Preparation method and application of processing type ACR for PVC transparent product

Abstract

The invention discloses a preparation method and application of processing type ACR for a PVC transparent product, and belongs to the field of ACR preparation. Comprising the following steps: step 1, mixing and reacting isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconate, diacetyl tartaric acid monoglyceride, aziridine isocyanate, azobisisoheptonitrile and deionized water to obtain a first mixed emulsion; 2, mixing the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol-polyoxyethylene ether and gamma-aminopropyltriethoxysilane, and then carrying out a reaction so as to obtain a mixed emulsion; and 3, drying the mixed emulsion in a spray drying manner to obtain the ACR auxiliary agent. The PVC transparent product produced by compounding the prepared ACR auxiliary agent and PVC has good transparency and thermal stability, and is low in cost, so that the performance of the PVC transparent product can be ensured on the premise of low cost.

Description

Technical Field

[0001] This invention belongs to the field of ACR preparation, specifically the preparation method and application of processable ACR for PVC transparent products. Background Technology

[0002] ACR additives are used to improve the performance of PVC production, effectively enhancing the processing fluidity, impact toughness, and transparency of PVC materials. However, in the production of transparent PVC products, the range of raw materials for ACR additive preparation is relatively narrow in order to ensure the transparency of the products themselves. Currently, ACR additives used in transparent PVC products have problems such as insufficient transparency and poor thermal stability in actual use. To ensure performance, ACR additives used in transparent PVC products generally use imported products such as PA-20 from Kanekachi of Japan. Although their performance is relatively good, their high price increases the production cost of transparent PVC products. Therefore, there is an urgent need for a high-performance and relatively low-cost processing ACR for transparent PVC products. Summary of the Invention

[0003] This invention provides a method for preparing a processable ACR for transparent PVC products and its application, thereby overcoming the deficiencies in the prior art.

[0004] This invention is achieved through the following technical solution: A method for preparing a processable ACR for transparent PVC products includes the following steps: Step 1: Mix and react isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water to obtain the first mixed emulsion. Step 2: The first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer and γ-aminopropyltriethoxysilane are mixed and reacted to obtain a mixed emulsion. Step 3: The mixed emulsion is dried by spray drying to obtain ACR additive.

[0005] In the preparation method of the processed ACR for PVC transparent products as described above, the mass ratio of isoborneol methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartaric acid monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water in step one is: 40-60: 40-60: 10-20: 5-15: 0.2-0.4: 0.2-0.4: 0.1-0.3: 0.4-0.6: 300-400.

[0006] In the preparation method of the processable ACR for PVC transparent products as described above, the reaction temperature in step one is 70-80℃, the reaction time is 4-6h, and the reaction is carried out in a closed reactor with nitrogen gas for protection.

[0007] In the preparation method of the processable ACR for PVC transparent products as described above, the mass ratio of the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer, and γ-aminopropyltriethoxysilane is 300-400: 30-50: 20-40: 0.2-0.4: 0.2-0.4: 0.3-0.5.

[0008] In the preparation method of the processable ACR for PVC transparent products as described above, the reaction temperature in step two is 75-85℃, the reaction time is 3-5h, and the reaction is carried out in a closed reactor with nitrogen gas for protection.

[0009] In the preparation method of the processable ACR for PVC transparent products as described above, a safety valve is installed on the reactor in steps one and two. When the pressure inside the reactor exceeds 0.8 MPa, the pressure is released through the safety valve to ensure safe production.

[0010] In the preparation method of the processing type ACR for PVC transparent products as described above, the spray drying temperature in step three is 150-180℃, the air inlet velocity is 15-20m / s, the air outlet temperature is controlled at 80-90℃, and the residence time of the material in the drying tower is 10-15s.

[0011] In the preparation method of the processable ACR for PVC transparent products as described above, the moisture content of the dried particles in step three is controlled below 0.5%, the particle size distribution range is 10-50μm, and the feeding rate is 200-300kg / h to ensure that the mixed emulsion can be uniformly atomized and fully contacted with hot air, thereby improving drying efficiency and product quality stability. After drying, the particles are collected by a cyclone separator and then screened to remove particles with a particle size greater than 50μm.

[0012] In the preparation method of the processing type ACR for PVC transparent products as described above, the particles with a particle size greater than 50 μm separated by the cyclone separator are crushed and screened again to ensure that the particle size is less than 50 μm.

[0013] The application of processed ACR in PVC transparent products, wherein the amount of ACR added is 3-5% of the mass of PVC, the particles of both are fed into a twin-screw extruder and melt-blended at a temperature of 170-190℃ and a screw speed of 300-400r / min, and then extruded and granulated to obtain PVC composite material.

[0014] The advantages of this invention are: In this invention, the core layer uses a compound of isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, and di-n-butyl itaconic acid, which can impart good flexibility and internal plasticizing effect to the ACR additive, helping to improve the melt flow of PVC materials during processing. The compound use of diacetyl tartaric acid monoglyceride and sodium ditridecyl sulfosuccinate can effectively improve the dispersion stability of monomers in the aqueous phase and ensure the uniformity of the polymerization reaction. The introduction of aziridine isocyanate and maleimide undecanoic acid succinimide can optimize the network structure of ACR molecular chains through crosslinking reaction, enhance its compatibility with PVC matrix, and thus improve the mechanical properties and thermal stability of composite materials. Azobisisoheptanenitrile decomposes under suitable temperature conditions to generate free radicals, which initiate the copolymerization reaction of monomers and provide sufficient reaction kinetics for the formation of the first mixed emulsion. The shell material of this invention is a blend of methyl methacrylate and polycarbonate. Methyl methacrylate has a high refractive index and transparency, which can be well matched with the refractive index of the PVC matrix, reducing interfacial light scattering and thus improving the transparency of the product. Polycarbonate can further enhance the heat resistance and mechanical strength of the ACR additive, complementing the flexibility of methyl methacrylate and improving the overall performance of the PVC composite material. The blend of fatty alcohol polyoxyethylene ether and polyoxyethylene-polyoxypropylene block graft copolymer can regulate the surface tension of the emulsion during the shell polymerization stage, promote the stable formation of the core-shell structure, and improve the dispersion uniformity of the ACR additive in the PVC matrix. The siloxane groups in γ-aminopropyltriethoxysilane can react chemically with the ACR molecular chain and the hydroxyl groups on the surface of the PVC matrix to form chemical bonds, effectively enhancing the interfacial bonding force, reducing interfacial defects, and further improving the transparency and mechanical property stability of the composite material. This invention can quickly remove deionized water and form small molecule particles through spray drying, avoiding the problem of thermal degradation of additives caused by prolonged high temperature in traditional drying methods; The PVC transparent products produced by combining the ACR additive prepared by this invention with PVC have good transparency and thermal stability, and are low in cost. Therefore, the performance of PVC transparent products can be ensured at a low cost. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0016] Example 1 Step 1: Isoborneol methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water are added to a closed reactor and reacted at 70°C for 6 hours under nitrogen protection to obtain the first mixed emulsion. The mass ratio of isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water is 40:40:10:5:0.2:0.2:0.1:0.4:300. Step 2: Add the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer and γ-aminopropyltriethoxysilane to a closed reactor and react at 75°C for 5 hours under nitrogen protection to obtain the mixed emulsion. The mass ratio of the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer, and γ-aminopropyltriethoxysilane is 300:30:20:0.2:0.2:0.3-0.5. Step 3: The mixed emulsion is dried by spray drying to obtain the ACR additive; The spray drying temperature is 150-180℃, the air inlet velocity is 15-20m / s, the air outlet temperature is controlled at 80-90℃, and the material residence time in the drying tower is 10-15s. The moisture content of the dried granules is controlled below 0.5%, the particle size distribution range is 10-50μm, and the feeding rate is 200-300kg / h to ensure that the mixed emulsion can be uniformly atomized and fully contacted with hot air, thereby improving drying efficiency and product quality stability. After drying, the granules are collected by a cyclone separator and then screened to remove particles with a particle size greater than 50μm. Particles larger than 50 μm separated by the cyclone separator are crushed and screened again to ensure that the particle size is less than 50 μm.

[0017] Example 2 Step 1: Isoborneol methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water are added to a closed reactor and reacted at 80°C for 4 hours under nitrogen protection to obtain the first mixed emulsion. The mass ratio of isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water is 60:60:20:15:0.4:0.4:0.3:0.6:400. Step 2: Add the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer and γ-aminopropyltriethoxysilane to a closed reactor and react at 85°C for 3 hours under nitrogen protection to obtain the mixed emulsion. The mass ratio of the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer, and γ-aminopropyltriethoxysilane is 400:50:40:0.4:0.4:0.5. Step 3: The mixed emulsion is dried by spray drying to obtain the ACR additive; The spray drying temperature is 150-180℃, the air inlet velocity is 15-20m / s, the air outlet temperature is controlled at 80-90℃, and the material residence time in the drying tower is 10-15s. The moisture content of the dried granules is controlled below 0.5%, the particle size distribution range is 10-50μm, and the feeding rate is 200-300kg / h to ensure that the mixed emulsion can be uniformly atomized and fully contacted with hot air, thereby improving drying efficiency and product quality stability. After drying, the granules are collected by a cyclone separator and then screened to remove particles with a particle size greater than 50μm. Particles larger than 50 μm separated by the cyclone separator are crushed and screened again to ensure that the particle size is less than 50 μm.

[0018] Example 3 Step 1: Isoborneol methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water are added to a closed reactor and reacted at 75°C for 5 hours under nitrogen protection to obtain the first mixed emulsion. The mass ratio of isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water is 50:50:15:10:0.3:0.3:0.2:0.5:350. Step 2: Add the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer and γ-aminopropyltriethoxysilane to a closed reactor and react at 80°C for 4 hours under nitrogen protection to obtain the mixed emulsion. The mass ratio of the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer, and γ-aminopropyltriethoxysilane is 350:40:30:0.3:0.3:0.4. Step 3: The mixed emulsion is dried by spray drying to obtain the ACR additive; The spray drying temperature is 150-180℃, the air inlet velocity is 15-20m / s, the air outlet temperature is controlled at 80-90℃, and the material residence time in the drying tower is 10-15s. The moisture content of the dried granules is controlled below 0.5%, the particle size distribution range is 10-50μm, and the feeding rate is 200-300kg / h to ensure that the mixed emulsion can be uniformly atomized and fully contacted with hot air, thereby improving drying efficiency and product quality stability. After drying, the granules are collected by a cyclone separator and then screened to remove particles with a particle size greater than 50μm. Particles larger than 50 μm separated by the cyclone separator are crushed and screened again to ensure that the particle size is less than 50 μm.

[0019] The ACR additives prepared in Examples 1-3 were compounded with PVC at ratios of 3%, 4%, and 5%, and the granules were fed into a twin-screw extruder for melt blending at 180°C and a screw speed of 350 r / min. After extrusion and granulation, PVC composite materials were obtained, which were designated as Examples 1-3. PA-20 type ACR additives were compounded with PVC at ratios of 3%, 4%, and 5%, and PVC composite materials were prepared using the same method, which were designated as Comparative Examples 1-3. The PVC composite materials from Examples 1-3 and Comparative Examples 1-3 were used to prepare sheets with dimensions of 100 mm × 100 mm × 3 mm. The light transmittance was tested according to GB / T 2410-2008, the tensile strength according to GB / T 1040.2-2006, and the heat distortion temperature according to GB / T 1634.2-2019. Test results show that the light transmittance of Examples 1-3 is above 97%, the tensile strength is greater than 50 MPa, and the heat distortion temperature is above 80℃. In contrast, the light transmittance of Comparative Examples 1-3 is the highest at 96%, the tensile strength is the highest at 48 MPa, and the heat distortion temperature is the highest at 79.5℃. The ACR additives prepared in Examples 1-3 of this invention have slightly better performance than those in Comparative Examples 1-3. However, the production cost and sales price of this invention are more than 50% lower than those of corresponding ACR additives from abroad. Therefore, the ACR additives prepared in this invention can effectively reduce costs while ensuring performance.

[0020] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a processable ACR for transparent PVC products, characterized in that: Includes the following steps: Step 1: Mix and react isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartrate monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water to obtain the first mixed emulsion. Step 2: The first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer and γ-aminopropyltriethoxysilane are mixed and reacted to obtain a mixed emulsion. Step 3: The mixed emulsion is dried by spray drying to obtain ACR additive.

2. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: The mass ratio of isobornyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, di-n-butyl itaconic acid, diacetyl tartaric acid monoglyceride, sodium ditridecyl sulfosuccinate, aziridine isocyanate, maleimide undecanoate succinimide, azobisisoheptanenitrile, and deionized water in step one is 40-60: 40-60: 10-20: 5-15: 0.2-0.4: 0.2-0.4: 0.1-0.3: 0.4-0.6: 300-400.

3. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: The reaction temperature in step one is 70-80℃, the reaction time is 4-6h, and the reaction is carried out in a closed reactor with nitrogen gas for protection.

4. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: The mass ratio of the first mixed emulsion, methyl methacrylate, polycarbonate, fatty alcohol polyoxyethylene ether, polyoxyethylene-polyoxypropylene block graft copolymer, and γ-aminopropyltriethoxysilane is 300-400: 30-50: 20-40: 0.2-0.4: 0.2-0.4: 0.3-0.

5.

5. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: The reaction temperature in step two is 75-85℃, the reaction time is 3-5h, and the reaction is carried out in a closed reactor with nitrogen gas for protection.

6. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: Safety valves are installed on the reactors in steps one and two. When the pressure inside the reactor exceeds 0.8 MPa, the pressure is released through the safety valves to ensure safe production.

7. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: In step three, the spray drying temperature is 150-180℃, the air inlet velocity is 15-20m / s, the air outlet temperature is controlled at 80-90℃, and the residence time of the material in the drying tower is 10-15s.

8. The method for preparing a processable ACR for PVC transparent products according to claim 1, characterized in that: In step three, the moisture content of the dried particles is controlled below 0.5%, the particle size distribution range is 10-50μm, and the feeding rate is 200-300kg / h to ensure that the mixed emulsion can be uniformly atomized and fully contacted with hot air, thereby improving drying efficiency and product quality stability. After drying, the particles are collected by a cyclone separator and then screened to remove particles with a diameter greater than 50μm.

9. The method for preparing a processable ACR for PVC transparent products according to claim 8, characterized in that: Particles with a diameter greater than 50 μm separated by the cyclone separator are crushed and screened again to ensure that the particle size is less than 50 μm.

10. Application of processed ACR for PVC transparent products, characterized by: The ACR is added at 3-5% of the PVC mass. The two particles are fed into a twin-screw extruder and melt-blended at a temperature of 170-190℃ and a screw speed of 300-400r / min. After extrusion and granulation, a PVC composite material is obtained.