Outdoor anti-aging PP plate and preparation method thereof

Abstract

The invention relates to an outdoor anti-aging PP plate and a preparation method thereof, and belongs to the technical field of high polymer materials. The outdoor anti-aging PP plate comprises the following components in parts by weight: 40-80 parts of PP resin, 10-20 parts of glass fibers, 1-5 parts of an anti-aging modifier, 0.2-3 parts of a modified flame retardant, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant, hydroxybenzophenone in the modified anti-aging agent generates thermal vibration and releases energy when absorbing ultraviolet rays and being irradiated by the ultraviolet rays, and cooperates with butyltrimethoxysilane to protect the material from being damaged by the ultraviolet rays, and a maleimide group improves the glass transition temperature and the melting point and reduces the influence of high-temperature thermal aging; a B-O-C carbon layer is formed at a high temperature under the synergistic effect of boron and phosphorus of the modified flame retardant, flame-retardant gas is released, and the modified flame retardant and phosphorus-oxygen double bonds are synergistically flame-retardant, so that the flame-retardant property is remarkably improved; the outdoor anti-aging PP plate prepared by the invention not only has excellent anti-aging performance, but also has a good flame-retardant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to an outdoor anti-aging PP board and a preparation method thereof. Background Art

[0002] PP board, also known as polypropylene board, is one of the most environmentally friendly engineering thermoplastics. It is widely used in food packaging, medical equipment, household goods and other fields due to its excellent chemical corrosion resistance, heat resistance and impact resistance.

[0003] However, with the improvement of modern life quality, the environmental protection and safety of plastics have received increasing attention. Traditional PP products are easily exposed to strong ultraviolet radiation during long-term outdoor use, which damages the molecular structure and causes further aging of the material. In addition, PP materials are derived from petrochemical materials and are composed of hydrocarbon elements. They are flammable and can easily be ignited to cause fires. These problems limit the wider and deeper application of PP materials. Therefore, the development of an outdoor aging-resistant PP board with excellent performance has important practical significance and application value. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an outdoor aging-resistant PP board and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: An outdoor anti-aging PP board comprises the following raw materials in parts by weight: 40-80 parts of PP resin, 10-20 parts of glass fiber, 1-5 parts of anti-aging modifier, 0.2-3 parts of modified flame retardant, 0.1-1 parts of lubricant, and 0.1-0.5 parts of antioxidant; The lubricant is ethylene bis stearamide; The antioxidant is antioxidant 1098.

[0006] The anti-aging modifier is prepared by the following method: Step A1: maleic anhydride, toluene and m-chloroaniline were mixed, stirred for reaction for 30 minutes, tetrahydrofuran was added, and stirring was continued for 5 minutes in an ice-water bath, triethylamine was added and mixed, and the mixture was reacted for 10 minutes, washed, filtered, and rotary evaporated, and butyltrimethoxysilane and ethanol-water mixed solution were added, and the mixture was reacted at 35° C. for 5 hours, washed, and vacuum dried to obtain a compound; Further, the dosage ratio of maleic anhydride, toluene, m-chloroaniline, tetrahydrofuran, triethylamine, butyltrimethoxysilane, and ethanol-water mixed solution is 3.67-4.9 g: 30-40 mL: 4.8-6.4 g: 10 mL: 1.12-2.58 g: 2.23-2.97 g: 150 mL, and the volume ratio of ethanol to water in the ethanol-water mixed solution is 4:1; First, maleic anhydride is used to react with the amino group of m-chloroaniline, and then the silanol group of the hydrolyzed butyltrimethoxysilane is used to react with the chlorine atom of m-chloroaniline to generate a compound; Step A2: uniformly mix oxybenzone, triethylamine and tetrahydrofuran, and then dropwise add acryloyl chloride in an ice bath for 1-2 hours, react in an ice bath for 5 hours, precipitate in ice water after the reaction, wash, and vacuum dry to obtain a pre-product; Further, the usage ratio of oxybenzone, triethylamine, tetrahydrofuran, and acryloyl chloride is 6.31-8.41 g: 1.7-3.5 mL: 20-30 mL: 3.40-4.53 g; Secondly, the hydroxyl group of oxybenzone is reacted with the acyl chloride of acryloyl chloride to generate a pre-product; Step A3: Disperse the compound evenly in xylene, add the pre-product and stir evenly, heat to 90°C under nitrogen protection for reaction for 4.5h, distill under reduced pressure, cool, wash, filter, and vacuum dry to obtain an anti-aging modifier; Further, the ratio of the compound, xylene, and pre-product is 0.01-0.02 mol: 70 mL: 0.01-0.02 mol; Finally, the anti-aging modifier is synthesized by copolymerizing the carbon-carbon double bonds of the pre-product and the compound.

[0007] The modified flame retardant is prepared by the following method: Step B1: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide and 4-vinylaniline were mixed, stirred at 150° C. for 9 h, filtered, washed, and dried under vacuum at 60° C. for 24 h to obtain an intermediate; Further, the usage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide, and 4-vinylaniline is 0.05-0.1 mol: 30-50 mL: 5.96-11.92 g; First, the carbon-carbon double bond of 4-vinylaniline is reacted with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to form an intermediate; Step B2: Mix phenylboric acid, the intermediate and deionized water, stir and reflux at 90° C. for 4 h, reduce the temperature to 40° C., continue stirring for 3 h, naturally cool to room temperature, filter, wash, dry, and grind in a ball mill for 5 min, sieve with an 80-mesh sieve plate to obtain a modified flame retardant; Further, the dosage ratio of phenylboric acid, intermediate, and deionized water is 3.05-6.1 g: 0.05-0.1 mol: 150-300 mL; Finally, the amino group of the intermediate reacts with the hydroxyl group of phenylboronic acid to generate a modified flame retardant.

[0008] A method for preparing an outdoor aging-resistant PP board specifically comprises the following steps: S1, mixing PP resin and glass fiber to prepare a premixed material; S2, adding the anti-aging modifier, modified flame retardant, lubricant and antioxidant to the premixed material, mixing evenly, stirring for 15-30 minutes, and drying at 70-80° C. for 2-3 hours to obtain a mixed base material; S3. The mixed base material is placed in a twin-screw extruder at 200-280°C for extrusion granulation, the screw speed is controlled at 450-500r / min, and the mixed base material is injected by an injection molding machine and cooled to obtain an outdoor aging-resistant PP board.

[0009] Beneficial effects of the present invention: The outdoor anti-aging PP board of the present invention not only has good anti-aging performance and effectively prolongs the service life of the material, but also has excellent flame retardant effect.

[0010] The anti-aging modifier prepared by the present invention has the advantage of its macromolecular polymer and shows performance that exceeds that of traditional small molecule anti-aging agents. The oxybenzone in the modified anti-aging agent can effectively absorb ultraviolet rays, and its hydroxyl hydrogen and carbonyl oxygen form a chelate ring by forming hydrogen bonds. When irradiated by ultraviolet rays, the molecule undergoes thermal vibration, causing the electron excitation to transition to a high energy level, and then releases energy by emitting weak long waves, effectively resisting high-energy ultraviolet rays. At the same time, the benzene ring and methoxy structure of oxybenzone can also effectively absorb ultraviolet rays and convert them into harmless heat energy, synergizing with butyltrimethoxysilane to protect the material from ultraviolet damage; in addition, the maleimide group increases the glass transition temperature and melting point of the material by enhancing the intermolecular force, increasing the rigidity and heat resistance of the molecular chain, and reducing the influence of high-temperature thermal aging.

[0011] The modified flame retardant prepared by the present invention not only improves the hydrolysis stability but also effectively reduces the generation of smoke through the synergistic effect of boron and phosphorus. In the initial stage of combustion, the boron-based components are dehydrated by heat, and carbonization is accelerated to form a glass-like protective layer to prevent the spread of combustion. The aromatic boric acid group forms a boron-oxygen network structure after being heated, and is further converted into a high-stability BOC carbon layer at high temperature. At the same time, the carbon layer is expanded by releasing non-combustible gas to form a heat-insulating and oxygen-isolating barrier, thereby significantly improving the flame retardant performance. In addition, the phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the intermediate, as a phosphaphenanthrene compound with high thermal stability, promotes the formation of a dense and continuous carbon layer during combustion, effectively isolates oxygen, blocks heat, inhibits combustion, and synergizes with the phosphorus-oxygen double bond to achieve flame retardancy and prolongs the service life. In addition, the modified flame retardant prepared by the present invention is halogen-free, helps to reduce environmental pollution and damage to the ecosystem, is harmless to human health, and achieves sustainable development. DETAILED DESCRIPTION

[0012] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0013] Embodiment 1: A method for preparing an outdoor aging-resistant PP board, comprising the following steps: S1. Weigh the raw materials by weight: 40 parts of PP resin, 10 parts of glass fiber, 1 part of anti-aging modifier (prepared in this embodiment), 0.2 parts of modified flame retardant (prepared in this embodiment), 0.1 parts of lubricant, and 0.1 parts of antioxidant; mix and stir the PP resin and the glass fiber to prepare a premixed material; S2, adding anti-aging modifier, modified flame retardant, ethylene bis stearic acid amide and antioxidant 1098 to the premixed material, mixing evenly, stirring for 15 minutes, and drying at 70° C. for 2 hours to obtain a mixed base material; S3, placing the mixed base material in a twin-screw extruder at 200°C for extrusion and granulation, controlling the screw speed at 450r / min, injection molding by an injection molding machine, cooling and molding, and obtaining an outdoor aging-resistant PP board; The anti-aging modifier is prepared by the following method: Step A1: 3.67 g of maleic anhydride, 30 mL of toluene and 4.8 g of m-chloroaniline were mixed, stirred for 30 min, and then 10 mL of tetrahydrofuran was added. After continuous stirring for 5 min in an ice-water bath, 1.12 g of triethylamine was added and mixed, and the mixture was reacted for 10 min. The mixture was washed, filtered, and rotary evaporated. Then, 2.23 g of butyltrimethoxysilane and 150 mL of ethanol-water mixed solution were added, and the mixture was reacted at 35° C. for 5 h. The mixture was washed and vacuum dried to obtain a compound. The volume ratio of ethanol to water in the ethanol-water mixed solution was 4:1. Step A2: 6.31 g of oxybenzone, 1.7 mL of triethylamine and 20 mL of tetrahydrofuran were mixed evenly, and then 3.40 g of acryloyl chloride was added dropwise under an ice bath for 1 h. The mixture was reacted under an ice bath for 5 h. After the reaction was completed, the mixture was precipitated in ice water, washed, and vacuum dried to obtain a pre-product; Step A3: Disperse 0.01 mol of the compound in 70 mL of xylene, add 0.01 mol of the pre-product and stir evenly, heat to 90° C. under nitrogen protection for 4.5 h, distill under reduced pressure, cool, wash, filter, and vacuum dry to obtain an anti-aging modifier; The modified flame retardant is prepared by the following method: Step B1: 0.05 mol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 30 mL N,N-dimethylformamide and 5.96 g 4-vinylaniline were mixed, stirred at 150° C. for 9 h, filtered, washed, and dried under vacuum at 60° C. for 24 h to obtain an intermediate; Step B2: Mix 3.05 g of phenylboric acid, 0.05 mol of the intermediate and 150 mL of deionized water, stir and reflux at 90 ° C for 4 h, reduce the temperature to 40 ° C, continue stirring for 3 h, naturally cool to room temperature, filter, wash, dry, and then put into a ball mill for 5 min, sieve with an 80-mesh sieve plate to obtain a modified flame retardant.

[0014] Embodiment 2: A method for preparing an outdoor aging-resistant PP board, comprising the following steps: S1. Weigh the raw materials by weight: 60 parts of PP resin, 15 parts of glass fiber, 3 parts of anti-aging modifier (prepared in this embodiment), 1.6 parts of modified flame retardant (prepared in this embodiment), 0.5 parts of lubricant, and 0.3 parts of antioxidant; mix and stir the PP resin and the glass fiber to prepare a premixed material; S2, adding anti-aging modifier, modified flame retardant, ethylene bis stearic acid amide and antioxidant 1098 to the premixed material, mixing evenly, stirring for 22 minutes, and drying at 75° C. for 2.5 hours to obtain a mixed base material; S3, placing the mixed base material in a twin-screw extruder at 240°C for extrusion and granulation, controlling the screw speed at 475r / min, injection molding by an injection molding machine, cooling and molding, and obtaining an outdoor aging-resistant PP board; The anti-aging modifier is prepared by the following method: Step A1: 4.285 g of maleic anhydride, 35 mL of toluene and 5.6 g of m-chloroaniline were mixed, stirred for 30 min, and then 10 mL of tetrahydrofuran was added. After continuous stirring for 5 min in an ice-water bath, 1.85 g of triethylamine was added and mixed, and the mixture was reacted for 10 min. The mixture was washed, filtered, and rotary evaporated. Then, 2.6 g of butyltrimethoxysilane and 150 mL of ethanol-water mixed solution were added, and the mixture was reacted at 35° C. for 5 h. The mixture was washed and vacuum dried to obtain a compound. The volume ratio of ethanol to water in the ethanol-water mixed solution was 4:1. Step A2: 7.36 g of oxybenzone, 2.6 mL of triethylamine and 25 mL of tetrahydrofuran were mixed evenly, and then 3.965 g of acryloyl chloride was added dropwise under an ice bath for 1.5 h. The mixture was reacted under an ice bath for 5 h. After the reaction was completed, the mixture was precipitated in ice water, washed, and vacuum dried to obtain a pre-product; Step A3: Disperse 0.015 mol of the compound in 70 mL of xylene, add 0.015 mol of the pre-product and stir evenly, heat to 90° C. under nitrogen protection for 4.5 h, distill under reduced pressure, cool, wash, filter, and vacuum dry to obtain an anti-aging modifier; The modified flame retardant is prepared by the following method: Step B1: 0.075 mol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 mL N,N-dimethylformamide and 8.94 g 4-vinylaniline were mixed, stirred at 150° C. for 9 h, filtered, washed, and dried under vacuum at 60° C. for 24 h to obtain an intermediate; Step B2: Mix 4.575 g of phenylboric acid, 0.075 mol of the intermediate and 225 mL of deionized water, stir and reflux at 90°C for 4 h, reduce the temperature to 40°C, continue stirring for 3 h, naturally cool to room temperature, filter, wash, dry, and then put into a ball mill for 5 min, sieve with an 80-mesh sieve plate to obtain a modified flame retardant.

[0015] Embodiment 3: A method for preparing an outdoor aging-resistant PP board, comprising the following steps: S1. Weigh the raw materials by weight: 80 parts of PP resin, 20 parts of glass fiber, 5 parts of anti-aging modifier (prepared in this embodiment), 3 parts of modified flame retardant (prepared in this embodiment), 1 part of lubricant, and 0.5 part of antioxidant; mix and stir the PP resin and the glass fiber to prepare a premixed material; S2, adding anti-aging modifier, modified flame retardant, ethylene bis stearic acid amide and antioxidant 1098 to the premixed material, mixing evenly, stirring for 30 minutes, and drying at 80° C. for 3 hours to obtain a mixed base material; S3, placing the mixed base material in a twin-screw extruder at 280°C for extrusion and granulation, controlling the screw speed at 500r / min, injection molding by an injection molding machine, cooling and molding, and obtaining an outdoor aging-resistant PP board; The anti-aging modifier is prepared by the following method: Step A1: 4.9 g of maleic anhydride, 40 mL of toluene and 6.4 g of m-chloroaniline were mixed, stirred for reaction for 30 min, and then 10 mL of tetrahydrofuran was added. After continuous stirring for 5 min in an ice-water bath, 2.58 g of triethylamine was added and mixed, and the mixture was reacted for 10 min. The mixture was washed, filtered, and rotary evaporated. Then, 2.97 g of butyltrimethoxysilane and 150 mL of ethanol-water mixed solution were added, and the mixture was reacted at 35° C. for 5 h. The mixture was washed and vacuum dried to obtain a compound. The volume ratio of ethanol to water in the ethanol-water mixed solution was 4:1. Step A2: 8.41 g of oxybenzone, 3.5 mL of triethylamine and 30 mL of tetrahydrofuran were mixed evenly, and then 4.53 g of acryloyl chloride was added dropwise under an ice bath for 2 h. The mixture was reacted under an ice bath for 5 h. After the reaction was completed, the mixture was precipitated in ice water, washed, and vacuum dried to obtain a pre-product; Step A3: Disperse 0.02 mol of the compound in 70 mL of xylene, add 0.02 mol of the pre-product and stir evenly, heat to 90° C. under nitrogen protection for 4.5 h, distill under reduced pressure, cool, wash, filter, and vacuum dry to obtain an anti-aging modifier; The modified flame retardant is prepared by the following method: Step B1: 0.1 mol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 50 mL N,N-dimethylformamide and 11.92 g 4-vinylaniline were mixed, stirred at 150° C. for 9 h, filtered, washed, and dried under vacuum at 60° C. for 24 h to obtain an intermediate; Step B2: Mix 6.1 g of phenylboric acid, 0.1 mol of the intermediate and 300 mL of deionized water, stir and reflux at 90°C for 4 h, reduce the temperature to 40°C, continue stirring for 3 h, naturally cool to room temperature, filter, wash, dry, and then put into a ball mill for 5 min, sieve with an 80-mesh sieve plate to obtain a modified flame retardant.

[0016] Comparative Example 1: This comparative example is an outdoor aging-resistant PP board. The difference from Example 3 is that an equal amount of 4,4'-thiobis(6-tert-butyl-3-methylphenol) is used to replace the anti-aging modifier prepared in Example 3, and the rest are the same.

[0017] Comparative Example 2: This comparative example is an outdoor aging-resistant PP board. The difference from Example 3 is that an equal amount of magnesium hydroxide is used to replace the modified flame retardant prepared in Example 3, and the rest are the same.

[0018] Performance test: The outdoor aging-resistant PP plates prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, and aging resistance tests were performed using a BLUESTAR--X65 xenon lamp in accordance with standard GB / T16422.2; the samples were placed in a UV aging box at 60°C, 0.86w / cm 2 , UV light for 1000h, test the difference in yellow index change, the larger the difference, the worse the anti-aging performance; GB / T 2048-1996 plastic combustion performance test method was used to test vertical combustion performance; the test results are shown in Table 1 below: Table 1

[0019] It can be seen from the test data in Table 1 that the outdoor aging-resistant PP board prepared by the present invention has excellent aging-resistant effect. It can also be seen from the above table that the outdoor aging-resistant PP board prepared by the present invention has good flame retardant properties.

[0020] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an outdoor aging-resistant PP board, characterized in that: The specific steps include: S1. Weigh the raw materials by weight: 40-80 parts of PP resin, 10-20 parts of glass fiber, 1-5 parts of anti-aging modifier, 0.2-3 parts of modified flame retardant, 0.1-1 parts of lubricant, and 0.1-0.5 parts of antioxidant; mix and stir the PP resin and the glass fiber to obtain a premixed material; S2, adding the anti-aging modifier, modified flame retardant, lubricant and antioxidant to the premixed material, mixing evenly, stirring for 15-30 minutes, and drying at 70-80° C. for 2-3 hours to obtain a mixed base material; S3, placing the mixed base material in a twin-screw extruder at 200-280°C for extrusion granulation, controlling the screw speed at 450-500r / min, injection molding by an injection molding machine, cooling and molding, and obtaining an outdoor aging-resistant PP board; The anti-aging modifier is prepared by the following method: Step A1: maleic anhydride, toluene and m-chloroaniline were mixed, stirred for reaction for 30 minutes, tetrahydrofuran was added, and stirring was continued for 5 minutes in an ice-water bath, triethylamine was added and mixed, and the mixture was reacted for 10 minutes, washed, filtered, and rotary evaporated, and butyltrimethoxysilane and ethanol-water mixed solution were added, and the mixture was reacted at 35° C. for 5 hours, washed, and vacuum dried to obtain a compound; Step A2: uniformly mix oxybenzone, triethylamine and tetrahydrofuran, and then dropwise add acryloyl chloride in an ice bath for 1-2 hours, react in an ice bath for 5 hours, precipitate in ice water after the reaction, wash, and vacuum dry to obtain a pre-product; Step A3: Disperse the compound evenly in xylene, add the pre-product and stir evenly, heat to 90°C under nitrogen protection for reaction for 4.5h, distill under reduced pressure, cool, wash, filter, and vacuum dry to obtain an anti-aging modifier.

2. The method for preparing an outdoor aging-resistant PP board according to claim 1, characterized in that: In step A1, the dosage ratio of maleic anhydride, toluene, m-chloroaniline, tetrahydrofuran, triethylamine, butyltrimethoxysilane, and ethanol-water mixed solution is 3.67-4.9 g: 30-40 mL: 4.8-6.4 g: 10 mL: 1.12-2.58 g: 2.23-2.97 g: 150 mL, and the volume ratio of ethanol to water in the ethanol-water mixed solution is 4:

1.

3. The method for preparing an outdoor aging-resistant PP board according to claim 1, characterized in that: In step A2, the usage ratio of oxybenzone, triethylamine, tetrahydrofuran and acryloyl chloride is 6.31-8.41 g: 1.7-3.5 mL: 20-30 mL: 3.40-4.53 g.

4. The method for preparing an outdoor aging-resistant PP board according to claim 1, characterized in that: In step A3, the usage ratio of the compound, xylene and pre-product is 0.01-0.02 mol:70 mL:0.01-0.02 mol.

5. The method for preparing an outdoor aging-resistant PP board according to claim 1, characterized in that: The modified flame retardant is prepared by the following method: Step B1: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide and 4-vinylaniline were mixed, stirred at 150° C. for 9 h, filtered, washed, and dried under vacuum at 60° C. for 24 h to obtain an intermediate; Step B2: Mix phenylboric acid, the intermediate and deionized water, stir and reflux at 90°C for 4 hours, reduce the temperature to 40°C, continue stirring for 3 hours, naturally cool to room temperature, filter, wash, dry, and grind in a ball mill for 5 minutes, sieve with an 80-mesh sieve plate to obtain a modified flame retardant.

6. The method for preparing an outdoor aging-resistant PP board according to claim 5, characterized in that: In step B1, the usage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide and 4-vinylaniline is 0.05-0.1 mol: 30-50 mL: 5.96-11.92 g.

7. The method for preparing an outdoor aging-resistant PP board according to claim 5, characterized in that: In step B2, the dosage ratio of phenylboric acid, intermediate and deionized water is 3.05-6.1 g: 0.05-0.1 mol: 150-300 mL.

8. The method for preparing an outdoor aging-resistant PP board according to claim 1, characterized in that: The lubricant is ethylene bis stearic acid amide, and the antioxidant is antioxidant 1098.

9. An outdoor aging-resistant PP board, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 8.

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