High-toughness and high-weather-resistance polypropylene material and preparation method thereof
By adding amino-terminated polybutadiene and 4-(4,6-dichloro-1,3,5-triazine-2-oxy)-2-hydroxybenzophenone to polypropylene material to generate a UV absorber, the problems of easy breakage at room temperature and outdoor aging of polypropylene material are solved, and the high toughness and weather resistance are improved, making it suitable for the processing and production of plastic products.
Patent Information
- Application Number
- CN202511408281.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-29
- Publication Date
- 2026-01-20
AI Technical Summary
Polypropylene materials are prone to breakage at room temperature and low temperature, have poor impact toughness, and are prone to aging under outdoor ultraviolet radiation, resulting in a decrease in material strength. Existing improvement methods lead to a decrease in overall weather resistance or impact strength.
A UV absorber was generated by reacting amino-terminated polybutadiene and 4-(4,6-dichloro-1,3,5-triazine-2-oxy)-2-hydroxybenzophenone into polypropylene. This absorber was then blended with an antioxidant, and a high-toughness, high-weather-resistant polypropylene material was prepared using a twin-screw extruder and a molding press.
It significantly improves the impact strength and elongation at break of polypropylene, reduces ultraviolet transmittance, and enhances the weather resistance of the material, making it suitable for the processing and production of plastic products.
Smart Images
Figure BDA0005620673410000021 
Figure BDA0005620673410000022
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of polypropylene materials, in particular to a high-toughness and high-weather-resistance polypropylene material and a preparation method thereof. BACKGROUND
[0002] Polypropylene is a general-purpose plastic with excellent comprehensive performance, is widely used in the field of daily plastic products such as food containers, household appliances, toys and outdoor furniture, and is low in cost, easy to process, non-toxic and odorless and good in chemical stability. However, it is easy to break at room temperature and low temperature, has poor impact toughness, is easy to age under the irradiation of ultraviolet rays outdoors, and thus leads to the decrease of the material strength. The above-mentioned defects limit the application of the polypropylene material in high toughness and outdoor scenes.
[0003] At present, the methods for improving the above-mentioned defects of the polypropylene include adding a blended elastomer and a ultraviolet absorber. For example, the flexible chain segment of polybutadiene is used to improve the plastic deformation capacity of the material and effectively improve the impact strength and elongation at break; the ultraviolet absorber of the dihydroxybenzophenone type is used to absorb ultraviolet rays and delay the aging of the material. If the toughening agent or the ultraviolet absorber is used alone, the overall weather resistance or impact strength of the material may be decreased. It is an urgent problem to be solved to prepare a new type of additive with the functions of toughening and ultraviolet resistance, so as to simultaneously improve the toughness and weather resistance of the polypropylene material. SUMMARY
[0004] (I) Technical problem solved:
[0005] In view of the defects of the prior art, the application provides a high-toughness and high-weather-resistance polypropylene material and a preparation method thereof, and solves the problems of poor toughness and weather resistance of the polypropylene material.
[0006] (II) Technical scheme: A preparation method of a high-toughness and high-weather-resistance polypropylene material is as follows:
[0007] S1, tetrahydrofuran, hydroxyl-terminated polybutadiene, p-toluenesulfonyl chloride and pyridine are added into a flask, and a sulfonic acid esterification reaction is carried out under stirring at 20-30 DEG C for 24-36 h; the product is added into a toluene solution containing ethylenediamine, and an aminolysis reaction is carried out under stirring at 100-110 DEG C for 12-18 h; the product is distilled under reduced pressure, washed with ethanol and dried to obtain amino-terminated polybutadiene; and the preparation reaction formula is as follows:
[0008]
[0009] S2, adding water, N,N-dimethylformamide, mass ratio of 100: (7.8-9.2): (1-1.2) of amino-terminated polybutadiene, 4-(4,6-dichloro-1,3,5-triazine-2-oxyl)-2-hydroxybenzophenone, sodium carbonate into the flask, stirring at 15-25℃ for 8-12h, filtering, washing the obtained filter cake with hot water, methanol, drying to obtain the ultraviolet absorber, the preparation reaction formula is:
[0010]
[0011] S3, adding mass ratio of 100: (3-8): (0.1-0.3) of polypropylene, ultraviolet absorber, antioxidant into the high-speed mixer, mixing, then extruding and granulating the material through a double-screw extruder, the temperature of each section is 150℃, 180℃, 200℃, 215℃, 210℃, and the rotation speed is 150-250rpm, then molding in a molding machine to obtain the high-toughness and high-weather-resistance polypropylene material.
[0012] Further, the mass ratio of hydroxyl-terminated polybutadiene, p-toluenesulfonyl chloride, pyridine, ethylenediamine is 100: (10.6-13.3): (9.7-12.8): (2.6-3.3).
[0013] Further, the temperature of the molding machine is 200-220℃, and the pressure is 5-10MPa.
[0014] (Three) beneficial technical effects: the amino-terminated polybutadiene is subjected to a polymerization reaction with 4-(4,6-dichloro-1,3,5-triazine-2-oxyl)-2-hydroxybenzophenone to obtain an ultraviolet absorber, which is then blended with polypropylene and an antioxidant to prepare a high-toughness and high-weather-resistance polypropylene material. The polybutadiene toughening structure is conducive to improving the impact strength and elongation at break of the polypropylene. The benzophenone group as an efficient ultraviolet absorption group converts ultraviolet light into harmless heat energy, significantly reducing the ultraviolet transmittance of the polypropylene material, and the ultraviolet transmittance continuously decreases and the ultraviolet resistance of the polypropylene continuously increases with the increase of the amount of the ultraviolet absorber. The triazine ring as a bridge connects the polybutadiene and the benzophenone, successfully integrating the toughening structure and the ultraviolet resistance structure, endowing the polypropylene with excellent toughness and weather resistance, and being suitable for the processing and production of plastic products, and being helpful to improve the quality of plastic products. DETAILED DESCRIPTION
[0015] The above summary of the application will be further described in detail in combination with specific embodiments, but it should not be understood that the scope of the above subject matter of the application is limited to the following examples.
[0016] 4-(4,6-dichloro-1,3,5-triazin-2-yl)oxy-2-hydroxybenzophenone was prepared according to the method in the journal "Synthetic Fiber Industry", December 2016, Vol. 39, No. 6, document "Synthesis and structure performance research of benzophenone-triazine ultraviolet absorber", and the structural formula is as follows:
[0017] Example 1: A method for preparing a high-toughness and high-weather-resistance polypropylene material is as follows:
[0018] S1, 400 mL of tetrahydrofuran, 200 g of hydroxyl-terminated polybutadiene (average molecular weight of about 4500, same below), 26.6 g of p-toluenesulfonyl chloride, and 19.4 g of pyridine were added to a flask, and a sulfonate esterification reaction was carried out by stirring at 25°C for 24 h. In a nitrogen atmosphere, the product was added to 80 mL of a toluene solution containing 6.6 g of ethylenediamine, and an aminolysis reaction was carried out by stirring at 110°C for 12 h. After vacuum distillation, ethanol washing, and drying, an amino-terminated polybutadiene was obtained.
[0019] S2, 800 mL of water, 200 mL of N,N-dimethylformamide, 500 g of amino-terminated polybutadiene, 46 g of 4-(4,6-dichloro-1,3,5-triazin-2-yl)oxy-2-hydroxybenzophenone, and 5 g of sodium carbonate were added to a flask, and a reaction was carried out by stirring at 15°C for 10 h. After filtration, the obtained filter cake was washed with hot water and methanol, and dried to obtain an ultraviolet absorber.
[0020] S3, 2 kg of polypropylene, 60 g of the ultraviolet absorber, and 6 g of antioxidant 1010 were added to a high-speed mixer, and after mixing, the materials were extruded and granulated through a twin-screw extruder, with the temperature of each section being 150°C, 180°C, 200°C, 215°C, and 210°C, and the rotation speed being 150 rpm. Then, a high-toughness and high-weather-resistance polypropylene material was obtained by molding in a molding machine at 220°C and 5 MPa.
[0021] Example 2: A method for preparing a high-toughness and high-weather-resistance polypropylene material is as follows:
[0022] S1, 500 mL of tetrahydrofuran, 200 g of hydroxyl-terminated polybutadiene, 21.2 g of p-toluenesulfonyl chloride, and 25.6 g of pyridine were added to a flask, and a sulfonate esterification reaction was carried out by stirring at 20°C for 36 h. In a nitrogen atmosphere, the product was added to a toluene solution containing 5.2 g of ethylenediamine, and an aminolysis reaction was carried out by stirring at 100°C for 15 h. After vacuum distillation, ethanol washing, and drying, an amino-terminated polybutadiene was obtained.
[0023] S2, to the flask was added 750 mL of water, 250 mL of N,N-dimethylformamide, 500 g of amino-terminated polybutadiene, 39 g of 4-(4,6-dichloro-1,3,5-triazin-2- yl)-2-hydroxybenzophenone, 6 g of sodium carbonate, and the mixture was stirred at 20 °C for 12 h. The resulting filter cake was washed with hot water and methanol and dried to obtain the ultraviolet absorber.
[0024] S3, to the high-speed mixer was added 2 kg of polypropylene, 90 g of the ultraviolet absorber, and 4 g of antioxidant 1010. After mixing, the material was extruded and pelletized by a twin-screw extruder at 150 °C, 180 °C, 200 °C, 215 °C, and 210 °C, and at a rotation speed of 200 rpm. Then, the material was molded into a high-toughness and high-weather-resistance polypropylene material by a molding machine at 200 °C and 10 MPa.
[0025] Example 3: A high-toughness and high-weather-resistance polypropylene material was prepared as follows:
[0026] S1, to the flask was added 600 mL of tetrahydrofuran, 200 g of hydroxyl-terminated polybutadiene, 23.9 g of p-toluenesulfonyl chloride, and 22.5 g of pyridine. The mixture was stirred at 30 °C for 30 h to perform a sulfonate esterification reaction. The product was added to a toluene solution containing 5.9 g of ethylenediamine, and the mixture was stirred at 105 °C for 18 h to perform an aminolysis reaction. The product was distilled under reduced pressure, washed with ethanol, and dried to obtain amino-terminated polybutadiene.
[0027] S2, to the flask was added 500 mL of water, 200 mL of N,N-dimethylformamide, 500 g of amino-terminated polybutadiene, 46 g of 4-(4,6-dichloro-1,3,5-triazin-2- yl)-2-hydroxybenzophenone, and 5.5 g of sodium carbonate. The mixture was stirred at 25 °C for 8 h. The resulting filter cake was washed with hot water and methanol and dried to obtain the ultraviolet absorber.
[0028] S3, to the high-speed mixer was added 2 kg of polypropylene, 120 g of the ultraviolet absorber, and 2 g of antioxidant 1010. After mixing, the material was extruded and pelletized by a twin-screw extruder at 150 °C, 180 °C, 200 °C, 215 °C, and 210 °C, and at a rotation speed of 250 rpm. Then, the material was molded into a high-toughness and high-weather-resistance polypropylene material by a molding machine at 210 °C and 7.5 MPa.
[0029] Example 4: A high-toughness and high-weather-resistance polypropylene material was prepared as follows:
[0030] S1, to the flask was added 600 mL of tetrahydrofuran, 200 g of hydroxyl-terminated polybutadiene, 21.2 g of p-toluenesulfonyl chloride, 19.4 g of pyridine, and the mixture was stirred at 30°C for 36 h to perform a sulfonate reaction. The product was added to 80 mL of a toluene solution containing 6.6 g of ethylenediamine under a nitrogen atmosphere, and the mixture was stirred at 100°C for 12 h to perform an aminolysis reaction. The mixture was distilled under reduced pressure, washed with ethanol, and dried to obtain an amino-terminated polybutadiene.
[0031] S2, to the flask was added 800 mL of water, 225 mL of N,N-dimethylformamide, 500 g of amino-terminated polybutadiene, 43 g of 4-(4,6-dichloro-1,3,5-triazin-2-oxyl)-2-hydroxybenzophenone, and 5 g of sodium carbonate, and the mixture was stirred at 15°C for 12 h to perform a reaction. The resulting filter cake was washed with hot water and methanol, and dried to obtain an ultraviolet absorber.
[0032] S3, to the high-speed mixer was added 2 kg of polypropylene, 160 g of the ultraviolet absorber, and 4 g of antioxidant 1010, and the mixture was mixed and then extruded and pelletized by a twin-screw extruder at 150°C, 180°C, 200°C, 215°C, and 210°C at a rotation speed of 150 rpm. Then, the mixture was molded into a high-toughness and high-weather-resistance polypropylene material by a molding machine at 200°C and 8 MPa.
[0033] The difference between Comparative Example 1 and Example 1 is that no ultraviolet absorber was added.
[0034] S1, to the high-speed mixer was added 2 kg of polypropylene and 6 g of antioxidant 1010, and the mixture was mixed and then extruded and pelletized by a twin-screw extruder at 150°C, 180°C, 200°C, 215°C, and 210°C at a rotation speed of 150 rpm. Then, the mixture was molded into a polypropylene material by a molding machine at 220°C and 5 MPa.
[0035] The difference between Comparative Example 2 and Example 1 is that an amino-terminated polybutadiene was used instead of an ultraviolet absorber.
[0036] S1, to the flask was added 400 mL of tetrahydrofuran, 200 g of hydroxyl-terminated polybutadiene, 26.6 g of p-toluenesulfonyl chloride, and 19.4 g of pyridine, and the mixture was stirred at 25°C for 24 h to perform a sulfonate reaction. The product was added to 80 mL of a toluene solution containing 6.6 g of ethylenediamine under a nitrogen atmosphere, and the mixture was stirred at 110°C for 12 h to perform an aminolysis reaction. The mixture was distilled under reduced pressure, washed with ethanol, and dried to obtain an amino-terminated polybutadiene.
[0037] S2, 2 kg of polypropylene, 60 g of the terminal amino polybutadiene, 6 g of antioxidant 1010 were added into a high-speed mixer, after mixing, the material was extruded and granulated by a twin-screw extruder, the temperature of each section was 150 °C, 180 °C, 200 °C, 215 °C, 210 °C, and the rotating speed was 150 rpm, then the material was molded into polypropylene material by a molding machine at 220 °C and 5 MPa.
[0038] The difference between Comparative Example 3 and Example 1 is that 2,4-dichloro-6-phenoxy-1,3,5-triazine is used instead of 4-(4,6-dichloro-1,3,5-triazin-2- yl)-2-hydroxybenzophenone:
[0039] S1, 800 mL of water, 200 mL of N,N-dimethylformamide, 500 g of polyetheramine D2000, 46 g of 4-(4,6-dichloro-1,3,5-triazin-2-yl)-2-hydroxybenzophenone, and 5 g of sodium carbonate were added into a flask, and the mixture was stirred at 15 °C for 10 h, then filtered, the obtained filter cake was washed with hot water and methanol, and dried to obtain an ultraviolet absorber.
[0040] S2, 800 mL of water, 200 mL of N,N-dimethylformamide, 500 g of polyetheramine D2000, 46 g of 4-(4,6-dichloro-1,3,5-triazin-2-yl)-2-hydroxybenzophenone, and 5 g of sodium carbonate were added into a flask, and the mixture was stirred at 15 °C for 10 h, then filtered, the obtained filter cake was washed with hot water and methanol, and dried to obtain an ultraviolet absorber.
[0041] S3, 2 kg of polypropylene, 60 g of the ultraviolet absorber, and 6 g of antioxidant 1010 were added into a high-speed mixer, after mixing, the material was extruded and granulated by a twin-screw extruder, the temperature of each section was 150 °C, 180 °C, 200 °C, 215 °C, 210 °C, and the rotating speed was 150 rpm, then the material was molded into polypropylene material by a molding machine at 220 °C and 5 MPa.
[0042] The difference between Comparative Example 4 and Example 1 is that polyetheramine D2000 is used instead of the terminal amino polybutadiene:
[0043] S1, 800 mL of water, 200 mL of N,N-dimethylformamide, 500 g of polyetheramine D2000, 46 g of 4-(4,6-dichloro-1,3,5-triazin-2-yl)-2-hydroxybenzophenone, and 5 g of sodium carbonate were added into a flask, and the mixture was stirred at 15 °C for 10 h, then filtered, the obtained filter cake was washed with hot water and methanol, and dried to obtain an ultraviolet absorber.
[0044] S2, 2 kg of polypropylene, 60 g of ultraviolet absorber, 6 g of antioxidant 1010 were added to a high-speed mixer, after mixing, the material was extruded and granulated by a twin-screw extruder, the temperature of each section was 150℃, 180℃, 200℃, 215℃, 210℃, and the rotation speed was 150 rpm, then the material was molded into polypropylene material by a molding machine at 220℃ and 5 MPa.
[0045] The impact strength of the polypropylene material was tested according to GB / T 1843-2008. The elongation at break was tested according to GB / T 1040.1-2018.
[0046] The anti-ultraviolet performance (ultraviolet transmittance) was tested as follows: the ultraviolet transmittance of the polypropylene material at 365 nm was measured by using a UV1000F type ultraviolet transmittance analyzer.
[0047] Table 1 Mechanical properties and weather resistance of polypropylene material
[0048] Impact strength (KJ / m 2 ) Elongation at break (%) Ultraviolet transmittance (%) Example 1 4.14 65.3 23.1 Example 2 5.88 112.7 13.6 Example 3 7.29 105.1 4.2 Example 4 5.55 83.0 1.8 Comparative Example 1 3.40 51.8 55.3 Comparative Example 2 4.69 68.5 52.7 Comparative Example 3 4.11 63.2 51.8 Comparative Example 4 3.52 53.4 22.7
[0049] Compared with Comparative Example 1, the ultraviolet absorber in Examples 1-4 was prepared by reacting amino-terminated polybutadiene with 4-(4,6-dichloro-1,3,5-triazin-2-oxyl)-2-hydroxybenzophenone, and then blended with polypropylene and antioxidant to prepare a polypropylene material with high toughness and weather resistance. The toughness and weather resistance of the material are improved mainly due to the combined effect of the polybutadiene segment and the dihydroxybenzophenone group. The flexible polybutadiene segment can absorb impact energy, thereby improving the impact strength and elongation at break of the material. The dihydroxybenzophenone group, as an efficient ultraviolet absorption group, converts ultraviolet light into harmless heat energy, significantly reducing the ultraviolet transmittance of the polypropylene material, and as the amount of ultraviolet absorber increases, the ultraviolet transmittance continues to decrease and the anti-ultraviolet effect is enhanced.
[0050] Comparative Example 1 does not contain ultraviolet absorber, polybutadiene, or dihydroxybenzophenone ultraviolet absorption group, resulting in low impact strength and elongation at break of the polypropylene material, and extremely high ultraviolet transmittance, which does not have the characteristics of high toughness and anti-ultraviolet, and cannot meet the requirements of high performance. In Comparative Example 2, amino-terminated polybutadiene is used instead of ultraviolet absorber, which lacks dihydroxybenzophenone ultraviolet absorption group, resulting in high ultraviolet transmittance of the polypropylene material and lower weather resistance than some examples. In Comparative Example 3, 2,4-dichloro-6-phenoxy-1,3,5-triazine is polymerized with amino-terminated polybutadiene to obtain an ultraviolet absorber that does not contain dihydroxybenzophenone ultraviolet absorption group, and the ultraviolet transmittance is higher than that of all examples, and the weather resistance of the obtained polypropylene material is poor.
[0051] Comparative Example 4 carried out a polymerization reaction of polyetheramine D2000 and 4-(4,6-dichloro-1,3,5-triazin-2-yloxy)-2-hydroxybenzophenone, and the obtained ultraviolet absorber did not contain a polybutadiene toughening structure, resulting in low impact strength and elongation at break of the polypropylene.
[0052] Although the present application has been described in detail by way of preferred embodiments, the application is not limited to the preferred embodiments. Various equivalent modifications and alterations can be made to the embodiments of the present application without deviating from the spirit and scope of the application, and such modifications and alterations should be considered to fall within the scope of the present application.
Claims
1. A method for preparing a high-toughness, high-weather-resistant polypropylene material, characterized in that, The preparation method of the polypropylene material is as follows: Step (1), adding tetrahydrofuran, hydroxyl-terminated polybutadiene, p-toluenesulfonyl chloride, pyridine into a flask, stirring to carry out sulfonate reaction, adding the product into a toluene solution containing ethylenediamine, stirring to carry out aminolysis reaction, reducing pressure distillation, ethanol washing, drying to obtain amino-terminated polybutadiene; Step (2), adding water, N,N-dimethylformamide, amino-terminated polybutadiene, 4-(4,6-dichloro-1,3,5-triazin-2-oxyl)-2-hydroxybenzophenone, sodium carbonate into a flask, stirring to carry out reaction, filtering, washing the obtained filter cake with hot water and methanol, drying to obtain an ultraviolet absorber; Step (3), adding polypropylene, the ultraviolet absorber, and an antioxidant into a high-speed mixer, mixing, then extruding and granulating the mixture through a twin-screw extruder, and then molding the granules in a molding machine to obtain the high-toughness and high-weather-resistance polypropylene material.
2. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (1), the mass ratio of the hydroxyl-terminated polybutadiene, the p-toluenesulfonyl chloride, the pyridine, and the ethylenediamine is 100:(10.6-13.3):(9.7-12.8):(2.6-3.3).
3. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (1), the sulfonate reaction is carried out at a temperature of 20-30℃ for 24-36h.
4. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (1), the aminolysis reaction is carried out at a temperature of 100-110℃ for 12-18h with condensation reflux.
5. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (2), the mass ratio of the amino-terminated polybutadiene, the 4-(4,6-dichloro-1,3,5-triazin-2-oxyl)-2-hydroxybenzophenone, and the sodium carbonate is 100:(7.8-9.2):(1-1.2).
6. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (2), the stirring reaction is carried out at a temperature of 15-25℃ for 8-12h.
7. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (3), the mass ratio of the polypropylene, the ultraviolet absorber, and the antioxidant is 100:(3-8):(0.1-0.3).
8. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (3), the temperature of each section of the twin-screw extruder is 150℃, 180℃, 200℃, 215℃, and 210℃, and the rotation speed is 150-250rpm.
9. The method for preparing the high-toughness and high-weather-resistance polypropylene material according to claim 1, characterized in that, In step (3), the temperature of the molding machine is 200-220℃, and the pressure is 5-10MPa.
10. A high-toughness and high-weather-resistance polypropylene material prepared by the preparation method of any one of claims 1-9.