CN112375171B - Preparation method of polypropylene material - Google Patents
Preparation method of polypropylene material Download PDFInfo
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- CN112375171B CN112375171B CN202011173554.3A CN202011173554A CN112375171B CN 112375171 B CN112375171 B CN 112375171B CN 202011173554 A CN202011173554 A CN 202011173554A CN 112375171 B CN112375171 B CN 112375171B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
The invention relates to a preparation method of a polypropylene material, in particular to a preparation method of a high-impact polypropylene material, belonging to the technical field of high polymer materials. The invention provides a preparation method of a polypropylene material, which comprises the steps of selecting a proper main catalyst (UDC104) by optimizing a polymerization process technology, and polymerizing propylene through a loop and a gas phase reactor under the combined action of the main catalyst, a cocatalyst (triethylaluminum) and an external electron donor (DIPDMS) to obtain polypropylene powder; uniformly mixing the polypropylene powder with an antioxidant, an auxiliary antioxidant and a nucleating agent, and extruding by an extruder to obtain a polypropylene material with a melt flow rate of 5-15 g/10 min; the method can effectively improve the ethylene content and the rubber phase component content in the gas phase copolymerization stage in the process of producing the impact-resistant polypropylene, and can prevent fine powder from sticking a kettle and materials from caking in the gas phase copolymerization stage, thereby effectively improving the impact resistance and the stress whitening resistance of the product.
Description
Technical Field
The invention relates to a preparation method of a polypropylene material, in particular to a preparation method of a high impact polypropylene material, and belongs to the technical field of high polymer materials.
Background
The impact polypropylene has the rigidity of propylene homopolymer and the impact resistance of ethylene propylene rubber component, has good rigidity-toughness balance, and is widely applied to the fields of automobiles, household appliances, injection molding containers and the like. Among them, the higher the content of the rubber phase is, the better the impact resistance of the product is, and the higher the content of ethylene in the rubber phase is, the better the stress whitening resistance of the product is, therefore, increasing the ethylene content in the impact polypropylene becomes the goal pursued by researchers. However, in the actual production process, when the ethylene content in the polymerization system reaches the upper limit of the production capacity of the existing polymerization process, the content of the ethylene-propylene rubber component and the ethylene content in the rubber phase cannot be further improved, the impact resistance and the stress whitening resistance of the product are also limited, and the impact-resistant polypropylene with higher ethylene content obtained by the method in the prior art has better application prospect and market competitiveness. High ethylene content impact polypropylenes are typically produced by a multi-stage polymerization process. The homopolymerization of propylene in the first reactor is carried out to obtain propylene polymer, and then the propylene polymer is conveyed to the next reactor to carry out the copolymerization of propylene and ethylene, and polymers mainly comprising ethylene-propylene random copolymers are generated in the pores of propylene polymer particles. Currently, the vast majority of impact polypropylenes utilize ethylene as a comonomer, and the propylene-ethylene copolymerization is carried out in a gas phase reactor.
For the Spheripol polymerization process with a liquid-phase loop reactor connected in series with a gas-phase fluidized bed reactor, the polymerization activity of the Ziegler-Natta catalyst is remarkably reduced in the second gas-phase copolymerization stage after the polymerization activity of the first liquid-phase homopolymerization stage is rapidly released. Meanwhile, in order to prevent the rubber phase from forming or wrapping on the surface of the polymer particles entering the second reactor, which causes sticky materials, an anti-sticking agent is added in the second polymerization step to inhibit the polymerization activity on the surface of the polymer particles, so that the rubber phase is formed only in the inner pores of the polymer particles. The addition of the anti-sticking agent further reduces the polymerization activity of the gas-phase copolymerization. The rubber phase content in the product is determined by the capacity control of the second polymerization step, namely the polymerization activity and the residence time of the materials in the reactor, and after the polymerization activity is greatly consumed, the capacity control can be carried out only through the residence time of the materials. However, for the existing domestic Spheripol polymerization production device, due to the limitation of the design and construction scale of a gas phase reactor, when the material level of a fluidized bed reaches the maximum limit, the retention time of the material in a gas phase copolymerization stage is not long enough, the regulation and control range of the production process is limited, and the rubber phase content of an impact-resistant polypropylene product cannot meet the index requirement easily.
In summary, the existing problems are that when the impact polypropylene product is prepared, the productivity of the second gas-phase copolymerization stage needs to be regulated and controlled to obtain a rubber phase component with a specific content, and when the later polymerization activity of the ziegler natta catalyst is insufficient and the residence time of the gas-phase copolymerization reaction is short due to the small construction scale of the gas-phase reactor, the fine powder is often stuck to the kettle, the material is caked, and the second polymerization productivity cannot be regulated and controlled. Therefore, a method is needed to be found, so that the capacity of the gas-phase copolymerization reaction in the second step can be conveniently regulated and controlled under the condition of limited residence time in the gas-phase copolymerization stage, an impact-resistant polypropylene product with specific rubber phase content is obtained, meanwhile, the modification cost and energy consumption of the device are not increased, and the capability of the process device for producing the product brand is widened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a polypropylene material.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a polypropylene material comprises the following steps:
(1) adding propylene, a main catalyst, a cocatalyst and an external electron donor into a polymerization reactor to obtain polypropylene;
(2) adding the polypropylene, propylene and hydrogen in the step (1) into a first loop reactor for polymerization reaction, and controlling the concentration of the hydrogen and the density of gas in the first loop reactor to obtain a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization reaction, and controlling the concentration of the hydrogen and the density of gas in the second loop reactor to obtain a product B;
(4) removing liquid-phase propylene from the product B obtained in the step (3), adding the product B into a gas-phase reaction kettle, and controlling the temperature, the pressure and the gas-phase ratio of the gas-phase kettle to obtain polypropylene powder;
(5) and (5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and then extruding the mixture by an extruder to obtain the polypropylene material.
The invention provides a preparation method of a polypropylene material, which comprises the steps of selecting a proper main catalyst (UDC104) by optimizing a polymerization process technology, and polymerizing propylene through a loop and a gas phase reactor to obtain polypropylene powder under the combined action of the main catalyst, a cocatalyst (triethyl aluminum) and an external electron donor (DIPDMS); and uniformly mixing the polypropylene powder with the antioxidant, the auxiliary antioxidant and the nucleating agent, and extruding by an extruder to obtain the polypropylene material with the melt flow rate of 5-15 g/10 min.
As a preferred embodiment of the preparation method of the present invention, in step (1), the main catalyst is UDC104, the cocatalyst is triethylaluminum, and the external electron donor is DIPDMS; the mass ratio of the cocatalyst to the external electron donor is 1-15: 1.
As a preferable embodiment of the preparation method of the present invention, in the step (2), the hydrogen concentration is 1500 to 3000ppm, and the density of the gas in the first loop reactor is 500 to 560kg/m 3 。
In a preferred embodiment of the preparation method of the present invention, in the step (3), the hydrogen concentration is 1500 to 3000ppm, and the density of the gas in the second loop reactor is 500 to 560kg/m 3 (ii) a And the melt flow rate of the product B is 25-35 g/10min according to GB/T3682-2000 determination.
In the preferred embodiment of the preparation method of the invention, in the step (4), the liquid-phase propylene removal mode of the product B is flash evaporation, the temperature of the gas phase kettle is 80-85 ℃, the pressure of the gas phase kettle is 1.1-1.4 MPa, and the gas phase ratio of the gas phase kettle is 0.35-0.45.
As a preferable embodiment of the preparation method, in the step (4), the ethylene content of the polypropylene powder is 12-17%; according to GB/T3682-2000, the melt flow rate of the polypropylene powder is 5-15 g/10 min.
As a preferable embodiment of the preparation method of the present invention, in the step (5), the primary antioxidant is 1076, which has a chemical name of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester; the auxiliary antioxidant is 168, and the chemical name is as follows: tris (2, 4-di-tert-butylphenyl) phosphite; the nucleating agent is sodium benzoate; the melt flow rate of the polypropylene material is 5-15 g/10min according to GB/T3682-2000 determination.
As a preferable embodiment of the preparation method of the present invention, in the step (5), the temperatures of the first zone to the fifth zone of the extruder barrel are 180 ℃, 190 ℃, 200 ℃ and 200 ℃, respectively, the die temperature of the extruder barrel is 260 ℃, and the temperature of the pelletizing water of the extruder is 65 ℃.
The invention provides a preparation method of a polypropylene material, which adopts a process method of combining a body and a gas phase, takes UDC104 as a main catalyst, takes DIPDMS as an external electron donor, controls the concentration of triethyl aluminum/the external electron donor to be 1-15, controls the concentration of hydrogen in a first ring pipe to be 1500-3000 ppm, and controls the density to be 500-560 kg/m 3 (ii) a The second loop has a hydrogen concentration of 1500-3000 ppm and a density of 500-560 kg/m 3 The melt flow rate of the second loop pipe product is 25-35 g/10 min; then controlling the temperature of the gas phase kettle to be 80 +/-5 ℃, the pressure to be 1.1-1.4 MPa and the gas phase ratio to be 0.35-0.45, and obtaining polypropylene powder with the ethylene content of 12-17% and the melt flow rate of 5-15 g/10 min; the high impact polypropylene material with the melt flow rate of 5-15 g/10min is prepared by uniformly mixing polypropylene powder, an antioxidant, an auxiliary antioxidant and a nucleating agent and then extruding the mixture by an extruder.
The invention provides a preparation method of a polypropylene material, which can ensure that the capacity of the gas-phase copolymerization reaction in the second step can be conveniently regulated and controlled in the gas-phase copolymerization stage under the condition of limited residence time, obtain an impact-resistant polypropylene product with specific rubber phase content, simultaneously does not increase the modification cost and energy consumption of a device, and widens the capability of a process device for producing product brands.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the polypropylene material provided by the invention can effectively improve the ethylene content and the rubber phase component content in the gas phase copolymerization stage in the process of producing the impact-resistant polypropylene, and can prevent fine powder from sticking a kettle and material from caking in the gas phase copolymerization stage.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the following examples and comparative examples, the primary antioxidant was octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the secondary antioxidant was tris (2, 4-di-tert-butylphenyl) phosphite, and the nucleating agent was sodium benzoate.
Example 1
The embodiment of the present invention provides a method for preparing a polypropylene material, including the following steps:
(1) adding propylene, a main catalyst (UDC104), a cocatalyst (triethylaluminum) and an external electron donor (DIPDMS) into a polymerization reactor, wherein the mass ratio of the cocatalyst to the external electron donor is 10 under the combined action of the main catalyst, the cocatalyst and the external electron donor, and polymerizing the propylene to generate polypropylene through a prepolymerization reactor;
(2) adding the polypropylene, the propylene and the hydrogen in the step (1) into a first loop reactor for polymerization reaction, controlling the concentration of the hydrogen in the first loop to be 2000ppm, and controlling the density of slurry in the first loop reactor to be 550kg/m 3 Obtaining a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization, controlling the concentration of the hydrogen in the second loop reactor to be 1800ppm, and controlling the density of slurry in the second loop reactor to be 550kg/m 3 Obtaining a product B; the melt flow rate of the product B is 27g/10min according to GB/T3682-2000;
(4) adding the product B obtained in the step (3) into a gas phase reaction kettle after flash evaporation for removing liquid phase propylene, and controlling the temperature of the gas phase kettle to be 80 ℃, the pressure to be 1.15MPa and the gas phase ratio to be 0.42 to obtain polypropylene powder with the ethylene content of 15 percent and the melt flow rate of 10.2g/10min (determined according to GB/T3682-2000);
(5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and extruding the mixture by an extruder to obtain the polypropylene material (the melt flow rate is 9.8g/10min according to GB/T3682-2000); wherein the temperature of the barrel of the extruder is 180 ℃, 190 ℃, 200 ℃, 260 ℃ of the die head, and 65 ℃ of the granulating water.
Example 2
The embodiment of the present invention provides a method for preparing a polypropylene material, including the following steps:
(1) adding propylene, a main catalyst (UDC104), a cocatalyst (triethylaluminum) and an external electron donor (DIPDMS) into a polymerization reactor, wherein the mass ratio of the cocatalyst to the external electron donor is 5 under the combined action of the main catalyst, the cocatalyst and the external electron donor, and polymerizing the propylene to generate polypropylene through a prepolymerization reactor;
(2) adding the polypropylene, the propylene and the hydrogen in the step (1) into a first loop reactor for polymerization reaction, controlling the concentration of the hydrogen in the first loop to be 1800ppm, and controlling the density of slurry in the first loop reactor to be 545kg/m 3 Obtaining a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization, controlling the concentration of the hydrogen in the second loop reactor to be 2000ppm, and controlling the density of slurry in the second loop reactor to be 545kg/m 3 Obtaining a product B; the melt flow rate of the product B is 26g/10min according to GB/T3682-2000;
(4) adding the product B obtained in the step (3) into a gas phase reaction kettle after flash evaporation for removing liquid phase propylene, and controlling the temperature of the gas phase kettle to be 80 ℃, the pressure to be 1.15MPa and the gas phase ratio to be 0.42 to obtain polypropylene powder with the ethylene content of 14 percent and the melt flow rate of 9.5g/10min (determined according to GB/T3682-2000);
(5) uniformly mixing the polypropylene powder obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and extruding by an extruder to obtain the polypropylene material (the melt flow rate is 10g/10 min); wherein the temperature of the barrel of the extruder is 180 ℃, 190 ℃, 200 ℃, 260 ℃ of a die head and 65 ℃ of the granulating water.
Example 3
The embodiment of the present invention provides a method for preparing a polypropylene material, including the following steps:
(1) adding propylene, a main catalyst (UDC104), a cocatalyst (triethylaluminum) and an external electron donor (DIPDMS) into a polymerization reactor, wherein the mass ratio of the cocatalyst to the external electron donor is 8 under the combined action of the main catalyst, the cocatalyst and the external electron donor, and polymerizing the propylene to generate polypropylene through a prepolymerization reactor;
(2) adding the polypropylene, the propylene and the hydrogen in the step (1) into a first loop reactor for polymerization, controlling the concentration of the hydrogen in the first loop to be 2100ppm, and controlling the density of slurry in the first loop reactor to be 550kg/m 3 Obtaining a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization, controlling the concentration of the hydrogen in the second loop reactor to be 1800ppm, and controlling the density of slurry in the second loop reactor to be 555kg/m 3 Obtaining a product B; the melt flow rate of the product B is 28g/10min according to GB/T3682-2000;
(4) adding the product B obtained in the step (3) into a gas phase reaction kettle after flash evaporation for removing liquid phase propylene, and controlling the temperature of the gas phase kettle to be 80 ℃, the pressure to be 1.15MPa and the gas phase ratio to be 0.42 to obtain polypropylene powder with the ethylene content of 16 percent and the melt flow rate of 11.6g/10min (determined according to GB/T3682-2000);
(5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and then extruding the mixture by an extruder to obtain the polypropylene material (the melt flow rate is 10.7g/10 min); wherein the temperature of the barrel of the extruder is 180 ℃, 190 ℃, 200 ℃, 260 ℃ of a die head and 65 ℃ of the granulating water.
Example 4
The embodiment of the present invention provides a method for preparing a polypropylene material, including the following steps:
(1) adding propylene, a main catalyst (UDC104), a cocatalyst (triethyl aluminum) and an external electron donor (DIPDMS) into a polymerization reactor, wherein the mass ratio of the cocatalyst to the external electron donor is 3 under the combined action of the main catalyst, the cocatalyst and the external electron donor, and polymerizing the propylene to generate polypropylene through a prepolymerization reactor;
(2) adding the polypropylene, the propylene and the hydrogen in the step (1) into a first loop reactor for polymerization reaction, controlling the concentration of the hydrogen in the first loop reactor to be 1500ppm, and controlling the density of slurry in the first loop reactor to be 500kg/m 3 Obtaining a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization, controlling the concentration of the hydrogen in the second loop reactor to be 1500ppm, and controlling the density of slurry in the second loop reactor to be 500kg/m 3 Obtaining a product B; the melt flow rate of the product B is 25g/10min according to GB/T3682-2000;
(4) adding the product B obtained in the step (3) into a gas phase reaction kettle after flash evaporation for removing liquid phase propylene, and controlling the temperature of the gas phase kettle to be 82 ℃, the pressure to be 1.1MPa and the gas phase ratio to be 0.35 to obtain polypropylene powder with the ethylene content of 17 percent and the melt flow rate of 15g/10min (determined according to GB/T3682-2000);
(5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and extruding the mixture by an extruder to obtain the polypropylene material (the melt flow rate is 15g/10min according to GB/T3682-2000); wherein the temperature of the barrel of the extruder is 180 ℃, 190 ℃, 200 ℃, 260 ℃ of a die head and 65 ℃ of the granulating water.
Example 5
The embodiment of the present invention provides a method for preparing a polypropylene material, including the following steps:
(1) adding propylene, a main catalyst (UDC104), a cocatalyst (triethyl aluminum) and an external electron donor (DIPDMS) into a polymerization reactor, wherein the mass ratio of the cocatalyst to the external electron donor is 12 under the combined action of the main catalyst, the cocatalyst and the external electron donor, and polymerizing the propylene to generate polypropylene through a prepolymerization reactor;
(2) subjecting the polypropylene of the step (1)Adding propylene and hydrogen into a first loop reactor for polymerization reaction, controlling the hydrogen concentration in the first loop to be 3000ppm, and controlling the density of slurry in the first loop reactor to be 560kg/m 3 Obtaining a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization, controlling the concentration of the hydrogen in the second loop to be 3000ppm, and controlling the density of slurry in the second loop reactor to be 560kg/m 3 Obtaining a product B; the melt flow rate of the product B is 35g/10min according to GB/T3682-2000;
(4) adding the product B obtained in the step (3) into a gas phase reaction kettle after flash evaporation for removing liquid phase propylene, and controlling the temperature of the gas phase kettle to be 85 ℃, the pressure to be 1.4MPa and the gas phase ratio to be 0.45 to obtain polypropylene powder with the ethylene content of 12 percent and the melt flow rate of 13g/10min (determined according to GB/T3682-2000);
(5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and extruding the mixture by an extruder to obtain the polypropylene material (the melt flow rate is 13g/10min according to GB/T3682-2000); wherein the temperature of the barrel of the extruder is 180 ℃, 190 ℃, 200 ℃, 260 ℃ of a die head and 65 ℃ of the granulating water.
Comparative example 1
The comparative example is a preparation method of a polypropylene material, comprising the following steps:
the comparative example is a preparation method of the polypropylene material, which comprises the following steps:
(1) adding propylene, a main catalyst (DQC401), a cocatalyst (triethyl aluminum) and an external electron Donor (Donor-D) into a polymerization reactor, wherein the mass ratio of the cocatalyst to the external electron Donor is 20 under the combined action of the main catalyst, the cocatalyst and the external electron Donor, and polymerizing the propylene to generate polypropylene through a prepolymerization reactor;
(2) adding the polypropylene, the propylene and the hydrogen in the step (1) into a first loop reactor for polymerization, controlling the concentration of the hydrogen in the first loop to be 3500ppm, and controlling the density of slurry in the first loop reactor to be 600kg/m 3 Obtaining a product A;
(3) adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization, controlling the concentration of the hydrogen in the second loop to be 3500ppm, and controlling the density of slurry in the second loop reactor to be 600kg/m 3 Obtaining a product B, wherein the melt flow rate of the product B is 30g/10 min;
(4) adding the product B obtained in the step (3) into a gas phase reaction kettle after flash evaporation for removing liquid phase propylene, and controlling the temperature of the gas phase kettle to be 80 ℃, the pressure to be 1.2MPa and the gas phase ratio to be 0.48 to obtain polypropylene powder with the ethylene content of 8 percent and the melt flow rate of 18g/10 min;
(5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and then extruding the mixture by an extruder to obtain the polypropylene material (the melt flow rate is 18g/10 min); wherein the temperature of the barrel of the extruder is 180 ℃, 190 ℃, 200 ℃, 260 ℃ of a die head and 65 ℃ of the granulating water.
Effect example 1
The polypropylene powder prepared by the preparation methods of examples 1-5 and comparative example 1 is subjected to detection of relevant indexes of mechanical properties, wherein the relevant indexes comprise melt Mass Flow Rate (MFR), ethylene content, rubber content, tensile strength, impact strength of a simply supported beam, flexural modulus and thermal deformation temperature.
TABLE 1 detection results of mechanical property related indexes of high impact polypropylene materials
From the above table 1, it can be seen that the ethylene content, the rubber content and the impact strength of the simply supported beam in the examples 1-5 are significantly higher than those in the comparative example 1, and it can be seen that the ethylene content and the rubber phase component content in the gas phase copolymerization stage can be effectively increased in the process of producing the impact resistant polypropylene by the preparation method of the polypropylene material provided by the present invention, and the impact resistance of the product can be effectively improved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. The preparation method of the polypropylene material is characterized by comprising the following steps:
(1) adding propylene, a main catalyst, a cocatalyst and an external electron donor into a polymerization reactor to obtain polypropylene; the main catalyst is UDC104, the cocatalyst is triethyl aluminum, and the external electron donor is DIPDMS; the mass ratio of the cocatalyst to the external electron donor is 1-15: 1
(2) Adding the polypropylene, propylene and hydrogen in the step (1) into a first loop reactor for polymerization reaction, and controlling the concentration of the hydrogen and the density of gas in the first loop reactor to obtain a product A; the hydrogen concentration is 1500-3000 ppm, and the density of the gas in the first loop reactor is 500-560 kg/m 3 ；
(3) Adding the product A, propylene and hydrogen in the step (2) into a second loop reactor for polymerization reaction, and controlling the concentration of the hydrogen and the density of gas in the second loop reactor to obtain a product B; the hydrogen concentration is 1500-3000 ppm, and the density of the gas in the second loop reactor is 500-560 kg/m 3 (ii) a The melt flow rate of the product B is 25-35 g/10min according to GB/T3682-2000;
(4) removing liquid phase propylene from the product B obtained in the step (3), adding the product B into a gas phase reaction kettle, and controlling the temperature, the pressure and the gas phase ratio of the gas phase kettle to obtain polypropylene powder; the liquid phase propylene removal mode of the product B is flash evaporation, the temperature of the gas phase kettle is 80-85 ℃, the pressure of the gas phase kettle is 1.1-1.4 MPa, and the gas phase ratio of the gas phase kettle is 0.35-0.45;
(5) and (5) uniformly mixing the polypropylene powder material obtained in the step (4) with a main antioxidant, an auxiliary antioxidant and a nucleating agent, and then extruding the mixture by an extruder to obtain the polypropylene material.
2. The preparation method of claim 1, wherein in the step (4), the ethylene content of the polypropylene powder is 12-17%; the melt flow rate of the polypropylene powder is 5-15 g/10min according to GB/T3682-2000.
3. The method according to claim 1, wherein in the step (5), the primary antioxidant is octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the secondary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, and the nucleating agent is sodium benzoate; the melt flow rate of the polypropylene material is 5-15 g/10min according to GB/T3682-2000 determination.
4. The method according to claim 1, wherein in the step (5), the temperatures of the first to fifth zones of the extruder barrel are 180 ℃, 190 ℃, 200 ℃, the die temperature of the extruder barrel is 260 ℃, and the temperature of the pellet water of the extruder is 65 ℃.
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