Preparation method of yellowing-resistant flame-retardant plastic
By introducing ethylene potassium trifluoroborate and allylhydrazine hydrochloride into the polypropylene particles, and using silicon, tungsten, and yttrium plasma currents to form an amorphous silicon thin film, the antibacterial and electrostatic problems of plastic products are solved, mechanical properties are improved, and high strength and wear resistance are achieved.
Patent Information
- Application Number
- CN202510836069.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2025-08-15
AI Technical Summary
Existing plastic products have problems such as poor antibacterial properties, easy to produce static electricity and insufficient mechanical properties, especially the use of antistatic agents during processing, resulting in damage to the material structure and degradation of mechanical properties.
Modified by introducing ethylene potassium trifluoroborate and allylhydrazine hydrochloride into the polypropylene particles, modified polypropylene is formed, and amorphous silicon thin film is bombarded on its surface by mixed plasma currents of silicon, tungsten and yttrium, and combined with doping of tungsten and yttrium elements, a conductive network is formed to improve antistatic and mechanical properties.
The plastic properties of antibacterial, antistatic, wear-resistant and high mechanical strength are achieved, and the comprehensive performance of plastic is improved by inhibiting bacterial growth, reducing the electrostatic friction coefficient and enhancing the overall strength of the material.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polypropylene particle preparation, in particular to a method for preparing yellowing-resistant flame-retardant plastic. Background Art
[0002] Plastic products are widely used in modern life, including kitchen appliances, food packaging, medical supplies, and children's products. These plastics are made from organic polymers, and during their production, organic additives are added to facilitate processing or achieve certain performance requirements. These organic compounds can easily breed bacteria on the plastic surface, posing a health risk to users. Therefore, antimicrobial plastics have become a very important functional plastic.
[0003] Furthermore, as polymer materials are increasingly used, their drawbacks are becoming increasingly apparent, with static electricity being one of them. To eliminate static electricity on the surface of materials, various antistatic agents are added to polymer materials. However, while antistatic agents eliminate static electricity on the surface of materials, they also bring about many other problems. These include poor heat resistance, easy decomposition during processing, poor compatibility with the matrix resin, destruction of the original structure of the polymer material, and reduction of the material's mechanical properties. Therefore, it is particularly important to invent a modified polypropylene particle with antistatic, antibacterial, and high strength properties. Summary of the Invention
[0004] The object of the present invention is to provide a yellowing-resistant flame-retardant plastic and a preparation method thereof, so as to solve the problems existing in the prior art.
[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a yellowing-resistant flame-retardant plastic and a preparation method thereof, comprising the following preparation steps: (1) Under nitrogen protection, 11-23 parts of potassium ethylene trifluoroborate, 5-17 parts of allylhydrazine hydrochloride, 74-132 parts of toluene, and 46-78 parts of acetonitrile were mixed uniformly, the rotation speed was adjusted to 140 rpm, 2-4 parts of catalyst were added, propylene gas was introduced to a certain pressure, the temperature was raised to 60-70°C, and the reaction was carried out for 4-8 hours. During the reaction, propylene gas was continuously introduced to maintain the pressure constant. After the reaction was completed, the air was connected, 15-29 parts of hydrochloric acid ethanol solution was added, and the mixture was stirred for 40-60 minutes. The solid was filtered and washed with deionized water 3 times, and dried at 70-90°C for 6-10 hours to obtain modified polypropylene; (2) adding 85-119 parts of modified polypropylene, 3-7 parts of lubricant, 5-11 parts of antioxidant, and 1-5 parts of benzotriazole light stabilizer into a mixer and mixing for 30-40 minutes, putting the mixture into a mixing extruder, extruding the mixture, and pelletizing the mixture to obtain modified polypropylene pellets; (3) Place the modified polypropylene particles in a vacuum of 5.0x10-3 Pa environment, then, filled with argon, and cleaned in sequence at a bias voltage of 300V and an ion beam voltage of 900V, each time for 10 minutes, and introduced a mixed plasma by magnetron sputtering silicon target, tungsten target, and yttrium target, and controlled the silicon, tungsten, and yttrium plasma currents. Under the conditions of an argon flow rate of 45sccm and a bias voltage of -60V, the deposition was carried out for 4 to 6 hours to obtain antistatic and antibacterial modified polypropylene particles.
[0006] Furthermore, the certain pressure in step (1) is 5 MPa.
[0007] Furthermore, the catalyst in step (1) is any one of a Ziegler-Natta catalyst, a Phillips catalyst, and a Metallocene catalyst.
[0008] Furthermore, the concentration of hydrochloric acid in the hydrochloric acid ethanol solution in step (1) is 3 mol / L.
[0009] Furthermore, the lubricant in step (2) is any one of stearic acid acetamide, distearamide, and oxidized polyethylene wax.
[0010] Furthermore, the antioxidant in step (2) is any one of butylated hydroxytoluene, antioxidant 1010, and antioxidant 1076.
[0011] Furthermore, the temperature of the mixer in step (2) is 160-180°C.
[0012] Furthermore, the parameters of the mixing extruder in step (2) are head temperature 155~185℃, screw speed 200~230r / min, extrusion pressure 10~12MPa, shear rate 220~240s -1 .
[0013] Furthermore, the flow rate of the argon gas in step (3) is 40 sccm.
[0014] Furthermore, in step (3), the silicon, tungsten, and yttrium plasma currents are 2.5 A, 0.3 A, and 0.4 A, respectively.
[0015] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses silicon, tungsten and yttrium mixed plasma current bombardment to modify C-C bonds and C-H bonds in polypropylene particles to form active chains, which combine with the mixed plasma. At the same time, the active chains react with each other to form a stable cross-linked structure, which prevents the active chains from continuing to overflow, and then in-situ grows an amorphous silicon film on the surface of the polypropylene, significantly improving the surface hardness and overall mechanical strength of the polypropylene, while also improving the flame retardant properties of the plastic. Tungsten doping can reduce the friction coefficient of the amorphous silicon film, reduce wear when friction occurs, and thus improve the wear resistance of the plastic and enhance the mechanical properties. Yttrium is combined with tungsten to fill defects in the polypropylene and film grains, refine the grains, increase the grain boundary area, and enhance the barrier effect of the grain boundaries on dislocations, thereby reducing the dislocation density of the material and improving the mechanical strength and flexibility of the material. On this basis, tungsten and yttrium elements have good electrical conductivity and form a conductive network on the surface, which allows generated static charges to be quickly discharged, achieving an antistatic effect.
[0016] Among them, modified polypropylene is prepared by the polymerization of propylene with potassium ethylene trifluoroborate and allylhydrazine hydrochloride; the introduction of fluorine and boron elements through potassium ethylene trifluoroborate can penetrate the bacterial cell membrane, destroy the bacterial metabolic process, inhibit the growth and reproduction of bacteria, and achieve an antibacterial effect. At the same time, the presence of potassium ions can increase its conductivity and hygroscopicity by adsorbing water molecules in the air, thereby achieving an antistatic effect, assisting the chloride ions in allylhydrazine hydrochloride to further enhance the antibacterial properties. On this basis, the hydrazide structure has a high reactivity, and cooperates with the plasma current to make the amorphous silicon film more tightly bonded, thereby further enhancing the mechanical strength. DETAILED DESCRIPTION
[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0018] In order to more clearly illustrate the method provided by the present invention, the following examples are provided in detail. The test methods for various indicators of the antistatic and antibacterial modified polypropylene particles prepared in the following examples are as follows: Tensile strength: The plastic particles of the examples and comparative examples were made into 0.3 mm films for tensile strength testing, which was conducted in accordance with GB / T 13022.
[0019] Abrasion test: Take the same weight of the embodiment and the comparative example, and test the wear resistance of the plastics with reference to GB / T 3960, and record the wear quality.
[0020] Surface resistance: The same weight of the examples and comparative examples were used to make square plates of 100 mm × 100 mm × 3 mm, and the test was performed according to GB / T 1410.
[0021] Antibacterial rate: Take the example and comparative example of the same mass and test them according to QB / T 2591.
[0022] Example 1 (1) Under nitrogen protection, 11 parts of potassium ethylene trifluoroborate, 5 parts of allylhydrazine hydrochloride, 74 parts of toluene, and 46 parts of acetonitrile were mixed uniformly, the rotation speed was adjusted to 140 rpm, 2 parts of Ziegler-Natta catalyst were added, propylene gas was introduced to 5 MPa, the temperature was raised to 60°C, and the reaction was carried out for 4 hours. During the reaction, propylene gas was continuously introduced to maintain the pressure constant. After the reaction was completed, the air was connected, 15 parts of 3 mol / L hydrochloric acid ethanol solution was added, and the mixture was stirred for 40 minutes. The solid was filtered and washed with deionized water three times, and dried at 70°C for 6 hours to obtain modified polypropylene; (2) 85 parts of modified polypropylene, 3 parts of stearic acid acetamide, 5 parts of dibutyl hydroxytoluene, and 1 part of phenyltriazole light stabilizer were added to a mixer and mixed at 160°C for 30 minutes, and then put into a mixing extruder for extrusion. The parameters were head temperature of 155°C, screw speed of 200 r / min, extrusion pressure of 10 MPa, and shear rate of 220s -1 , pelletizing to obtain modified polypropylene particles; (3) Place the modified polypropylene particles in a vacuum of 5.0x10 -3 Pa environment, then, argon was filled at a flow rate of 40sccm, and cleaning was carried out in sequence at a bias voltage of 300V and an ion beam voltage of 900V, each time for 10 minutes, and mixed plasma was introduced by magnetron sputtering silicon target, tungsten target, and yttrium target, and the silicon, tungsten, and yttrium plasma currents were controlled to 2.5A, 0.3A, and 0.4A, respectively. Under the conditions of argon flow rate of 45sccm and bias voltage of -60V, deposition was carried out for 4h to obtain antistatic and antibacterial modified polypropylene particles.
[0023] Example 2 (1) Under nitrogen protection, 17 parts of potassium ethylene trifluoroborate, 11 parts of allylhydrazine hydrochloride, 103 parts of toluene, and 62 parts of acetonitrile were mixed uniformly, the rotation speed was adjusted to 140 rpm, 3 parts of Phillips catalyst were added, propylene gas was introduced to 5 MPa, the temperature was raised to 65°C, and the reaction was carried out for 6 hours. During the reaction, propylene gas was continuously introduced to maintain the pressure constant. After the reaction was completed, the air was connected, 22 parts of 3 mol / L hydrochloric acid ethanol solution was added, and the mixture was stirred for 50 minutes. The solid was filtered and washed with deionized water three times, and dried at 80°C for 8 hours to obtain modified polypropylene; (2) 102 parts of modified polypropylene, 5 parts of distearamide, 8 parts of antioxidant 1010, and 3 parts of benzotriazole light stabilizer were added to a mixer and mixed at 170°C for 35 minutes, and then put into a mixing extruder for extrusion. The parameters were head temperature of 170°C, screw speed of 215 r / min, extrusion pressure of 11 MPa, and shear rate of 230s -1 , pelletizing to obtain modified polypropylene particles; (3) Place the modified polypropylene particles in a vacuum of 5.0x10 -3 Pa environment, then, argon was filled at a flow rate of 40sccm, and cleaning was carried out in sequence at a bias voltage of 300V and an ion beam voltage of 900V, each time for 10 minutes. Mixed plasma was introduced by magnetron sputtering silicon target, tungsten target, and yttrium target, and the silicon, tungsten, and yttrium plasma currents were controlled to 2.5A, 0.3A, and 0.4A, respectively. Under the conditions of argon flow rate of 45sccm and bias voltage of -60V, deposition was carried out for 4~6h to obtain antistatic and antibacterial modified polypropylene particles.
[0024] Example 3 (1) Under nitrogen protection, 23 parts of potassium ethylene trifluoroborate, 17 parts of allylhydrazine hydrochloride, 132 parts of toluene, and 78 parts of acetonitrile were mixed uniformly, the rotation speed was adjusted to 140 rpm, 4 parts of Metallocene catalyst were added, propylene gas was introduced to 5 MPa, the temperature was raised to 70°C, and the reaction was carried out for 8 hours. During the reaction, propylene gas was continuously introduced to maintain a constant pressure. After the reaction was completed, air was connected, 29 parts of 3 mol / L hydrochloric acid ethanol solution was added, and the mixture was stirred for 60 minutes. The solid was filtered and washed with deionized water three times, and dried at 790°C for 10 hours to obtain modified polypropylene; (2) 119 parts of modified polypropylene, 7 parts of oxidized polyethylene wax, 11 parts of antioxidant 1076, and 5 parts of benzotriazole light stabilizer were added to a mixer and mixed at 180°C for 40 minutes, and then put into a mixing extruder for extrusion. The parameters were head temperature of 185°C, screw speed of 230 r / min, extrusion pressure of 12 MPa, and shear rate of 240 s -1 , pelletizing to obtain modified polypropylene particles; (3) Place the modified polypropylene particles in a vacuum of 5.0x10 -3 Pa environment, then, argon was filled at a flow rate of 40sccm, and cleaning was carried out in sequence at a bias voltage of 300V and an ion beam voltage of 900V, each time for 10 minutes. Mixed plasma was introduced by magnetron sputtering silicon target, tungsten target, and yttrium target, and the silicon, tungsten, and yttrium plasma currents were controlled to 2.5A, 0.3A, and 0.4A, respectively. Under the conditions of argon flow rate of 45sccm and bias voltage of -60V, deposition was carried out for 4~6h to obtain antistatic and antibacterial modified polypropylene particles.
[0025] Comparative Example 1 The difference between Comparative Example 1 and Example 2 lies in the difference in step (1). Step (1) is modified as follows: under nitrogen protection, 11 parts of allylhydrazine hydrochloride, 103 parts of toluene, and 62 parts of acetonitrile are mixed uniformly, the rotation speed is adjusted to 140 rpm, 3 parts of Phillips catalyst are added, propylene gas is introduced to 5 MPa, the temperature is raised to 65°C, and the reaction is carried out for 6 hours. During the reaction, propylene gas is continuously introduced to maintain a constant pressure. After the reaction is completed, the air is connected, 22 parts of a hydrochloric acid ethanol solution with a hydrochloric acid concentration of 3 mol / L is added, and the mixture is stirred for 50 minutes. The solid is filtered off, washed three times with deionized water, and dried at 80°C for 8 hours to obtain modified polypropylene. The remaining steps are the same as those in Example 2.
[0026] Comparative Example 2: The difference between Comparative Example 2 and Example 2 lies in step (1). Step (1) is modified as follows: Under nitrogen protection, 17 parts of potassium ethylene trifluoroborate, 103 parts of toluene, and 62 parts of acetonitrile are uniformly mixed, the rotation speed is adjusted to 140 rpm, 3 parts of Phillips catalyst are added, propylene gas is introduced to 5 MPa, the temperature is raised to 65°C, and the reaction is carried out for 6 hours. During the reaction, propylene gas is continuously introduced to maintain a constant pressure. After the reaction is completed, air is connected, 22 parts of 3 mol / L hydrochloric acid ethanol solution is added, and the mixture is stirred for 50 minutes. The solid is filtered and washed three times with deionized water. It is dried at 80°C for 8 hours to obtain modified polypropylene. The remaining steps are the same as those in Example 2.
[0027] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that step (3) is different. Step (3) is changed to: placing the modified polypropylene particles in a vacuum of 5.0x10 -3 Pa environment, then, argon gas was introduced at a flow rate of 40 sccm, and cleaning was performed sequentially at a bias voltage of 300 V and an ion beam voltage of 900 V, each for 10 minutes. A mixed plasma was introduced by magnetron sputtering a tungsten target and a yttrium target, and the tungsten and yttrium plasma currents were controlled to 0.3 A and 0.4 A, respectively. Under the conditions of an argon flow rate of 45 sccm and a bias voltage of -60 V, deposition was performed for 4 to 6 hours to obtain antistatic and antibacterial modified polypropylene particles. The remaining steps were the same as in Example 2.
[0028] Comparative Example 4: The difference between Comparative Example 4 and Example 2 lies in the difference in step (3). Step (3) is changed to: placing the modified polypropylene particles in a vacuum of 5.0x10 -3Pa environment, then, argon gas was introduced at a flow rate of 40 sccm, and cleaning was performed sequentially at a bias voltage of 300 V and an ion beam voltage of 900 V, each for 10 minutes. A mixed plasma was introduced by magnetron sputtering a silicon target and a yttrium target, and the silicon and yttrium plasma currents were controlled to 2.5 A and 0.4 A, respectively. Under the conditions of an argon flow rate of 45 sccm and a bias voltage of -60 V, deposition was performed for 4 to 6 hours to obtain antistatic and antibacterial modified polypropylene particles. The remaining steps were the same as in Example 2.
[0029] Comparative Example 5: The difference between Comparative Example 5 and Example 2 is that step (3) is different. Step (3) is changed to: placing the modified polypropylene particles in a vacuum of 5.0x10 -3 Pa environment, then, argon gas was introduced at a flow rate of 40 sccm, and cleaning was performed sequentially at a bias voltage of 300 V and an ion beam voltage of 900 V, each for 10 minutes. A mixed plasma was introduced by magnetron sputtering a silicon target and a tungsten target, and the silicon and tungsten plasma currents were controlled to 2.5 A and 0.3 A, respectively. Under the conditions of an argon flow rate of 45 sccm and a bias voltage of -60 V, deposition was performed for 4 to 6 hours to obtain antistatic and antibacterial modified polypropylene particles. The remaining steps were the same as in Example 2.
[0030] Comparative Example 6: The difference between Comparative Example 6 and Example 2 is that there is no step (3), and step (2) is changed to: 102 parts of modified polypropylene, 10 parts of silicon dioxide, 2 parts of tungsten dioxide, 2 parts of yttrium oxide, 5 parts of distearamide, 8 parts of antioxidant 1010, and 3 parts of benzotriazole light stabilizer are added to a mixer and mixed at 170°C for 35 minutes, and then put into a mixing extruder for extrusion. The parameters are: head temperature of 170°C, screw speed of 215r / min, extrusion pressure of 11MPa, shear rate of 230s -1 The remaining steps are the same as those in Example 2.
[0031] Effect Examples Table 1 below shows the performance analysis results of the antistatic and antibacterial modified polypropylene particles of Examples 1 to 3 of the present invention and Comparative Examples 1 to 6.
[0032] From the comparison of the experimental data of Examples 1, 2, and 3 with those of Comparative Example 1, it can be found that the introduction of fluorine and boron elements by potassium ethylene trifluoroborate can penetrate the bacterial cell membrane, destroy the bacterial metabolic process, inhibit the growth and reproduction of bacteria, and achieve an antibacterial effect. At the same time, the presence of potassium ions can increase its conductivity and hygroscopicity by adsorbing water molecules in the air, thereby achieving an antistatic effect. From the comparison of the experimental data of Examples 1, 2, and 3 with those of Comparative Example 2, it can be found that the chloride ions in allylhydrazine hydrochloride can inhibit the growth and reproduction of bacteria and enhance the antibacterial properties. At the same time, the hydrazide structure has a high reactivity and cooperates with the plasma current to make the amorphous silicon film more tightly bonded, further enhancing the mechanical strength. From the comparison of the experimental data of Examples 1, 2, and 3 with those of Comparative Example 3, it can be found that the in situ growth of amorphous silicon film on the surface of polypropylene particles can significantly improve the mechanical strength of polypropylene and increase the wear resistance. From the comparison of the experimental data of Examples 1, 2, and 3 with those of Comparative Example 4, it can be found that the doping of tungsten element , which can reduce the friction coefficient of the amorphous silicon film, reduce wear when friction occurs, thereby improving the wear resistance of the plastic, enhancing the mechanical properties, and forming a conductive network on the surface, so that the generated static charge is quickly leaked, achieving an antistatic effect; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 5, it can be found that the yttrium element can fill the defects of the polypropylene and the film grains, refine the grains, increase the grain boundary area, and enhance the barrier effect of the grain boundary on dislocations, thereby reducing the dislocation density of the material, improving the mechanical strength and flexibility of the material, and at the same time forming a conductive network on the surface, so that the generated static charge is quickly leaked, achieving an antistatic effect; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 6, it can be found that the CC bonds and CH bonds in the modified polypropylene particles are bombarded by plasma current to form active chains, which are combined with the mixed plasma. At the same time, the active chains react with each other to form a stable cross-linked structure, which prevents the active chains from continuing to overflow, and significantly improves the overall mechanical strength of the polypropylene.
[0033] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.
Claims
1. A method for preparing yellowing-resistant flame-retardant plastics, characterized in that: The method comprises the following preparation steps: (1) Under nitrogen protection, 17 parts of potassium ethylene trifluoroborate, 11 parts of allylhydrazine hydrochloride, 103 parts of toluene, and 62 parts of acetonitrile were mixed uniformly, the rotation speed was adjusted to 140 rpm, 3 parts of Phillips catalyst were added, propylene gas was introduced to 5 MPa, the temperature was raised to 65°C, and the reaction was carried out for 6 hours. During the reaction, propylene gas was continuously introduced to maintain the pressure constant. After the reaction was completed, the air was connected, 22 parts of 3 mol / L hydrochloric acid ethanol solution was added, and the mixture was stirred for 50 minutes. The solid was filtered and washed with deionized water three times, and dried at 80°C for 8 hours to obtain modified polypropylene; (2) 102 parts of modified polypropylene, 5 parts of distearamide, 8 parts of antioxidant 1010, and 3 parts of benzotriazole light stabilizer were added to a mixer and mixed at 170°C for 35 minutes, and then put into a mixing extruder for extrusion. The parameters were head temperature of 170°C, screw speed of 215 r / min, extrusion pressure of 11 MPa, and shear rate of 230s -1 , pelletizing to obtain modified polypropylene particles; (3) Place the modified polypropylene particles in a vacuum of 5.0x10 -3 Pa environment, then, argon was filled at a flow rate of 40sccm, and cleaning was carried out in sequence at a bias voltage of 300V and an ion beam voltage of 900V, each time for 10 minutes. Mixed plasma was introduced by magnetron sputtering silicon target, tungsten target, and yttrium target, and the silicon, tungsten, and yttrium plasma currents were controlled to 2.5A, 0.3A, and 0.4A, respectively. Under the conditions of argon flow rate of 45sccm and bias voltage of -60V, deposition was carried out for 4~6h to obtain antistatic and antibacterial modified polypropylene particles.