High-strength CPVC / ASA double-alloy material and preparation method thereof

Abstract

The invention relates to the technical field of plastic alloys, in particular to a high-strength CPVC / ASA double-alloy material and a preparation method thereof. The high-strength CPVC / ASA double-alloy material is prepared from the following raw materials in parts by mass: 20 to 50 parts of ASA, 20 to 40 parts of chlorinated polyvinyl chloride, 1 to 2 parts of 3-aminopropyltriethoxysilane, 1 to 5 parts of glutaraldehyde, 1 to 5 parts of carboxyl-terminated polyamidoamine, 5 to 10 parts of aminated glass fiber, 1 to 2 parts of lubricant and 1 to 2 parts of antioxidant. The use of the plasticizer can be reduced, the processing thermal stability of the CPVC / ASA double-alloy material can be effectively improved, system melting mixing and smooth product processing forming are finally guaranteed, the CPVC / ASA double-alloy material has high impact strength, high fluidity and rigid-tough balance of a product, the cracking phenomenon is not prone to occurring when the CPVC / ASA double-alloy material is applied to a sounding pipe, the impact resistance of the product can be greatly improved, and the service life of the product is prolonged. The reliability of the sounding pipe is enhanced, and the sounding pipe is suitable for large-scale popularization and application.

Description

Technical Field

[0001] The present invention relates to the technical field of plastic alloys, and particularly relates to a high-strength CPVC / ASA double alloy material and a preparation method thereof. Background Art

[0002] ASA is a ternary polymer composed of acrylonitrile, styrene, and acrylate rubber. The structure of ASA is similar to that of ABS. It retains the good mechanical and physical properties of ABS as an engineering plastic, and has good weather resistance, high-temperature resistance, and anti-static properties. However, it is brittle, which limits its application range.

[0003] Chlorinated polyvinyl chloride resin (CPVC) is a product obtained by further chlorination modification of polyvinyl chloride resin, and has excellent flame retardancy, heat resistance, etc. However, if it is used for ASA modification, the two are not easy to process, it is difficult to ensure the full play of the material's performance, the processing and molding are difficult, and at the same time, the impact strength of the modified product is low.

[0004] If CPVC and ASA are compounded and blended for modification, although plasticizers can be added to improve the processing situation, it will cause a decrease in thermal stability and tensile strength. At present, how to effectively improve the compatibility and fluidity of CPVC / ASA alloy materials, improve the tensile strength, and enhance the thermal stability has become an urgent technical problem to be solved. Summary of the Invention

[0005] The purpose of the present invention is to solve the disadvantages existing in the prior art, and to provide a high-strength CPVC / ASA double alloy material and a preparation method thereof.

[0006] A high-strength CPVC / ASA double alloy material, the raw materials of which include, by mass: 20-50 parts of ASA, 20-40 parts of chlorinated polyvinyl chloride, 1-2 parts of 3-aminopropyltriethoxysilane, 1-5 parts of glutaraldehyde, 1-5 parts of terminal carboxyl polyamidoamine, 5-10 parts of aminated glass fiber, 1-2 parts of lubricant, 1-2 parts of antioxidant, and 1-2 parts of stabilizer.

[0007] Preferably, the lubricant is ethoxylated octadecylamine or / and sodium dodecylsulfonate.

[0008] Preferably, the antioxidant is 4,4'-methylenebis(2,6-di-tert-butylphenol).

[0009] Preferably, the stabilizer is calcium-zinc stabilizer or hydrotalcite.

[0010] Preferably, the aminated glass fiber is prepared by the following steps: adding glass fiber into sodium hydroxide solution, ultrasonically treating for 1 - 2 h, filtering, washing, drying in vacuum, feeding into sulfuric acid solution, ultrasonically treating for 10 - 30 min, filtering, washing until neutral, drying in vacuum, adding into ethanol aqueous solution, adding aminopropyltriethoxysilane, refluxing and stirring at 70 - 90 °C for 1 - 2 h, filtering, washing, and drying.

[0011] More preferably, the mass ratio of glass fiber to aminopropyltriethoxysilane is 5 - 15:1 - 3.

[0012] More preferably, the ultrasonic frequency is 25 - 32 kHz.

[0013] More preferably, the concentration of sodium hydroxide solution is 0.5 - 1.5 mol / L, and the concentration of sulfuric acid solution is 1 - 2 mol / L.

[0014] The preparation method of the above high-strength CPVC / ASA double alloy material includes the following steps: S1. Adding chlorinated polyvinyl chloride into ethanol aqueous solution, ultrasonically treating for 1 - 2 h, adding 3-aminopropyltriethoxysilane, ultrasonically treating for 1 - 3 h, filtering, washing, drying in vacuum, adding into water, adding glutaraldehyde, stirring at 40 - 50 °C for 1 - 2 h, washing, drying at 40 - 60 °C for 1 - 2 h to obtain pretreated chlorinated polyvinyl chloride; S2. Adding the pretreated chlorinated polyvinyl chloride into deionized water, adding terminal carboxyl polyamidoamine and stirring for 1 - 2 h, cooling to room temperature, filtering, washing, drying in vacuum, stirring with aminated glass fiber, lubricant, and antioxidant for 2 - 6 min, adding stabilizer and stirring for 1 - 3 min to obtain a premix; S3. Adding ASA from the main feeding port into a twin-screw extruder, adding the premix from the side feeding port into the twin-screw extruder for extrusion, the temperature before the side feeding port is 175 - 195 °C, the temperature after the side feeding port is 190 - 200 °C, and the die head temperature is 160 - 180 °C.

[0015] Preferably, in S1, the ultrasonic frequency is 25 - 30 kHz. Beneficial effects

[0016] In the present invention, chlorinated polyvinyl chloride is successively modified with 3-aminopropyltriethoxysilane and glutaraldehyde, and then crosslinked with carboxyl-terminated polyamidoamine, which can effectively increase the surface activity of chlorinated polyvinyl chloride and has a good binding effect with aminated glass fiber. The addition of aminated glass fiber can effectively improve the rigidity of the system, as well as the folding resistance and flexural strength. At the same time, it has a high binding strength with chlorinated polyvinyl chloride and will not precipitate in the system even when the addition amount is too large, effectively enhancing the toughness of the plastic alloy and improving its impact strength. Subsequently, it is compounded with ASA, with a good binding effect, which can effectively ensure the structural stability of the product, uniform dispersion of components, good thermal stability, high tensile strength, and good mechanical properties.

[0017] The present invention can reduce the use of plasticizers, effectively improve the processing thermal stability of CPVC / ASA double alloy materials, and ultimately ensure the smooth melting mixing of the system and the successful molding of product processing. It has high impact strength and high fluidity, with a balance of rigidity and toughness in the product. When applied to acoustic logging tubes, it is not easy to crack, can greatly improve the impact resistance of the product, has excellent stability, and enhances the reliability of acoustic logging tubes, being suitable for large-scale popularization and application. Brief Description of the Drawings

[0018] Figure 1 It is a comparison chart of the tensile strength and flexural strength of the CPVC / ASA double alloy materials obtained in Example 5 and Comparative Examples 1-2.

[0019] Figure 2 It is a comparison chart of the notched impact strength at room temperature and low temperature (-30°C) of the CPVC / ASA double alloy materials obtained in Example 5 and Comparative Examples 1-2.

[0020] Figure 3 It is a comparison chart of the Vicat softening temperature and the dimensional change rate after heating of the CPVC / ASA double alloy materials obtained in Example 5 and Comparative Examples 1-2. Detailed Embodiments

[0021] The present invention will be further illustrated below in conjunction with specific embodiments.

[0022] The ASA used below is from BASF Germany, with the grade of 778TE, and its melt volume flow rate (220°C / 10.0 kg) is 5.00 cm 3 / 10 min. The chlorinated polyvinyl chloride used below is purchased from a certain Xin New Material Technology Co., Ltd. in Shanghai, with the model of IN-F02 and an average particle size of 300 μm. Example 1

[0023] A high-strength CPVC / ASA double alloy material, the raw materials of which include: 200 g of ASA, 200 g of chlorinated polyvinyl chloride, 10 g of 3-aminopropyltriethoxysilane, 10 g of glutaraldehyde, 10 g of 2.0-generation carboxyl-terminated polyamidoamine, 50 g of aminated glass fiber, 10 g of ethoxylated octadecylamine, 10 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 10 g of hydrotalcite.

[0024] The aminated glass fiber is prepared by the following steps: adding 50 g of glass fiber into 300 g of a sodium hydroxide solution with a concentration of 0.5 mol / L, ultrasonically treating for 1 h with an ultrasonic frequency of 25 kHz, filtering, washing, drying in vacuum, feeding it into 300 g of a sulfuric acid solution with a concentration of 1 mol / L, ultrasonically treating for 10 min, filtering, washing with water until neutral, drying in vacuum, adding it into 300 g of an ethanol aqueous solution with a mass fraction of 40%, adding 10 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, refluxing and stirring at a temperature of 70 °C for 1 h with a stirring speed of 100 r / min, filtering, washing with ethanol, and drying.

[0025] The preparation method of the above high-strength CPVC / ASA double alloy material includes the following steps: S1. Add chlorinated polyvinyl chloride into 1000 g of an ethanol aqueous solution with a mass fraction of 40%, ultrasonically treat for 1 h with an ultrasonic frequency of 25 kHz, add 3-aminopropyltriethoxysilane and ultrasonically treat for 1 h, filter, wash, dry in vacuum, add it into 1000 g of water, add glutaraldehyde, stir at a temperature of 40 °C for 1 h, wash with deionized water, and dry at a temperature of 40 °C for 1 h to obtain pretreated chlorinated polyvinyl chloride; S2. Add the pretreated chlorinated polyvinyl chloride into 1000 g of deionized water, add carboxyl-terminated polyamidoamine and stir for 1 h with a stirring temperature of 70 °C, cool to room temperature, filter, wash, dry in vacuum, send it together with aminated glass fiber, ethoxylated octadecylamine, and 4,4'-methylenebis(2,6-di-tert-butylphenol) into a high-speed mixer, stir at a speed of 100 r / min for 2 min, add hydrotalcite and stir for 1 min to obtain a premix; S3. Add ASA from the main feeding port into a twin-screw extruder, add the premix from the side feeding port into the twin-screw extruder for extrusion. The temperature before the side feeding port is 175 °C, the temperature after the side feeding port is 190 °C, the die head temperature is 160 °C, and the length-diameter ratio of the screws of the twin-screw extruder is 20:1. Example 2

[0026] A high-strength CPVC / ASA double alloy material, the raw materials of which include: 500 g of ASA, 400 g of chlorinated polyvinyl chloride, 20 g of 3-aminopropyltriethoxysilane, 50 g of glutaraldehyde, 50 g of 4.0-generation carboxyl-terminated polyamidoamine, 100 g of amino-functionalized glass fiber, 20 g of sodium dodecylsulfonate, 20 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 20 g of hydrotalcite.

[0027] The amino-functionalized glass fiber is prepared by the following steps: adding 150 g of glass fiber into 600 g of sodium hydroxide solution with a concentration of 1.5 mol / L, ultrasonically treating for 2 h with an ultrasonic frequency of 32 kHz, filtering, washing, drying in vacuum, feeding it into 600 g of sulfuric acid solution with a concentration of 2 mol / L, ultrasonically treating for 30 min, filtering, washing with water until neutral, drying in vacuum, adding it into 600 g of ethanol aqueous solution with a mass fraction of 60%, adding 30 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, refluxing and stirring at a temperature of 90 °C for 2 h with a stirring speed of 500 r / min, filtering, washing with ethanol, and drying.

[0028] The preparation method of the above high-strength CPVC / ASA double alloy material includes the following steps: S1. Adding chlorinated polyvinyl chloride into 1500 g of ethanol aqueous solution with a mass fraction of 60%, ultrasonically treating for 2 h with an ultrasonic frequency of 30 kHz, adding 3-aminopropyltriethoxysilane and ultrasonically treating for 3 h, filtering, washing, drying in vacuum, adding it into 1500 g of water, adding glutaraldehyde, stirring at a temperature of 50 °C for 2 h, washing with deionized water, and drying at a temperature of 60 °C for 2 h to obtain pretreated chlorinated polyvinyl chloride; S2. Adding the pretreated chlorinated polyvinyl chloride into 1500 g of deionized water, adding carboxyl-terminated polyamidoamine and stirring for 2 h with a stirring temperature of 80 °C, cooling to room temperature, filtering, washing, drying in vacuum, and feeding it together with the amino-functionalized glass fiber, sodium dodecylsulfonate, and 4,4'-methylenebis(2,6-di-tert-butylphenol) into a high-speed mixer, stirring at a speed of 500 r / min for 6 min, adding hydrotalcite and stirring for 3 min to obtain a premix; S3. Adding ASA from the main feed port into a twin-screw extruder, adding the premix from the side feed port into the twin-screw extruder for extrusion, the temperature before the side feed port is 195 °C, the temperature after the side feed port is 200 °C, the die head temperature is 180 °C, and the length-diameter ratio of the twin-screw extruder is 30:1. Example 3

[0029] A high-strength CPVC / ASA dual alloy material, the raw materials of which include: 300 g of ASA, 350 g of chlorinated polyvinyl chloride, 13 g of 3-aminopropyltriethoxysilane, 40 g of glutaraldehyde, 20 g of 3.0-generation carboxyl-terminated polyamidoamine, 90 g of aminated glass fiber, 12 g of ethoxylated octadecylamine, 17 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 13 g of calcium-zinc stabilizer.

[0030] The aminated glass fiber is prepared by the following steps: Add 80 g of glass fiber to 500 g of a sodium hydroxide solution with a concentration of 0.8 mol / L, ultrasonically treat for 100 min, the ultrasonic frequency is 26 kHz, filter, wash, vacuum dry, then send it into 500 g of a sulfuric acid solution with a concentration of 1.2 mol / L, ultrasonically treat for 25 min, filter, wash with water until neutral, vacuum dry, add it to 400 g of an ethanol aqueous solution with a mass fraction of 55%, add 15 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, reflux and stir at a temperature of 85 °C for 80 min, the stirring speed is 400 r / min, filter, wash with ethanol, and dry.

[0031] The preparation method of the above high-strength CPVC / ASA dual alloy material includes the following steps: S1. Add chlorinated polyvinyl chloride to 1100 g of an ethanol aqueous solution with a mass fraction of 55%, ultrasonically treat for 80 min, the ultrasonic frequency is 29 kHz, add 3-aminopropyltriethoxysilane and ultrasonically treat for 1.5 h, filter, wash, vacuum dry, add it to 1300 g of water, add glutaraldehyde, stir at a temperature of 42 °C for 100 min, wash with deionized water, and dry at a temperature of 45 °C for 100 min to obtain pretreated chlorinated polyvinyl chloride; S2. Add the pretreated chlorinated polyvinyl chloride to 1100 g of deionized water, add carboxyl-terminated polyamidoamine and stir for 100 min, the stirring temperature is 73 °C, cool to room temperature, filter, wash, vacuum dry, and send it together with aminated glass fiber, ethoxylated octadecylamine, and 4,4'-methylenebis(2,6-di-tert-butylphenol) into a high-speed mixer, stir at a speed of 400 r / min for 3 min, add calcium-zinc stabilizer and stir for 2.5 min to obtain a premix; S3. Add ASA from the main feed port to a twin-screw extruder, add the premix from the side feed port to the twin-screw extruder for extrusion, the temperature before the side feed port is 180 °C, the temperature after the side feed port is 198 °C, the die head temperature is 165 °C, and the length-diameter ratio of the screws of the twin-screw extruder is 28:1. Example 4

[0032] A high-strength CPVC / ASA dual alloy material, the raw materials of which include: 400 g of ASA, 250 g of chlorinated polyvinyl chloride, 17 g of 3-aminopropyltriethoxysilane, 20 g of glutaraldehyde, 40 g of 3.0-generation carboxyl-terminated polyamidoamine, 70 g of amino-functionalized glass fiber, 18 g of sodium dodecyl sulfonate, 13 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 17 g of calcium-zinc stabilizer.

[0033] The amino-functionalized glass fiber is prepared by the following steps: Add 120 g of glass fiber to 400 g of sodium hydroxide solution with a concentration of 1.2 mol / L, perform ultrasonic treatment for 80 min, the ultrasonic frequency is 29 kHz, filter, wash, vacuum dry, then send it into 400 g of sulfuric acid solution with a concentration of 1.8 mol / L, perform ultrasonic treatment for 15 min, filter, wash with water until neutral, vacuum dry, add it to 500 g of ethanol aqueous solution with a mass fraction of 45%, add 25 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, reflux and stir at a temperature of 75 °C for 100 min, the stirring speed is 200 r / min, filter, wash with ethanol, and dry.

[0034] The preparation method of the above high-strength CPVC / ASA dual alloy material includes the following steps: S1. Add chlorinated polyvinyl chloride to 1300 g of ethanol aqueous solution with a mass fraction of 45%, perform ultrasonic treatment for 100 min, the ultrasonic frequency is 26 kHz, add 3-aminopropyltriethoxysilane and perform ultrasonic treatment for 2.5 h, filter, wash, vacuum dry, add it to 1100 g of water, add glutaraldehyde, stir at a temperature of 48 °C for 80 min, wash with deionized water, and dry at a temperature of 55 °C for 80 min to obtain pretreated chlorinated polyvinyl chloride; S2. Add the pretreated chlorinated polyvinyl chloride to 1300 g of deionized water, add carboxyl-terminated polyamidoamine and stir for 80 min, the stirring temperature is 77 °C, cool to room temperature, filter, wash, vacuum dry, send it into a high-speed mixer together with amino-functionalized glass fiber, sodium dodecyl sulfonate, and 4,4'-methylenebis(2,6-di-tert-butylphenol), stir at a speed of 200 r / min for 5 min, add calcium-zinc stabilizer and stir for 1.5 min to obtain a premix; S3. Add ASA from the main feed port to a twin-screw extruder, add the premix from the side feed port to the twin-screw extruder for extrusion, the temperature before the side feed port is 190 °C, the temperature after the side feed port is 192 °C, the die head temperature is 175 °C, and the length-diameter ratio of the screws of the twin-screw extruder is 22:1. Example 5

[0035] A high-strength CPVC / ASA double alloy material, the raw materials of which include: 350 g of ASA, 300 g of chlorinated polyvinyl chloride, 15 g of 3-aminopropyltriethoxysilane, 30 g of glutaraldehyde, 30 g of 3.0 generation carboxyl-terminated polyamidoamine, 80 g of aminated glass fiber, 15 g of ethoxylated octadecylamine, 15 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 15 g of calcium-zinc stabilizer.

[0036] The aminated glass fiber is prepared by the following steps: adding 100 g of glass fiber into 450 g of sodium hydroxide solution with a concentration of 1 mol / L, ultrasonically treating for 90 min, the ultrasonic frequency is 27 kHz, filtering, washing, vacuum drying, feeding it into 450 g of sulfuric acid solution with a concentration of 1.5 mol / L, ultrasonically treating for 20 min, filtering, washing with water until neutral, vacuum drying, adding it into 450 g of ethanol aqueous solution with a mass fraction of 45%, adding 20 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, refluxing and stirring at a temperature of 80 °C for 90 min, the stirring speed is 300 r / min, filtering, washing with ethanol, and drying.

[0037] The preparation method of the above high-strength CPVC / ASA double alloy material includes the following steps: S1. Add chlorinated polyvinyl chloride into 1200 g of ethanol aqueous solution with a mass fraction of 50%, ultrasonically treat for 90 min, the ultrasonic frequency is 27 kHz, add 3-aminopropyltriethoxysilane and ultrasonically treat for 2 h, filter, wash, vacuum dry, add it into 1200 g of water, add glutaraldehyde, stir at a temperature of 45 °C for 90 min, wash with deionized water, and dry at a temperature of 50 °C for 90 min to obtain pretreated chlorinated polyvinyl chloride; S2. Add the pretreated chlorinated polyvinyl chloride into 1200 g of deionized water, add carboxyl-terminated polyamidoamine and stir for 90 min, the stirring temperature is 75 °C, cool to room temperature, filter, wash, vacuum dry, send it together with aminated glass fiber, ethoxylated octadecylamine, and 4,4'-methylenebis(2,6-di-tert-butylphenol) into a high-speed mixer, stir at a speed of 300 r / min for 4 min, add calcium-zinc stabilizer and stir for 2 min to obtain a premix; S3. Add ASA from the main feed port into a twin-screw extruder, add the premix from the side feed port into the twin-screw extruder for extrusion, the temperature before the side feed port is 185 °C, the temperature after the side feed port is 195 °C, the die head temperature is 170 °C, and the length-diameter ratio of the twin-screw extruder screw is 25:1.

[0038] Comparative Example 1 A high-strength CPVC / ASA double alloy material, the raw materials of which include: 350 g of ASA, 300 g of chlorinated polyvinyl chloride, 15 g of 3-aminopropyltriethoxysilane, 30 g of glutaraldehyde, 30 g of 3.0-generation carboxyl-terminated polyamidoamine, 80 g of glass fiber, 15 g of ethoxylated octadecylamine, 15 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 15 g of calcium-zinc stabilizer.

[0039] The preparation method of the above high-strength CPVC / ASA double alloy material includes the following steps: S1. Add chlorinated polyvinyl chloride to 1200 g of an ethanol aqueous solution with a mass fraction of 50% and perform ultrasonic treatment for 90 min. The ultrasonic frequency is 27 kHz. Add 3-aminopropyltriethoxysilane and perform ultrasonic treatment for 2 h. Filter, wash, and vacuum dry. Then add it to 1200 g of water, add glutaraldehyde, stir at a temperature of 45 °C for 90 min, wash with deionized water, and dry at a temperature of 50 °C for 90 min to obtain pretreated chlorinated polyvinyl chloride. S2. Add the pretreated chlorinated polyvinyl chloride to 1200 g of deionized water, add carboxyl-terminated polyamidoamine and stir for 90 min. The stirring temperature is 75 °C. Cool to room temperature, filter, wash, and vacuum dry. Then send it together with glass fiber, ethoxylated octadecylamine, and 4,4'-methylenebis(2,6-di-tert-butylphenol) into a high-speed mixer and stir at a speed of 300 r / min for 4 min. Add calcium-zinc stabilizer and stir for 2 min to obtain a premix. S3. Add ASA from the main feeding port to a twin-screw extruder, and add the premix from the side feeding port to the twin-screw extruder for extrusion. The temperature before the side feeding port is 185 °C, the temperature after the side feeding port is 195 °C, and the die head temperature is 170 °C. The length-diameter ratio of the twin-screw extruder is 25:1.

[0040] Comparative Example 2 A high-strength CPVC / ASA double alloy material, the raw materials of which include: 350 g of ASA, 300 g of chlorinated polyvinyl chloride, 15 g of 3-aminopropyltriethoxysilane, 30 g of glutaraldehyde, 30 g of 3.0-generation carboxyl-terminated polyamidoamine, 80 g of aminated glass fiber, 15 g of ethoxylated octadecylamine, 15 g of 4,4'-methylenebis(2,6-di-tert-butylphenol), and 15 g of calcium-zinc stabilizer.

[0041] The amino-functionalized glass fiber is prepared by the following steps: Add 100 g of glass fiber into 450 g of sodium hydroxide solution with a concentration of 1 mol / L, ultrasonically treat for 90 min, the ultrasonic frequency is 27 kHz, filter, wash, vacuum dry, then send it into 450 g of sulfuric acid solution with a concentration of 1.5 mol / L, ultrasonically treat for 20 min, filter, wash with water until neutral, vacuum dry, add it into 450 g of ethanol aqueous solution with a mass fraction of 45%, add 20 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, reflux and stir at a temperature of 80 °C for 90 min, the stirring speed is 300 r / min, filter, wash with ethanol, and dry.

[0042] The preparation method of the above high-strength CPVC / ASA dual alloy material includes the following steps: S1. Add chlorinated polyvinyl chloride into 1200 g of ethanol aqueous solution with a mass fraction of 50%, ultrasonically treat for 90 min, the ultrasonic frequency is 27 kHz, add 3-aminopropyltriethoxysilane and ultrasonically treat for 2 h, filter, wash, vacuum dry, add it into 1200 g of water, add glutaraldehyde, stir at a temperature of 45 °C for 90 min, wash with deionized water, and dry at a temperature of 50 °C for 90 min to obtain pretreated chlorinated polyvinyl chloride; S2. Feed the pretreated chlorinated polyvinyl chloride, amino-functionalized glass fiber, ethoxylated octadecylamine, and 4,4'-methylenebis(2,6-di-tert-butylphenol) into a high-speed mixer, stir at a speed of 300 r / min for 4 min, add calcium-zinc stabilizer and terminal carboxyl polyamidoamine and stir for 2 min to obtain a premix; S3. Feed ASA into the twin-screw extruder from the main feeding port, feed the premix into the twin-screw extruder from the side feeding port and extrude, the temperature before the side feeding port is 185 °C, the temperature after the side feeding port is 195 °C, the die head temperature is 170 °C, and the length-diameter ratio of the twin-screw extruder screw is 25:1.

[0043] Make the CPVC / ASA dual alloy materials obtained in Example 5 and Comparative Examples 1-2 into sheets, and then conduct mechanical property tests on each group of sheet specimens as follows: (1) Determine the tensile strength of each group of specimens with reference to GB / T 1040.2-2022 Plastics - Determination of tensile properties - Part 2: Test conditions for moulded and extruded plastics; (2) Determine the flexural strength of each group of specimens with reference to GB / T 9341-2008 Plastics - Determination of flexural properties; (3) Determine the normal temperature and low temperature (-30 °C) notched impact strength of each group of specimens with reference to GB / T 1843-2008 Plastics - Determination of Izod impact strength.

[0044] (4)The Vicat softening temperature of each group of specimens was determined with reference to GB / T 1633-2000 Determination of Vicat Softening Temperature (VST) of Thermoplastics.

[0045] (5)The dimensional change rate after heating of each group of specimens was determined with reference to GB / T 4085-2015 Semi-rigid Polyvinyl Chloride Tiles.

[0046] As Figures 1 to 3 shown, the tensile strength, flexural strength, impact strength and Vicat softening temperature of the CPVC / ASA dual alloy material obtained in Example 5 were the highest, while the dimensional change rate after heating was the smallest, being superior to Comparative Examples 1-2 (P < 0.05).

[0047] The applicant believes that the reason for the above results is as follows: in the present invention, chlorinated polyvinyl chloride is successively modified with 3-aminopropyltriethoxysilane and glutaraldehyde, and then crosslinked with terminal carboxyl polyamidoamine, which can effectively increase the surface activity of chlorinated polyvinyl chloride and has a good binding effect with aminated glass fiber. The addition of aminated glass fiber can effectively improve the rigidity of the system and the folding resistance and flexural strength, and at the same time has a high binding strength with chlorinated polyvinyl chloride, and will not precipitate in the system even if the addition amount is too large, effectively enhancing the toughness of the plastic alloy and improving its impact strength. Subsequently, it is compounded with ASA, and the binding effect is good, which can effectively ensure the structural stability of the product, the components are evenly dispersed, the thermal stability is good, the tensile strength is high, and the mechanical properties are good.

[0048] The above is only the preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. A high-strength CPVC / ASA dual alloy material, characterized in that: The raw materials include, by mass, 20-50 parts of ASA, 20-40 parts of chlorinated polyvinyl chloride, 1-2 parts of 3-aminopropyltriethoxysilane, 1-5 parts of glutaraldehyde, 1-5 parts of terminal carboxyl polyamide amine, 5-10 parts of amino glass fiber, 1-2 parts of lubricant, 1-2 parts of antioxidant and 1-2 parts of stabilizer.

2. The high-strength CPVC / ASA dual alloy material according to claim 1, characterized in that: The lubricant is ethoxylated octadecylamine and / or sodium dodecyl sulfonate.

3. The high-strength CPVC / ASA dual alloy material according to claim 1, characterized in that: The antioxidant is 4,4'-methylenebis(2,6-di-tert-butylphenol).

4. The high-strength CPVC / ASA dual alloy material according to claim 1, characterized in that: The stabilizer is calcium zinc stabilizer or hydrotalcite.

5. The high-strength CPVC / ASA dual alloy material according to claim 1, characterized in that: The amino-treated glass fiber is prepared by the following steps: adding the glass fiber to a sodium hydroxide solution for ultrasonic treatment for 1-2 hours, filtering, washing, vacuum drying, sending the glass fiber to a sulfuric acid solution for ultrasonic treatment for 10-30 minutes, filtering, washing to neutrality, vacuum drying, adding to an ethanol aqueous solution, adding aminopropyltriethoxysilane, reflux stirring at 70-90° C. for 1-2 hours, filtering, washing, and drying.

6. The high-strength CPVC / ASA dual alloy material according to claim 5, characterized in that: The mass ratio of glass fiber to aminopropyltriethoxysilane is 5-15:1-3.

7. The high-strength CPVC / ASA dual alloy material according to claim 5, characterized in that: The ultrasound frequency is 25-32kHz.

8. The high-strength CPVC / ASA dual alloy material according to claim 5, characterized in that: The concentration of sodium hydroxide solution is 0.5-1.5 mol / L, and the concentration of sulfuric acid solution is 1-2 mol / L.

9. A method for preparing the high-strength CPVC / ASA dual alloy material according to any one of claims 1 to 8, characterized in that: The steps include: S1, adding chlorinated polyvinyl chloride to an ethanol aqueous solution and ultrasonically treating it for 1-2 hours, adding 3-aminopropyltriethoxysilane and ultrasonically treating it for 1-3 hours, filtering, washing, vacuum drying, adding to water, adding glutaraldehyde, stirring at 40-50° C. for 1-2 hours, washing, and drying at 40-60° C. for 1-2 hours to obtain pretreated chlorinated polyvinyl chloride; S2, adding pretreated chlorinated polyvinyl chloride to deionized water, adding carboxyl-terminated polyamide amine thereto and stirring for 1-2 hours, cooling to room temperature, filtering, washing, vacuum drying, stirring with amino glass fiber, lubricant, antioxidant for 2-6 minutes, adding stabilizer and stirring for 1-3 minutes to obtain a premix; S3. Add ASA into the twin-screw extruder from the main feed port, add the premix into the twin-screw extruder from the side feed port for extrusion, the temperature before the side feed port is 175-195°C, the temperature after the side feed port is 190-200°C, and the die head temperature is 160-180°C.

10. The method for preparing the high-strength CPVC / ASA dual alloy material according to claim 9, characterized in that: In S1, the ultrasound frequency is 25-30kHz.

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