the form of liquid drops, and obtaining an olefin polymerization product after the polymerization reaction is finished;
the inert liquid does not react with any substance in the reaction system;
the mass of the dissolved part of the inert liquid in the reaction solvent of the slurry polymerization reaction system is less than 10 wt% of the introduced amount of the inert liquid;
the volume of inert liquid in the slurry polymerization system is less than 10% of the total liquid volume.
2. The inert liquid-assisted olefin polymerization process of claim 1, wherein the inert liquid has the formula (C) y1 H y2 O y3 X y4 Si y5 P y6 ) n Y1 is 1-15, y2 is 0-31, y3 is 0-47, y4 is 0-37, and y4>0 (when y2 is 0), y5 is 0-32, y6 is 0-33, and n is 1-1000; x isF. One of Cl and Br.
3. The inert liquid assisted olefin polymerization process of claim 2 wherein the inert liquid is (C) 4 H 7 F 3 OSi) n, n being 10-1000, or (CF) 2 O) n, n is 10-3000.
4. The inert liquid assisted olefin polymerization process of claim 1, wherein the inert liquid droplet size ranges from 0.1 μm to 10 mm.
5. The inert liquid assisted olefin polymerization process of claim 1, wherein the collision frequency of the inert liquid droplets with the polymer particles is from 5 to 500 Hz.
6. The inert liquid-assisted olefin polymerization process of claim 1, wherein the procatalyst of the slurry polymerization reaction system is selected from the group consisting of ziegler-natta catalyst, metallocene catalyst, transition metal catalyst, inorganic chromium catalyst and organic chromium catalyst; the cocatalyst of the slurry polymerization reaction system is alkyl aluminum or alkyl aluminoxane.
7. The inert liquid-assisted olefin polymerization process of claim 1, wherein the reaction temperature of the slurry polymerization reaction system is in the range of-10 ℃ to 160 ℃.
8. The inert liquid assisted olefin polymerization process of claim 1, wherein the pressure of the slurry polymerization reaction system is from 0.1 to 10 MPa.
9. The inert liquid-assisted olefin polymerization process of claim 1, wherein the reactive monomer of the polymerization reaction system is one or more of alpha-olefins having 2 to 10 carbon atoms.
10. The inert liquid assisted olefin polymerization process of claim 1, wherein the reaction solvent is selected from alkanes having less than 15 carbon atoms.
11. A polymer product prepared according to the inert liquid assisted olefin polymerization process of claims 1-10, wherein the molecular weight of the polymer product is 100-10000kg/mol and the initial storage modulus at 160 ℃ is 0.06-1.8 MPa.
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Patent Citations (5)
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| CN109438594A (en) * | 2018-11-26 | 2019-03-08 | 宁波大学 | A method of preparing extrahigh-molecular weight polyolefins |
| CN112321759A (en) * | 2020-11-18 | 2021-02-05 | 浙江大学 | Polyolefin with low shear modulus and application thereof |
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