Preparation process of high-strength and high-thermal-stability PVC material for decorative film

Abstract

The invention relates to the technical field of polyvinyl chloride, and discloses a preparation process of a high-strength and high-thermal-stability PVC (polyvinyl chloride) material for a decorative film, which comprises the following steps: mixing polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, cyano polyesteramide, a stabilizer, a plasticizer, an antioxidant and the like, extruding in a twin-screw extruder, and granulating, the PVC material with high strength and high thermal stability is obtained. The cyano polyesteramide can improve the compatibility between ABS and PVC, so that the material has better mechanical properties, the polyesteramide has a hyperbranched molecular chain structure and plays a certain role in toughening, the compatibility between ABS and PVC is better, the vicat softening temperature of the material is increased, the thermal stability of the material is enhanced, and when the cyano polyesteramide is applied to materials such as decorative films, the material has better mechanical properties. Decorative films and the like can have good heat resistance and are not prone to aging and yellowing.

Description

Technical Field

[0001] The invention relates to the technical field of polyvinyl chloride, in particular to a preparation process of a high-strength and high-thermal-stability PVC material for decorative films. Background Art

[0002] Polyvinyl chloride (PVC) boasts excellent mechanical strength, corrosion resistance, insulation, and flame retardancy, making it widely used in decorative film materials, pipes, cables, and building materials. However, PVC suffers from poor thermal stability and is susceptible to thermal decomposition and yellowing at high temperatures, which can reduce its mechanical properties. ABS (acrylonitrile-butadiene-styrene) copolymer offers excellent mechanical properties, high-temperature resistance, and chemical stability. Its alloys, blended with PVC, exhibit even better performance.

[0003] Polyvinyl chloride (PVC) and ABS (ABS) have poor compatibility, typically requiring the addition of additives such as compatibilizers. Chinese patent application CN117004151A discloses a PVC / ABS alloy material, its preparation method, and its application. Using epoxidized soybean oil-grafted polyphosphazene microspheres or dendritic PAMAM as the primary lubricant, the material improves compatibility with both PVC and ABS, enhancing the alloy's toughness and flame retardancy. However, the patent does not improve the Vicat softening temperature or thermal stability of the PVC / ABS material. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the present invention provides a preparation process of a high-strength and high-thermal-stability PVC material for decorative films, which solves the problems of poor toughness and thermal stability of PVC materials.

[0005] The technical solution of the present invention: a preparation process of a high-strength and high-thermal-stability PVC material: (1) Add N-(2-cyanoethyl)diethanolamine, tris(2-butyramidoethyl)amine, and p-toluenesulfonic acid to a reaction flask, stir and carry out melt polycondensation reaction in a nitrogen atmosphere, cool, add methanol, filter, wash the precipitate with methanol, and dry to obtain cyano polyester amide. The preparation reaction formula is: .

[0006] (2) Polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, cyanopolyester amide, stabilizer, plasticizer, antioxidant and additives are mixed, and then extruded in a twin-screw extruder and granulated to obtain a high-strength and high-thermal stability PVC material.

[0007] Furthermore, the melt polycondensation in (1) is first carried out at 155-170°C for 30-50 minutes, and then vacuum is applied to control the vacuum degree to 30-60 Pa, and the reaction is continued for 2-3 hours.

[0008] Furthermore, the ratio of N-(2-cyanoethyl)diethanolamine (CAS No. 17209-72-2), tris(2-butyramidal acid ethyl)amine, and p-toluenesulfonic acid in (1) is (1.5-1.6) mol:1 mol:(0.012-0.016) mol.

[0009] Furthermore, the preparation process of tris(2-butyramic acid ethyl)amine includes: adding acetonitrile, tris(2-aminoethyl)amine (CAS No. 4097-89-6) in a ratio of 1 mol:(3.3-4.2) mol), and succinic anhydride to a reaction flask in an ice bath, followed by reacting at 20-25°C for 12-18 hours, removing the solvent by rotary evaporation, and separating the product by silica gel column chromatography to obtain tris(2-butyramic acid ethyl)amine. The preparation reaction formula is: .

[0010] Furthermore, the temperature of zones 1-6 of the twin-screw extruder in (2) is 130-175°C, and the screw speed is 150-250 r / min.

[0011] Furthermore, the ratio of polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, cyanopolyester amide, plasticizer, stabilizer, antioxidant and additive in (2) is (65-85) g: (15-35) g: (1.5-3) g: (3-8) g: (2.7-3.6): (0.3-0.6): (2.5-3.8).

[0012] Furthermore, the plasticizer includes dioctyl phthalate.

[0013] Furthermore, the antioxidant includes antioxidant 1010 or antioxidant 168.

[0014] Furthermore, the stabilizer includes a calcium zinc stabilizer.

[0015] Furthermore, the auxiliary agent includes zinc stearate, calcium stearate or polyethylene wax.

[0016] Furthermore, high-strength and high-thermal stability PVC materials are used in decorative films.

[0017] The beneficial technical effect of the present invention is as follows: N-(2-cyanoethyl)diethanolamine containing two hydroxyl groups and tris(2-butyramidal acid ethyl)amine containing three carboxyl groups are subjected to a hyperbranched melt polycondensation reaction to obtain cyano polyester amide, which is then mixed with polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, a stabilizer, an antioxidant, etc. and granulated to obtain a high-strength and high-thermal-stability PVC material.

[0018] The cyano polyester amide of the present invention contains a cyano group, which has a polarity similar to that of ABS, and the two have excellent compatibility. In addition, the amide bond -NH- group contained in the polyester amide can form a hydrogen bond with the polar chlorine atoms of polyvinyl chloride, thereby serving as a compatibilizer to improve the compatibility between ABS and PVC, and to make the material have better mechanical properties. The polyester amide has a hyperbranched molecular chain structure, which plays a certain toughening role and is conducive to improving the elongation at break, impact strength and toughness of the material.

[0019] The ABS of the present invention has better compatibility with PVC, a higher Vicat softening temperature, and enhanced thermal stability. When applied to materials such as decorative films, the decorative films can have good heat resistance and be less prone to aging and yellowing. DETAILED DESCRIPTION

[0020] In order to make the technical means, creative features, objectives and effects achieved by the present invention easier to understand, the present invention is further described below in conjunction with specific embodiments. However, the following embodiments are only preferred embodiments of the present invention and are not exhaustive. Based on the embodiments in the embodiments, other embodiments obtained by those skilled in the art without making any creative work are all within the scope of protection of the present invention.

[0021] Example 1 (1) Add 500 mL of acetonitrile, 20 mmol of tris(2-aminoethyl)amine, and 66 mmol of succinic anhydride to a reaction flask in an ice bath, and then react at 25°C for 18 h. The solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography and eluted with methanol and dichloromethane solution to obtain tris(2-butyramidal acid ethyl)amine.

[0022] (2) Add 75 mmol of N-(2-cyanoethyl)diethanolamine, 50 mmol of tris(2-butyramic acid ethyl)amine, and 0.73 mmol of p-toluenesulfonic acid to the reaction flask. In a nitrogen atmosphere, heat to 165 ° C. Stir and react for 30 minutes. Then evacuate and control the vacuum degree to 50 Pa. React for 3 hours. After cooling, add methanol. After filtering, wash the precipitate with methanol and dry it to obtain cyano polyester amide.

[0023] (3) 8.5 kg of polyvinyl chloride, 1.5 kg of acrylonitrile-butadiene-styrene copolymer, 0.15 kg of cyanopolyester amide, 0.8 kg of calcium zinc stabilizer, 0.36 kg of plasticizer dioctyl phthalate, 0.3 kg of antioxidant 1010, 0.19 kg of zinc stearate, 0.13 kg of calcium stearate, and 60 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 200 r / min, and granulated to obtain a PVC material with high strength and high thermal stability.

[0024] Example 2 (1) Add 600 mL of acetonitrile, 20 mmol of tris(2-aminoethyl)amine, and 84 mmol of succinic anhydride to a reaction flask in an ice bath, and then react at 20°C for 12 h. The solvent is removed by rotary evaporation. The product is separated by silica gel column chromatography and eluted with methanol and dichloromethane solution to obtain tris(2-butyramidal acid ethyl)amine.

[0025] (2) Add 80 mmol of N-(2-cyanoethyl)diethanolamine, 50 mmol of tris(2-butyramic acid ethyl)amine, and 0.6 mmol of p-toluenesulfonic acid to the reaction flask. In a nitrogen atmosphere, heat to 170 °C and stir to react for 30 min. Then evacuate the flask and control the vacuum degree to 50 Pa. React for 2 h. After cooling, add methanol, filter, wash the precipitate with methanol, and dry to obtain cyano polyester amide.

[0026] (3) 8 kg of polyvinyl chloride, 2 kg of acrylonitrile-butadiene-styrene copolymer, 0.2 kg of cyanopolyester amide, 0.6 kg of calcium zinc stabilizer, 0.34 kg of plasticizer dioctyl phthalate, 0.4 kg of antioxidant 168, 0.18 kg of zinc stearate, 0.1 kg of calcium stearate, and 70 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 150 r / min, and granulated to obtain a PVC material with high strength and high thermal stability.

[0027] Example 3 (1) 78 mmol of N-(2-cyanoethyl)diethanolamine, 50 mmol of tris(2-butyramidal acid ethyl)amine (prepared in Example 1), and 0.8 mmol of p-toluenesulfonic acid were added to a reaction flask. The mixture was heated to 155°C in a nitrogen atmosphere and stirred for 50 min. The mixture was then evacuated to a vacuum degree of 30 Pa and reacted for 3 h. After cooling, methanol was added, the precipitate was filtered, washed with methanol, and dried to obtain cyanopolyesteramide.

[0028] (2) 7 kg of polyvinyl chloride, 3 kg of acrylonitrile-butadiene-styrene copolymer, 0.25 kg of cyanopolyester amide, 0.5 kg of calcium zinc stabilizer, 0.3 kg of plasticizer dioctyl phthalate, 0.6 kg of antioxidant 168, 0.15 kg of zinc stearate, 0.1 kg of calcium stearate, and 50 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 250 r / min, and granulated to obtain a PVC material with high strength and high thermal stability.

[0029] Example 4 (1) 75 mmol of N-(2-cyanoethyl)diethanolamine, 50 mmol of tris(2-butyramidal acid ethyl)amine (prepared in Example 1), and 0.66 mmol of p-toluenesulfonic acid were added to a reaction flask. The mixture was heated to 170°C in a nitrogen atmosphere and stirred for 30 min. The mixture was then evacuated to a vacuum degree of 60 Pa and reacted for 2 h. After cooling, methanol was added, the precipitate was filtered, washed with methanol, and dried to obtain cyanopolyesteramide.

[0030] (2) 6.5 kg of polyvinyl chloride, 3.5 kg of acrylonitrile-butadiene-styrene copolymer, 0.3 kg of cyanopolyester amide, 0.3 kg of calcium zinc stabilizer, 0.27 kg of plasticizer dioctyl phthalate, 0.6 kg of antioxidant 1010, 0.12 kg of zinc stearate, 90 g of calcium stearate, and 40 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 250 r / min, and granulated to obtain a PVC material with high strength and high thermal stability.

[0031] Comparative Example 1: The difference between this comparative example and Example 1 is that cyanopolyesteramide is not added.

[0032] (1) 8.5 kg of polyvinyl chloride, 1.5 kg of acrylonitrile-butadiene-styrene copolymer, 0.8 kg of calcium zinc stabilizer, 0.36 kg of plasticizer dioctyl phthalate, 0.3 kg of antioxidant 1010, 0.19 kg of zinc stearate, 0.13 kg of calcium stearate, and 60 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 200 r / min, and granulated to obtain PVC material.

[0033] Comparative Example 2: The difference between this comparative example and Example 1 is that N-methyldiethanolamine is used instead of N-(2-cyanoethyl)diethanolamine when preparing polyesteramide.

[0034] (1) Add 75 mmol of N-methyldiethanolamine, 50 mmol of tris(2-butyramic acid ethyl)amine, and 0.73 mmol of p-toluenesulfonic acid to the reaction flask. In a nitrogen atmosphere, heat to 165 °C and stir to react for 30 min. Then evacuate the flask and control the vacuum degree to 50 Pa. React for 3 h. After cooling, add methanol, filter, wash the precipitate with methanol, and dry to obtain polyesteramide.

[0035] (2) 8.5 kg of polyvinyl chloride, 1.5 kg of acrylonitrile-butadiene-styrene copolymer, 0.15 kg of cyanopolyester amide, 0.8 kg of calcium zinc stabilizer, 0.36 kg of plasticizer dioctyl phthalate, 0.3 kg of antioxidant 1010, 0.19 kg of zinc stearate, 0.13 kg of calcium stearate, and 60 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 200 r / min, and granulated to obtain PVC material.

[0036] In Comparative Example 3, trimethylolpropane succinate was used instead of tris(2-ethylbutyramido)amine.

[0037] (1) Add 20 mmol of trimethylolpropane and 66 mmol of succinic anhydride to a flask, stir, heat to 120°C, react for 4 hours, cool, and separate the product by silica gel column chromatography. Elution with methanol and dichloromethane solution yields trimethylolpropane succinic acid monoester, with the structural formula: .

[0038] (2) Add 75 mmol of N-(2-cyanoethyl)diethanolamine, 50 mmol of tris(2-butyramic acid ethyl)amine, and 0.73 mmol of p-toluenesulfonic acid to the reaction flask. In a nitrogen atmosphere, heat to 165 ° C. Stir and react for 30 minutes. Then evacuate and control the vacuum degree to 50 Pa. React for 3 hours. After cooling, add methanol. After filtering, wash the precipitate with methanol and dry it to obtain cyanoethyl polyester.

[0039] (3) 8.5 kg of polyvinyl chloride, 1.5 kg of acrylonitrile-butadiene-styrene copolymer, 0.15 kg of cyano polyester, 0.8 kg of calcium zinc stabilizer, 0.36 kg of plasticizer dioctyl phthalate, 0.3 kg of antioxidant 1010, 0.19 kg of zinc stearate, 0.13 kg of calcium stearate, and 60 g of polyethylene wax were mixed, and then extruded in a twin-screw extruder with the temperatures of zones 1-6 being 130°C, 155°C, 170°C, 175°C, 175°C, and 170°C, and the screw speed being 200 r / min, and granulated to obtain PVC material.

[0040] The PVC material was placed in a flat vulcanizer and compression molded at 175°C under a pressure of 15 MPa to form a specimen. The tensile properties were tested according to GB / T 1040.1-2018, the impact strength was tested according to GB / T 1043.1-2008, and the Vicat softening temperature was tested according to GB / T 1633-2000.

[0041] Table 1 Properties of PVC materials , After testing, compared with Comparative Example 1, cyano polyester amide is added to the ABS / PVC material of Example 1. The cyano polyester amide contains a cyano group, has similar polarity to ABS, has excellent compatibility, and contains an amide bond. Its -NH- group can form a hydrogen bond with the polar chlorine atom of polyvinyl chloride, thereby acting as a compatibilizer, improving the compatibility between ABS and PVC, making the material have better mechanical properties and heat resistance, a higher Vicat softening temperature, and enhanced thermal stability. In addition, the polyester amide has a hyperbranched molecular chain structure, which plays a certain toughening role, which is beneficial to improving the elongation at break, impact strength and toughness of the material.

[0042] Comparative Example 2 uses N-methyldiethanolamine as raw material to prepare polyester amide, which does not contain cyano groups and has a large difference in polarity and compatibility with ABS. As a result, polyester amide cannot be used as a compatibilizer and does not improve the compatibility between ABS and PVC. The mechanical properties and heat resistance of the material are poor.

[0043] Comparative Example 3 uses trimethylolpropane succinate as raw material to prepare cyanopolyester, which does not contain amide bonds and has low hydrogen bonding with polyvinyl chloride. It does not improve the compatibility between PVC and ABS well, resulting in poor mechanical properties and heat resistance of the material.

[0044] The above description is only a preferred embodiment of the present invention and does not constitute any formal or substantial limitation to the present invention. It should be noted that ordinary technicians in this technical field can make several improvements and supplements without departing from the method of the present invention, and these improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A process for preparing a high-strength and high-thermal-stability PVC material, characterized in that: The preparation process comprises: (1) Add N-(2-cyanoethyl)diethanolamine, tris(2-butyramidoethyl)amine, and p-toluenesulfonic acid to a reaction flask, stir the reaction in a nitrogen atmosphere, cool the reaction, add methanol, filter, wash the precipitate with methanol, and dry it to obtain cyanopolyesteramide; (2) Polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, cyanopolyester amide, stabilizer, plasticizer, antioxidant and additives are mixed, and then extruded in a twin-screw extruder and granulated to obtain a high-strength and high-thermal stability PVC material.

2. The preparation process of the high-strength and high-thermal-stability PVC material according to claim 1, characterized in that: The reaction in (1) is first carried out at 155-170° C. for 30-50 min, and then vacuumed to control the vacuum degree to 30-60 Pa and reacted for 2-3 h.

3. The preparation process of the high-strength and high-thermal-stability PVC material according to claim 1, characterized in that: The ratio of N-(2-cyanoethyl)diethanolamine, tris(2-butyramidal acid ethyl)amine and p-toluenesulfonic acid in (1) is (1.5-1.6) mol: 1 mol: (0.012-0.016) mol.

4. The process for preparing the high-strength and high-thermal-stability PVC material according to claim 3, characterized in that: The preparation process of tris(2-butyramic acid ethyl)amine comprises: adding acetonitrile, tris(2-aminoethyl)amine and succinic anhydride in a ratio of 1 mol:(3.3-4.2) mol to a reaction bottle in an ice bath, then reacting at 20-25° C. for 12-18 hours, rotary evaporation to remove the solvent, and separating the product by silica gel column chromatography to obtain tris(2-butyramic acid ethyl)amine.

5. The process for preparing the high-strength and high-thermal-stability PVC material according to claim 1, characterized in that: The temperature of zones 1-6 of the twin-screw extruder in (2) is 130-175°C, and the screw speed is 150-250 r / min.

6. The process for preparing the high-strength and high-thermal-stability PVC material according to claim 1, characterized in that: The ratio of polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, cyanopolyester amide, plasticizer, stabilizer, antioxidant and additive in (2) is (65-85) g: (15-35) g: (1.5-3) g: (3-8) g: (2.7-3.6): (0.3-0.6): (2.5-3.8).

7. The process for preparing the high-strength and high-thermal-stability PVC material according to claim 6, characterized in that: The plasticizer includes dioctyl phthalate; the antioxidant includes antioxidant 1010 or antioxidant 168.

8. The process for preparing the high-strength and high-thermal-stability PVC material according to claim 6, characterized in that: The stabilizer includes calcium zinc stabilizer; the auxiliary agent includes zinc stearate, calcium stearate or polyethylene wax.

9. Use of a high-strength and high-thermal-stability PVC material obtained by the preparation process according to any one of claims 1 to 8 in a decorative film.