Nanometer enhanced impact modifier for polyvinyl chloride and preparation method of nanometer enhanced impact modifier

Abstract

The invention discloses a nano reinforced impact modifier for polyvinyl chloride and a preparation method thereof, and relates to the technical field of impact modifiers. The nano reinforced impact modifier is prepared from the following raw materials: a CNC (at) ACM compound, hyperbranched polyglycerol, amino-terminated hyperbranched polyamide, organic montmorillonite, maleic anhydride grafted POE, a silane coupling agent and nano zinc oxide; the CNC (at) ACM compound is prepared from acrylate rubber, silanized nano cellulose and p-toluenesulfonic acid; the preparation method of the nano-reinforced impact modifier comprises the following steps: pretreating nano-cellulose, synthesizing a CNC-coated ACM compound, pretreating auxiliary components, preparing a base material, and preparing the nano-reinforced impact modifier. The nano-enhanced impact modifier prepared by the invention can effectively enhance the mechanical properties and thermal properties of polyvinyl chloride.

Description

Technical Field

[0001] The present invention relates to the technical field of impact modifiers, in particular to a nano-enhanced impact modifier for polyvinyl chloride and a preparation method thereof. Background Art

[0002] Polyvinyl chloride (PVC) is a general-purpose plastic with high production volume and wide application. It is characterized by low cost, excellent chemical resistance, and balanced mechanical properties. It is widely used in building materials, packaging products, electronic appliances, and other fields. However, the presence of a large number of chlorine atoms in the PVC molecular chain and strong intermolecular forces lead to its significant low-temperature brittleness and low notched impact strength, which limits its application in scenarios with high impact resistance requirements. To improve this defect, impact modifiers have become an indispensable additive in PVC processing. They form an elastic dispersed phase in the PVC matrix, absorbing impact energy and inhibiting crack propagation, thereby improving the toughness of the material.

[0003] Currently commonly used impact modifiers for polyvinyl chloride include acrylic rubber, chlorinated polyethylene, methyl methacrylate-butadiene-styrene copolymer, etc. Among them, acrylic rubber is widely used due to its good compatibility with polyvinyl chloride and excellent weather resistance, but when added alone, it is easy to cause the rigidity of the material to decrease. In addition, most existing modifiers are difficult to balance the impact resistance and rigidity, and during high-temperature processing, the thermal stability of the composite material is easily reduced due to insufficient interfacial compatibility, and it is unable to meet the requirements of the high-end field for the comprehensive performance of polyvinyl chloride materials. The prior art with publication number CN118048043B discloses a high tensile strength impact modifier for polyvinyl chloride and a preparation method thereof. This prior art mainly relies on nitrile rubber coated lignin and modified nanopowders, which has limited improvement on the mechanical properties of polyvinyl chloride, insufficient balancing effect on rigidity and toughness, and is prone to performance degradation due to thermal degradation during high-temperature processing. The prior art with publication number CN119875022A discloses a transparent impact modifier for yellowing-resistant polyvinyl chloride and a preparation method thereof. The core of this prior art is to improve yellowing resistance and impact resistance. The overall mechanical performance improvement is limited to toughness alone, and the effect of maintaining the thermal properties of polyvinyl chloride at high temperatures is poor.

[0004] In summary, although the existing technical solutions have improved certain properties of impact modifiers to a certain extent, the following technical problems still exist: the mechanical properties and thermal properties of polyvinyl chloride have been limitedly improved. Summary of the Invention

[0005] In order to solve the above problems existing in the prior art, the present invention provides a nano-enhanced impact modifier for polyvinyl chloride and a preparation method thereof, and achieves the following invention objectives: to prepare a nano-enhanced impact modifier that can effectively enhance the mechanical properties and thermal properties of polyvinyl chloride.

[0006] To achieve the above objectives, the technical solutions adopted are as follows: A nano-enhanced impact modifier for polyvinyl chloride comprises the following raw materials, calculated by weight: 55-60 parts of a CNC@ACM composite, 6-8 parts of hyperbranched polyglycidol, 6-8 parts of amino-terminated hyperbranched polyamide, 4-6 parts of organized montmorillonite, 4-5 parts of maleic anhydride-grafted POE, 0.6-0.8 parts of a silane coupling agent, and 2-3 parts of nano-zinc oxide.

[0007] The CNC@ACM composite is prepared from acrylic rubber, silanized nanocellulose and p-toluenesulfonic acid.

[0008] The molecular weight of the hyperbranched polyglycidol is 800-2500 g / mol.

[0009] The amino-terminated hyperbranched polyamide has an amino-terminated functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0010] The grafting rate of the maleic anhydride grafted POE is 1.0%-1.5%.

[0011] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0012] The present invention also provides a method for preparing a nano-enhanced impact modifier for polyvinyl chloride, comprising the following steps: Step 1: Nanocellulose pretreatment Dried nanocellulose is added to toluene at a nanocellulose:toluene mass ratio of 1:(19-20), and ultrasonically dispersed for 30-40 minutes at a power of 300-400W. A silanization reagent is added at a silanization reagent:nanocellulose mass ratio of (0.3-0.5):1, under nitrogen protection, and the temperature is raised to 110-115°C for 6-8 hours. The mixture is then cooled to room temperature and centrifuged at 6000-7000 rpm for 15-20 minutes to collect the solid phase. After centrifugation, the mixture is washed 3-5 times with anhydrous ethanol and then dried at 50-60°C for 8-10 hours to obtain silanized nanocellulose. The nanocellulose has a diameter of 5-100 nm and a length of 50-350 nm. The silanization reagent is a mixture of methyltrimethoxysilane and triethylamine, with the triethylamine content being 8% by weight of the methyltrimethoxysilane.

[0013] Step 2: Synthesis of CNC@ACM composite The silanized nanocellulose was dispersed in toluene at a mass ratio of 1:(9-10) and ultrasonically treated at an ultrasonic power of 200-300 W for 30-40 min. After the ultrasonic treatment, acrylic rubber was added and stirred until fully dispersed. The mass ratio of acrylic rubber to silanized nanocellulose was (6-7):1. Then, p-toluenesulfonic acid was added. The amount of p-toluenesulfonic acid was 1.5-2% of the mass of the silanized nanocellulose. The temperature was raised to 110-115°C, the stirring rate was 300-400 rpm, and the reaction was stirred for 6-7 hours. After the reaction was completed, the mixture was cooled to room temperature, and excess ethanol was added and stirred until all solids were precipitated. The mixture was then centrifuged at a speed of 5000-6000 rpm for 10-15 min to collect the solid phase. The solid phase was washed with ethanol 3-5 times and then dried at 60-70°C for 8-9 hours to obtain a nanocellulose-coated acrylic rubber composite (CNC@ACM composite). The acrylic rubber is selected from model AR200.

[0014] Step 3: Pretreatment of auxiliary components The organic montmorillonite is dispersed in deionized water at a mass ratio of (1-2):40, and ultrasonic treatment is performed at a power of 300-400W for 20-30 minutes; then stirring is performed for 10-15 minutes at a stirring speed of 300-400rpm to obtain an organic montmorillonite dispersion; nano zinc oxide is added to deionized water at a mass ratio of nano zinc oxide to deionized water of 1:10, and ultrasonic treatment is performed at a power of 300-400W for 20-30 minutes to obtain a zinc oxide suspension; a silane coupling agent, ethanol, and deionized water are mixed at a mass ratio of 1:4:0.2, the temperature is raised to 40-45°C, and the mixture is reacted for 30-40 minutes to obtain a pre-hydrolyzed silane solution.

[0015] Step 4: Preparation of base materials The CNC@ACM composite is mixed with sodium lauryl sulfate and deionized water, and stirred in a mass ratio of 1:(0.2-0.3):(9-10). The mixture is stirred for 10-15 minutes at a stirring speed of 300-400 rpm. Hyperbranched polyglycidol is added, the temperature is raised to 50-55°C, the speed is increased to 400-500 rpm, and the mixture is stirred for 40-50 minutes. Then, amino-terminated hyperbranched polyamide is added, the temperature is raised to 60-65°C, and the reaction is continued for 40-50 minutes to obtain a base material.

[0016] Step 5: Prepare nano-enhanced impact modifier The maleic anhydride grafted POE is mixed with toluene, sodium lauryl sulfate and glycerol in a mass ratio of 2:(10-15):(0.8-1):(2.5-3) to obtain a maleic anhydride grafted POE pretreatment solution.

[0017] The method comprises the following steps: adding an organic montmorillonite dispersion and a pre-hydrolyzed silane solution to a base material, stirring the mixture evenly, and then performing ultrasonic treatment at a power of 400-500W for 40-50 minutes; adding a zinc oxide suspension, controlling the temperature at 50-60°C, stirring at a speed of 300-400 rpm, and stirring for reaction for 1-1.5 hours; heating the mixture to 60-70°C, slowly adding a maleic anhydride grafted POE pretreatment solution dropwise, and stirring for reaction for 1.5-2 hours; after the reaction is completed, centrifuging the mixture at a speed of 8000-9000 rpm for 20-30 minutes, and collecting a solid product; washing the solid product with anhydrous ethanol for 3-4 times, and then drying the solid product at a temperature of 60-70°C for 12-14 hours; grinding the solid product with a high-speed grinder, and passing the mixture through a 200-mesh sieve to obtain a nano-enhanced impact modifier.

[0018] The beneficial effects of the present invention are as follows: (1) The nano-enhanced impact modifier for polyvinyl chloride of the present invention effectively improves the mechanical properties of polyvinyl chloride. The notched impact strength of the polyvinyl chloride test sample at 23°C reaches 64.5-67.2KJ / m 2 , the tensile strength is 66.3-68.6MPa, the elongation at break is 372-384%, and the bending strength reaches 84.8-87.5MPa.

[0019] (2) The nano-enhanced impact modifier for polyvinyl chloride of the present invention has a significant effect on enhancing the thermal properties of polyvinyl chloride. The Congo red test paper color change time of the polyvinyl chloride test sample is 82-86 minutes, and the Vicat softening point is 88.1-89.5°C. DETAILED DESCRIPTION

[0020] To make the purpose, technical solutions and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0021] Example 1 A nano-enhanced impact modifier for polyvinyl chloride and its preparation method A nano-reinforced impact modifier for polyvinyl chloride comprises the following raw materials, calculated by weight: 55 parts of a CNC@ACM composite, 8 parts of hyperbranched polyglycidol, 8 parts of amino-terminated hyperbranched polyamide, 4 parts of organized montmorillonite, 4 parts of maleic anhydride-grafted POE, 0.6 parts of a silane coupling agent, and 2 parts of nano-zinc oxide.

[0022] The molecular weight of the hyperbranched polyglycidol is 800-2500 g / mol.

[0023] The amino-terminated hyperbranched polyamide has an amino-terminated functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0024] The grafting rate of the maleic anhydride grafted POE is 1.0%-1.5%.

[0025] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0026] The organic montmorillonite is selected from Nanomer ® I.44P.

[0027] A method for preparing a nano-enhanced impact modifier for polyvinyl chloride comprises the following steps: Step 1: Nanocellulose pretreatment Dried nanocellulose was added to toluene at a nanocellulose to toluene mass ratio of 1:19, and ultrasonically dispersed for 30 minutes at a power of 400W. A silanization reagent was added at a silanization reagent to nanocellulose mass ratio of 0.3:1, and nitrogen was purged. The temperature was raised to 110°C and the reaction was allowed to proceed for 8 hours. The mixture was then cooled to room temperature and centrifuged at 6000 rpm for 20 minutes to collect the solid phase. After centrifugation, the mixture was washed three times with anhydrous ethanol and then dried at 50°C for 10 hours to obtain silanized nanocellulose. The silanization reagent was a mixture of methyltrimethoxysilane and triethylamine, with the triethylamine being 8% by weight of the methyltrimethoxysilane.

[0028] Step 2: Synthesis of CNC@ACM composite Silanized nanocellulose was dispersed in toluene at a mass ratio of 1:9. Ultrasonic treatment was performed at 200 W for 40 minutes. After sonication, acrylic rubber was added and stirred until fully dispersed. The mass ratio of acrylic rubber to silanized nanocellulose was 6:1. Then, p-toluenesulfonic acid was added at a concentration of 1.5% of the mass of the silanized nanocellulose. The mixture was heated to 110°C and stirred at 300 rpm for 7 hours. After the reaction, the mixture was cooled to room temperature and stirred with excess ethanol until all solids precipitated. The mixture was then centrifuged at 5000 rpm for 15 minutes to collect the solid phase. The solid phase was washed three times with ethanol and then dried at 60°C for 9 hours to obtain a CNC@ACM composite. The acrylic rubber was AR200.

[0029] Step 3: Pretreatment of auxiliary components The organized montmorillonite is dispersed in deionized water at a mass ratio of 1:40, and ultrasonic treatment is performed at a power of 300 W for 30 minutes; then stirring is performed for 10 minutes at a stirring speed of 400 rpm to obtain an organized montmorillonite dispersion; nano zinc oxide is added to deionized water at a mass ratio of 1:10, and ultrasonic treatment is performed at a power of 300 W for 30 minutes to obtain a zinc oxide suspension; a silane coupling agent, ethanol, and deionized water are mixed at a mass ratio of 1:4:0.2, the temperature is raised to 40°C, and the mixture is reacted for 40 minutes to obtain a pre-hydrolyzed silane solution.

[0030] Step 4: Preparation of base materials The CNC@ACM composite was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.2:9 and stirred for 15 minutes at a rotation speed of 300 rpm. Hyperbranched polyglycidol was added, the temperature was raised to 50°C, the rotation speed was increased to 400 rpm, and the reaction was stirred for 50 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 60°C, and the reaction was continued for 50 minutes to obtain a base material.

[0031] Step 5: Prepare nano-enhanced impact modifier The maleic anhydride grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:10:0.8:2.5 to obtain a maleic anhydride grafted POE pretreatment solution.

[0032] The organic montmorillonite dispersion and pre-hydrolyzed silane solution were added to the base material, stirred evenly, and then ultrasonic treatment was performed at a power of 400 W for 50 minutes; zinc oxide suspension was added, the temperature was controlled at 50°C, the stirring speed was 300 rpm, and the stirring reaction was carried out for 1.5 hours; the temperature was raised to 60°C, and the maleic anhydride grafted POE pretreatment solution was slowly added dropwise, and then the stirring reaction was carried out for 2 hours; after the reaction was completed, centrifugation was carried out at a speed of 8000 rpm for 30 minutes to collect the solid product; the solid product was washed with anhydrous ethanol 3 times, and then dried at a temperature of 60°C for 14 hours; after drying, it was ground with a high-speed crusher and passed through a 200-mesh sieve to obtain a nano-reinforced impact modifier.

[0033] Example 2 A nano-enhanced impact modifier for polyvinyl chloride and its preparation method A nano-reinforced impact modifier for polyvinyl chloride comprises the following raw materials, calculated by weight: 58 parts of a CNC@ACM composite, 7 parts of hyperbranched polyglycidol, 7 parts of amino-terminated hyperbranched polyamide, 5 parts of organized montmorillonite, 5 parts of maleic anhydride-grafted POE, 0.8 parts of a silane coupling agent, and 3 parts of nano-zinc oxide.

[0034] The molecular weight of the hyperbranched polyglycidol is 800-2500 g / mol.

[0035] The amino-terminated hyperbranched polyamide has an amino-terminated functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0036] The grafting rate of the maleic anhydride grafted POE is 1.0%-1.5%.

[0037] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0038] The organic montmorillonite is selected from the model of Nanomer ® I.44P.

[0039] A method for preparing a nano-enhanced impact modifier for polyvinyl chloride comprises the following steps: Step 1: Nanocellulose pretreatment Dried nanocellulose was added to toluene at a nanocellulose to toluene mass ratio of 1:20, and ultrasonically dispersed for 30 minutes at a power of 400W. A silanization reagent was added at a silanization reagent to nanocellulose mass ratio of 0.4:1, and nitrogen was purged. The temperature was raised to 115°C and the reaction was allowed to proceed for 7 hours. The mixture was then cooled to room temperature and centrifuged at 7000 rpm for 20 minutes to collect the solid phase. After centrifugation, the mixture was washed four times with anhydrous ethanol and then dried at 60°C for 10 hours to obtain silanized nanocellulose. The silanization reagent was a mixture of methyltrimethoxysilane and triethylamine, with the triethylamine being 8% by weight of the methyltrimethoxysilane.

[0040] Step 2: Synthesis of CNC@ACM composite Silanized nanocellulose was dispersed in toluene at a mass ratio of 1:10 and subjected to ultrasonic treatment at 300W for 40 minutes. Acrylic rubber was then added and stirred until fully dispersed at a mass ratio of 7:1. p-Toluenesulfonic acid was then added at a concentration of 2% of the mass of the silanized nanocellulose. The mixture was heated to 115°C and stirred at 400 rpm for 7 hours. After the reaction, the mixture was cooled to room temperature and stirred with excess ethanol until all solids precipitated. The mixture was then centrifuged at 6000 rpm for 15 minutes to collect the solid phase. The solid phase was washed five times with ethanol and then dried at 70°C for 9 hours to obtain a CNC@ACM composite. The acrylic rubber was AR200.

[0041] Step 3: Pretreatment of auxiliary components The organic montmorillonite is dispersed in deionized water at a mass ratio of 1:40, and ultrasonic treatment is performed at a power of 400 W for 20 minutes; then stirring is performed for 15 minutes at a stirring speed of 300 rpm to obtain an organic montmorillonite dispersion; nano zinc oxide is added to deionized water at a mass ratio of 1:10, and ultrasonic treatment is performed at a power of 400 W for 30 minutes to obtain a zinc oxide suspension; a silane coupling agent, ethanol, and deionized water are mixed at a mass ratio of 1:4:0.2, the temperature is raised to 45°C, and the mixture is reacted for 40 minutes to obtain a pre-hydrolyzed silane solution.

[0042] Step 4: Preparation of base materials The CNC@ACM composite was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.3:10 and stirred for 15 minutes at a speed of 400 rpm. Hyperbranched polyglycidol was added, the temperature was raised to 55°C, the speed was increased to 500 rpm, and the reaction was stirred for 50 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 65°C, and the reaction was continued for 50 minutes to obtain a base material.

[0043] Step 5: Prepare nano-enhanced impact modifier The maleic anhydride grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:15:0.9:3 to obtain a maleic anhydride grafted POE pretreatment solution.

[0044] The organic montmorillonite dispersion and pre-hydrolyzed silane solution were added to the base material, stirred evenly, and then ultrasonic treatment was performed at a power of 500 W for 40 minutes; zinc oxide suspension was added, the temperature was controlled at 60°C, the stirring speed was 400 rpm, and the stirring reaction was carried out for 1.5 hours; the temperature was raised to 70°C, and the maleic anhydride grafted POE pretreatment solution was slowly added dropwise, and then the stirring reaction was carried out for 2 hours; after the reaction was completed, centrifugation was carried out at a speed of 9000 rpm for 30 minutes to collect the solid product; the solid product was washed with anhydrous ethanol 4 times, and then dried at a temperature of 70°C for 14 hours; after drying, it was ground with a high-speed crusher and passed through a 200-mesh sieve to obtain a nano-reinforced impact modifier.

[0045] Example 3 A nano-enhanced impact modifier for polyvinyl chloride and its preparation method A nano-reinforced impact modifier for polyvinyl chloride comprises the following raw materials, calculated by weight: 60 parts of a CNC@ACM composite, 6 parts of hyperbranched polyglycidol, 6 parts of amino-terminated hyperbranched polyamide, 6 parts of organized montmorillonite, 5 parts of maleic anhydride-grafted POE, 0.8 parts of a silane coupling agent, and 3 parts of nano-zinc oxide.

[0046] The molecular weight of the hyperbranched polyglycidol is 800-2500 g / mol.

[0047] The amino-terminated hyperbranched polyamide has an amino-terminated functionality of 4-14 and a molecular weight of 300-1400 g / mol.

[0048] The grafting rate of the maleic anhydride grafted POE is 1.0%-1.5%.

[0049] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0050] The organic montmorillonite is selected from Nanomer ® I.44P.

[0051] A method for preparing a nano-enhanced impact modifier for polyvinyl chloride comprises the following steps: Step 1: Nanocellulose pretreatment Dried nanocellulose was added to toluene at a nanocellulose to toluene mass ratio of 1:20, and ultrasonically dispersed for 40 minutes at a power of 300W. A silanization reagent was added at a silanization reagent to nanocellulose mass ratio of 0.5:1, and nitrogen was purged. The temperature was raised to 115°C and the reaction was allowed to proceed for 6 hours. The mixture was then cooled to room temperature and centrifuged at 7000 rpm for 15 minutes to collect the solid phase. After centrifugation, the mixture was washed five times with anhydrous ethanol and then dried at 60°C for 8 hours to obtain silanized nanocellulose. The silanization reagent was a mixture of methyltrimethoxysilane and triethylamine, with the triethylamine being 8% by weight of the methyltrimethoxysilane.

[0052] Step 2: Synthesis of CNC@ACM composite Silanized nanocellulose was dispersed in toluene at a mass ratio of 1:10 and subjected to ultrasonic treatment at 300W for 30 minutes. Acrylic rubber was then added and stirred until fully dispersed at a mass ratio of 7:1. p-Toluenesulfonic acid was then added at a concentration of 2% of the mass of the silanized nanocellulose. The mixture was heated to 115°C and stirred at 400 rpm for 6 hours. After the reaction, the mixture was cooled to room temperature and stirred with excess ethanol until all solids precipitated. The mixture was then centrifuged at 6000 rpm for 10 minutes to collect the solid phase. The solid phase was washed five times with ethanol and then dried at 70°C for 8 hours to obtain a CNC@ACM composite. The acrylic rubber was AR200.

[0053] Step 3: Pretreatment of auxiliary components The organized montmorillonite is dispersed in deionized water at a mass ratio of 1:20, and ultrasonic treatment is performed at a power of 400 W for 20 minutes; then stirring is performed for 15 minutes at a stirring speed of 300 rpm to obtain an organized montmorillonite dispersion; nano zinc oxide is added to deionized water at a mass ratio of 1:10, and ultrasonic treatment is performed at a power of 400 W for 20 minutes to obtain a zinc oxide suspension; a silane coupling agent, ethanol, and deionized water are mixed at a mass ratio of 1:4:0.2, the temperature is raised to 45°C, and the mixture is reacted for 30 minutes to obtain a pre-hydrolyzed silane solution.

[0054] Step 4: Preparation of base materials The CNC@ACM composite was mixed with sodium lauryl sulfate and deionized water in a mass ratio of 1:0.3:10 and stirred for 10 minutes at a speed of 400 rpm. Hyperbranched polyglycidol was added, the temperature was raised to 55°C, the speed was increased to 500 rpm, and the reaction was stirred for 40 minutes. Then, amino-terminated hyperbranched polyamide was added, the temperature was raised to 65°C, and the reaction was continued for 40 minutes to obtain a base material.

[0055] Step 5: Prepare nano-enhanced impact modifier The maleic anhydride grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:15:1:3 to obtain a maleic anhydride grafted POE pretreatment solution.

[0056] The organic montmorillonite dispersion and the pre-hydrolyzed silane solution were added to the base material, stirred evenly, and then ultrasonic treatment was performed at a power of 500 W for 40 minutes; zinc oxide suspension was added, the temperature was controlled at 60°C, the stirring speed was 400 rpm, and the stirring reaction was carried out for 1 hour; the temperature was raised to 70°C, and the maleic anhydride grafted POE pretreatment solution was slowly added dropwise, and then the stirring reaction was carried out for 1.5 hours; after the reaction was completed, centrifugation was carried out at a speed of 9000 rpm for 20 minutes to collect the solid product; the solid product was washed with anhydrous ethanol 4 times, and then dried at a temperature of 70°C for 12 hours; after drying, it was ground with a high-speed crusher and passed through a 200-mesh sieve to obtain a nano-reinforced impact modifier.

[0057] Comparative Example 1 An impact modifier comprises the following raw materials, calculated in parts by weight: 58 parts of acrylic rubber, 7 parts of hyperbranched polyglycidol, 7 parts of amino-terminated hyperbranched polyamide, 5 parts of organized montmorillonite, 5 parts of maleic anhydride-grafted POE, 0.8 parts of a silane coupling agent, and 3 parts of nano zinc oxide.

[0058] The molecular weight of the hyperbranched polyglycidol is 800-2500 g / mol.

[0059] The end amino functionality of the end amino hyperbranched polyamide is 4-14, and the molecular weight is 300-1400 g / mol.

[0060] The grafting rate of the maleic anhydride grafted POE is 1.0%-1.5%.

[0061] The silane coupling agent is 3-(2,3-epoxypropoxy) propyl trimethoxysilane.

[0062] The acrylic rubber is selected from AR200.

[0063] The organic montmorillonite is selected from Nanomer ® I.44P.

[0064] A preparation method of an impact modifier, comprising the following steps: Step one, auxiliary component pretreatment This step is the same as the "auxiliary component pretreatment" operation in Example 2.

[0065] Step two, preparation of base material The acrylic rubber, sodium lauryl sulfate and deionized water are mixed and stirred, the mass ratio of the acrylic rubber, sodium lauryl sulfate and deionized water is 1:0.3:10, stirring for 15 min at a speed of 400 rpm; hyperbranched polyglycidol is added, the temperature is raised to 55℃, the stirring speed is raised to 500 rpm, and the reaction is stirred for 50 min; then end amino hyperbranched polyamide is added, the temperature is raised to 65℃, and the reaction is continued for 50 min to obtain the base material.

[0066] Step three, preparation of impact modifier This step is the same as the "preparation of nano-enhanced impact modifier" operation in Example 2.

[0067] Comparative Example 2 An impact modifier, the raw material composition is: CNC@ACM composite 58 parts, hyperbranched polyglycidol 7 parts, end amino hyperbranched polyamide 7 parts, maleic anhydride grafted POE 5 parts, silane coupling agent 0.8 parts, nano zinc oxide 3 parts.

[0068] The molecular weight of the hyperbranched polyglycidol is 800-2500 g / mol.

[0069] The end amino functionality of the end amino hyperbranched polyamide is 4-14, and the molecular weight is 300-1400 g / mol.

[0070] The grafting rate of the maleic anhydride grafted POE is 1.0%-1.5%.

[0071] The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0072] A method for preparing an impact modifier comprises the following steps: Step 1: Nanocellulose pretreatment This step is the same as the "nanocellulose pretreatment" operation in Example 2.

[0073] Step 2: Synthesis of CNC@ACM composite This step is the same as the operation of “Synthesis of CNC@ACM Composite” in Example 2.

[0074] Step 3: Pretreatment of auxiliary components Nano-zinc oxide is added to deionized water in a mass ratio of nano-zinc oxide to deionized water of 1:10, and ultrasonic treatment is performed at a power of 300-400W and an ultrasonic time of 20-30 minutes to obtain a zinc oxide suspension; a silane coupling agent, ethanol, and deionized water are mixed in a mass ratio of 1:4:0.2, the temperature is raised to 40-45°C, and the reaction is carried out for 30-40 minutes to obtain a pre-hydrolyzed silane solution.

[0075] Step 4: Preparation of base materials This step is the same as the "base material preparation" operation in Example 2.

[0076] Step 5: Prepare the impact modifier The maleic anhydride grafted POE was mixed with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:15:0.9:3 to obtain a maleic anhydride grafted POE pretreatment solution.

[0077] The pre-hydrolyzed silane solution was added to the base material, stirred evenly, and then ultrasonic treatment was performed at a power of 500 W for 40 minutes; zinc oxide suspension was added, the temperature was controlled at 60°C, the stirring speed was 400 rpm, and the stirring reaction was carried out for 1.5 hours; the temperature was raised to 70°C, and the maleic anhydride grafted POE pretreatment solution was slowly added dropwise, and then the stirring reaction was carried out for 2 hours; after the reaction was completed, centrifugation was performed at a speed of 9000 rpm for 30 minutes to collect the solid product; the solid product was washed with anhydrous ethanol 4 times, and then dried at a temperature of 70°C for 14 hours; after drying, it was ground with a high-speed crusher and passed through a 200-mesh sieve to obtain an impact modifier.

[0078] Example 4 Performance Test (I) The impact modifier prepared in Example 1-3, Comparative Example 1-2 is used as raw material to prepare a polyvinyl chloride test sample, and the raw material is weighed in a ratio of 100 parts of PVC resin, 8 parts of impact modifier, 3 parts of calcium-zinc stabilizer, and 2 parts of lubricant; melt blending in a double screw extruder, screw speed is 150 r / min, temperature is 160-180℃, after extruding and granulating, injection molding is carried out to obtain a nano-enhanced impact polyvinyl chloride test sample. The notched impact strength test at 23℃ is carried out according to the test method specified in GB / T 1043.1-2008; the tensile strength and elongation at break test is carried out according to the test method specified in GB / T 1040-2018; the bending strength test is carried out according to the test method specified in GB / T 9341-2008. The specific test results are shown in Table 1.

[0079] Table 1

[0080] From the test results in Table 1, it can be seen that the nano-enhanced impact modifier prepared in Example 1-3 is used as raw material to prepare a polyvinyl chloride test sample, the notched impact strength at 23℃ reaches 64.5-67.2 KJ / m 2 , the tensile strength is 66.3-68.6 MPa, the elongation at break is 372-384%, and the bending strength reaches 84.8-87.5 MPa, which is significantly enhanced compared with the comparative example, which shows that the addition of CNC@ACM composite and organic montmorillonite in the nano-enhanced impact modifier of the application effectively improves the mechanical properties of the polyvinyl chloride test sample.

[0081] (II) The impact modifier prepared in Example 1-3, Comparative Example 1-2 is used as raw material to prepare a polyvinyl chloride test sample for thermal performance test, the polyvinyl chloride test sample is heated to 180℃ and kept constant, and the Congo red test paper discoloration time is recorded; the Vicat softening point test is carried out according to the test method specified in GB / T 1633-2000. The specific test results are shown in Table 2.

[0082] Table 2

[0083] From the test results in Table 2, it can be seen that the nano-enhanced impact modifier prepared in Example 1-3 is used as raw material to prepare a polyvinyl chloride test sample, the Congo red test paper discoloration time is 82-86 min, and the Vicat softening point is 88.1-89.5℃. It is proved that the nano-enhanced impact modifier prepared in the application has a significant enhancement effect on the thermal performance of the polyvinyl chloride test sample.

[0084] Obviously, there are many specific implementation methods that can be changed under the concept of the present invention. Here, it should be stated that any changes made under the inventive concept of the present invention will fall within the scope of protection of the present invention.

Claims

1. A nano-enhanced impact modifier for polyvinyl chloride, characterized in that: The nano-enhanced impact modifier is composed of the following raw materials, in parts by weight: 55-60 parts of CNC@ACM composite, 6-8 parts of hyperbranched polyglycidol, 6-8 parts of amino-terminated hyperbranched polyamide, 4-6 parts of organized montmorillonite, 4-5 parts of maleic anhydride grafted POE, 0.6-0.8 parts of silane coupling agent, and 2-3 parts of nano zinc oxide; The CNC@ACM composite is prepared from acrylic rubber, silanized nanocellulose, and p-toluenesulfonic acid; The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

2. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 1, characterized in that: The method includes the steps of pre-treating nanocellulose, synthesizing CNC@ACM composite, pre-treating auxiliary components, preparing base materials, and preparing nano-enhanced impact modifier; The nanocellulose pretreatment comprises the following steps: adding dried nanocellulose to toluene at a mass ratio of nanocellulose to toluene of 1:(19-20), and ultrasonically dispersing the mixture for 30-40 minutes; adding a silanization agent at a mass ratio of the silanization agent to the nanocellulose of (0.3-0.5):1, passing nitrogen gas for protection, heating the mixture to 110-115° C., and reacting the mixture for 6-8 hours; then cooling the mixture to room temperature, centrifuging, washing, and drying the mixture to obtain silanized nanocellulose.

3. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 2, characterized in that: The silanization agent is a mixture of methyltrimethoxysilane and triethylamine, and the triethylamine is 8% of the mass of methyltrimethoxysilane.

4. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 2, characterized in that: The method for synthesizing the CNC@ACM composite comprises dispersing silanized nanocellulose in toluene at a mass ratio of silanized nanocellulose to toluene of 1:(9-10), and ultrasonically treating the mixture for 30-40 minutes. After the ultrasonic treatment, acrylic rubber is added and stirred until fully dispersed. Then, p-toluenesulfonic acid is added in an amount of 1.5-2% of the mass of the silanized nanocellulose. The mixture is heated to 110-115° C. and stirred for 6-7 hours. After the reaction, the mixture is cooled to room temperature, and excess ethanol is added and stirred until all solids are precipitated. The mixture is then centrifuged, washed, and dried to obtain the CNC@ACM composite.

5. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 4, characterized in that: The mass ratio of the acrylic rubber to the silanized nanocellulose is (6-7):

1.

6. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 2, characterized in that: The auxiliary component pretreatment comprises the following steps: dispersing the organized montmorillonite in deionized water, performing ultrasonic treatment for 20-30 minutes, stirring for 10-15 minutes, and obtaining an organized montmorillonite dispersion; adding nano zinc oxide into the deionized water in a mass ratio of nano zinc oxide to deionized water of 1:10, and performing ultrasonic treatment for 20-30 minutes, and obtaining a zinc oxide suspension; and mixing a silane coupling agent, ethanol, and deionized water in a mass ratio of 1:4:0.2, heating the mixture to 40-45° C., and reacting the mixture for 30-40 minutes, and obtaining a pre-hydrolyzed silane solution.

7. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 2, characterized in that: The base material is prepared by mixing the CNC@ACM composite with sodium lauryl sulfate and deionized water and stirring for 10-15 minutes; adding hyperbranched polyglycidol, heating to 50-55° C., stirring and reacting for 40-50 minutes, and then adding amino-terminated hyperbranched polyamide, heating to 60-65° C., and continuing to react for 40-50 minutes to obtain the base material.

8. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 7, characterized in that: The mass ratio of the CNC@ACM composite, sodium lauryl sulfate, and deionized water is 1:(0.2-0.3):(9-10).

9. The method for preparing a nano-enhanced impact modifier for polyvinyl chloride according to claim 2, characterized in that: The nano-enhanced impact modifier is prepared by mixing maleic anhydride-grafted POE with toluene, sodium lauryl sulfate, and glycerol in a mass ratio of 2:(10-15):(0.8-1):(2.5-3) to obtain a maleic anhydride-grafted POE pretreatment solution; adding an organic montmorillonite dispersion and a pre-hydrolyzed silane solution to a base material, stirring evenly, and then performing an ultrasonic treatment for 40-50 minutes; adding a zinc oxide suspension, controlling the temperature at 50-60°C, and stirring for 1-1.5 hours; raising the temperature to 60-70°C, slowly adding the maleic anhydride-grafted POE pretreatment solution dropwise, and stirring for 1.5-2 hours; after the reaction, centrifuging, washing, drying, grinding, and passing through a 200-mesh sieve to obtain the nano-enhanced impact modifier.

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