High-gloss paint-spraying-free lamp plastic and preparation method thereof

Abstract

The invention relates to a high-gloss paint-spraying-free lamp plastic and a preparation method thereof, and belongs to the technical field of polymer composite materials. The plastic is prepared from the following components: 27 to 35 weight percent of ABS (Acrylonitrile Butadiene Styrene) resin, 4.2 to 5.5 weight percent of sensitizer, 2.4 to 3.2 weight percent of compatilizer, 0.15 to 0.2 weight percent of antioxidant, 0.1 to 0.13 weight percent of stabilizer, 1.9 to 2.4 weight percent of pigment and the balance of PC (Polycarbonate) resin, the brightening agent is substituted by active primary amine of trifluoroiodopropane and tetramethylenediamine, a terminal fluorine structure is introduced for modification, then dimethyl alkyl diacid and substituted secondary amine are subjected to amine-ester exchange, a macromolecular amide compound is formed, and compared with an existing lubricating brightening technology, the brightening agent is small in melting and mixing resistance, not prone to migration and high in lubricating property. The introduction of the fluorine element effectively reduces the surface energy of molecules of the brightener, so that the scattering of light on each phase interface is lower, the glossiness and brightness of the plastic are high, and the visual effect is brighter.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer composite materials, and in particular relates to a high-gloss paint-free lamp plastic and a preparation method thereof. Background Art

[0002] In the field of lamp manufacturing, alloy materials of polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS) are widely used due to their excellent comprehensive properties. PC / ABS materials combine the high strength and heat resistance of PC with the easy processing of ABS, and can meet the requirements of lamps for mechanical properties, weather resistance and appearance quality. However, traditional PC / ABS materials are insufficient in terms of surface gloss, and usually require subsequent painting treatment to improve the appearance, which not only increases production costs and process complexity, but may also cause environmental pollution problems.

[0003] In the prior art, in order to improve the surface gloss of PC / ABS materials, various lubricants are usually added to improve the fluidity of the melt, improve the surface quality of the product after molding, and improve the surface gloss. Among them, the most widely used are amide lubricants, which have both internal and external lubrication effects. However, the existing amide lubricants have insufficient dispersibility during the melt mixing process, and most of them are small molecular compounds. They are easy to migrate and segregate after molding, forming a large amount of inhomogeneous phases in the product, resulting in insufficient improvement in the overall gloss.

[0004] Therefore, the existing technology has obvious deficiencies in improving the glossiness of plastic lamps, and a new technical solution is urgently needed to solve the above problems and realize the industrial application of high-gloss paint-free lamp plastics. Summary of the invention

[0005] In order to solve the technical problems mentioned in the background technology, the object of the present invention is to provide a high-gloss paint-free lamp plastic and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A high-gloss paint-free lamp plastic, comprising: ABS resin 27-35wt%, brightener 4.2-5.5wt%, compatibilizer 2.4-3.2wt%, antioxidant 0.15-0.2wt%, stabilizer 0.1-0.13wt% and pigment 1.9-2.4wt%, the balance is PC resin.

[0007] The brightener is prepared by the following method: Step A1: premix triethylamine and tetrahydrofuran, add tetramethylenediamine and trifluoroiodopropane and mix well, introduce nitrogen protection, heat to 45-55°C under stirring at 40-60 rpm and react for 3-4 hours. After the reaction, remove tetrahydrofuran by rotary evaporation, wash the substrate with water and remove the aqueous phase, and dry to obtain an intermediate; Furthermore, the usage ratio of tetramethylenediamine, trifluoroiodopropane, triethylamine and tetrahydrofuran is 0.1 mol: 0.2 mol: 10-15 mL: 80-110 mL, and trifluoroiodopropane reacts with the active primary amine of tetramethylenediamine to graft the terminal fluorine structure.

[0008] Step A2: Alkyl dicarboxylic acid dimethyl ester, intermediate and anhydrous toluene are mixed, dry gas protection is introduced, trimethylaluminum is added and mixed, and the temperature is raised to 70-90°C with stirring at 60-90 rpm to react for 5.5-7 hours. After the reaction is completed, toluene is evaporated under reduced pressure, and the substrate is washed with ethanol and water in turn, and dried to obtain a brightener; Further, the alkyl diacid dimethyl ester is selected from one of dimethyl pimelate, dimethyl sebacate and dimethyl dodecanedioate.

[0009] Furthermore, the usage ratio of alkyl dicarboxylic acid dimethyl ester, intermediate, trimethyl aluminum and anhydrous toluene is 0.1 mol: 0.1 mol: 0.1-0.18 g: 150-200 mL, and the alkyl dicarboxylic acid dimethyl ester undergoes amine ester exchange with the secondary amine structure in the intermediate molecule to form a macromolecular amide compound.

[0010] Preferably, the compatibilizer is selected from maleic anhydride grafted ABS copolymer, which plays a good role in promoting compatibility in the PC / ABS system.

[0011] Preferably, the antioxidant is selected from a combination of antioxidant 1010 and antioxidant 168, wherein the hindered phenol antioxidant 1010 provides long-term stability, while the phosphite antioxidant 168 helps prevent oxidation during processing and reduce gloss loss caused by oxidation during processing and molding.

[0012] Preferably, the stabilizer is selected from ultraviolet absorber UV-P and light stabilizer 770. The ultraviolet absorber UV-P mainly works in the initial stage of ultraviolet irradiation, while the hindered amine light stabilizer 770 works throughout the entire photo-oxidation process, slowing down the light loss caused by photo-aging of the light source in the lamp to the plastic.

[0013] Preferably, the pigment is selected from aluminum pigments, which have strong hiding power and high gloss, and give the composite system a metallic glossy aesthetic feeling.

[0014] A preparation method of a high-gloss paint-free lamp plastic comprises the following steps: mixing raw materials of various components, plasticizing and mixing at 245±5°C, extruding and pelletizing to obtain the high-gloss paint-free lamp plastic.

[0015] Beneficial effects of the present invention: The invention discloses a brightener suitable for PC / ABS composite plastics. The brightener is prepared by replacing the active primary amine of trifluoroiodopropane with tetramethylenediamine, introducing terminal fluorine structure modification, and then performing amine ester exchange between dimethyl alkyl diacid and the substituted secondary amine to form a macromolecular amide compound, namely the brightener. Compared with the existing lubricating brightener system, the molecular main chain of the brightener contains a block of non-polar saturated alkyl chain, the side chain contains a polar fluorine structure, and has good compatibility with both polar PC matrix and weak polar ABS matrix. The amide structure in the brightener molecule does not contain hydrogen atoms and does not form a carbon group in the macromolecule of the composite system. Hydrogen bonds reduce the melt-mixing resistance during the blending process, and with the introduction of fluorine structure, the friction between the brightener molecules and the macromolecules of the composite system is greatly reduced, so that the brightener can be evenly dispersed in the composite system and give full play to the lubrication and brightening effect; in terms of molecular structure, the brightener is a macromolecular comb-type structure, which is not easy to migrate to the surface of the product during the thermoforming process, reducing the generation of inhomogeneous phases in the composite system and alleviating the scattering of light between phases. In addition, the introduction of fluorine elements effectively reduces the surface energy of the brightener molecules, making the scattering of light at the interface of each phase lower, making the gloss and brightness of the plastic high, and the visual effect brighter. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] Example 1, preparation of high gloss paint-free lamp plastic, the specific implementation method is as follows: 1. Preparation of Brightening Agent Step A1: premix triethylamine and tetrahydrofuran to form an alkaline mixed system, then add tetramethylenediamine and trifluoroiodopropane to mix, introduce nitrogen to replace the air in the reaction system, stir at 60rpm, control the temperature to 55°C, and react for 3h; in the above reaction, the amount ratio of tetramethylenediamine, trifluoroiodopropane, triethylamine and tetrahydrofuran is 0.1mol:0.2mol:15mL:110mL, after the reaction is completed, remove tetrahydrofuran by rotary evaporation, wash the rotary evaporation substrate with water, separate the liquid to remove the water phase and dry to obtain an intermediate.

[0018] Step A2: dimethyl dodecanedioate, the intermediate and anhydrous toluene are added and mixed, dry air is introduced to replace the air in the reaction system, trimethylaluminum is added and mixed, and the mixture is stirred at 90 rpm. The temperature is controlled at 90° C. and the reaction is carried out for 5.5 h. In the above reaction, the amount ratio of dimethyl dodecanedioate, the intermediate, trimethylaluminum and anhydrous toluene is 0.1 mol: 0.1 mol: 0.18 g: 200 mL. After the reaction is completed, toluene is evaporated under reduced pressure, and the substrate is washed with ethanol and water in turn, and dried to obtain a brightener.

[0019] 2. Preparation of high gloss paint-free lamp plastics Ingredients: 27wt% ABS resin, selected from PA-707 resin raw material; 4.2wt% brightener, which is prepared in this embodiment; 3.2wt% compatibilizer, selected from HW-102 maleic anhydride grafted ABS copolymer; 0.15wt% antioxidant, selected from antioxidant 1010 and antioxidant 168 in equal weight ratio; 0.13wt% stabilizer, selected from ultraviolet absorber UV-P and light stabilizer 770 in 2:1 weight ratio; 1.9wt% pigment, selected from SM8802 aluminum pigment; the remainder is PC resin, selected from PC-122 resin raw material.

[0020] Mixing: Add the above raw materials into a high speed mixer and mix at 600 rpm for 10 minutes, add into a twin screw extruder, plasticize and mix at 245±5°C, extrude and pelletize to obtain a high gloss paint-free lamp plastic.

[0021] Example 2, preparation of high gloss paint-free lamp plastic, the specific implementation method is as follows: 1. Preparation of Brightening Agent Step A1: premix triethylamine and tetrahydrofuran to form an alkaline mixed system, then add tetramethylenediamine and trifluoroiodopropane and mix well, introduce nitrogen to replace the air in the reaction system, stir at 40rpm, control the temperature to 45°C, and react for 4h; in the above reaction, the amount ratio of tetramethylenediamine, trifluoroiodopropane, triethylamine and tetrahydrofuran is 0.1mol:0.2mol:10mL:80mL, after the reaction is completed, remove tetrahydrofuran by rotary evaporation, wash the rotary evaporation substrate with water, separate the liquid to remove the water phase and dry to obtain an intermediate.

[0022] Step A2: dimethyl pimelate, the intermediate and anhydrous toluene are added and mixed, dry air is introduced to replace the air in the reaction system, trimethylaluminum is added and mixed, and the mixture is stirred at 60 rpm. The temperature is controlled at 70° C. and the reaction is carried out for 7 hours. In the above reaction, the amount ratio of dimethyl pimelate, the intermediate, trimethylaluminum and anhydrous toluene is 0.1 mol: 0.1 mol: 0.1 g: 150 mL. After the reaction is completed, toluene is evaporated under reduced pressure, and the substrate is washed with ethanol and water in turn, and dried to obtain a brightener.

[0023] 2. Preparation of high gloss paint-free lamp plastics Ingredients: 35wt% ABS resin, selected from PA-707 resin raw material; 5.5wt% brightener, which is prepared in this embodiment; 2.4wt% compatibilizer, selected from HW-102 maleic anhydride grafted ABS copolymer; 0.2wt% antioxidant, selected from antioxidant 1010 and antioxidant 168 in equal weight ratio; 0.1wt% stabilizer, selected from ultraviolet absorber UV-P and light stabilizer 770 in 2:1 weight ratio; 2.4wt% pigment, selected from SM8802 aluminum pigment; the remainder is PC resin, selected from PC-122 resin raw material.

[0024] Mixing: Add the above raw materials into a high speed mixer and mix at 600 rpm for 10 minutes, add into a twin screw extruder, plasticize and mix at 245±5°C, extrude and pelletize to obtain a high gloss paint-free lamp plastic.

[0025] Example 3, preparation of high gloss paint-free lamp plastic, the specific implementation method is as follows: 1. Preparation of Brightening Agent Step A1: premix triethylamine and tetrahydrofuran to form an alkaline mixed system, then add tetramethylenediamine and trifluoroiodopropane and mix well, introduce nitrogen to replace the air in the reaction system, stir at 60rpm, control the temperature to 50°C, and react for 3.5h; in the above reaction, the amount ratio of tetramethylenediamine, trifluoroiodopropane, triethylamine and tetrahydrofuran is 0.1mol:0.2mol:12mL:100mL, and after the reaction, remove tetrahydrofuran by rotary evaporation, wash the rotary evaporation substrate with water, separate the liquid to remove the water phase and dry to obtain an intermediate.

[0026] Step A2: dimethyl sebacate, the intermediate and anhydrous toluene are added and mixed, dry air is introduced to replace the air in the reaction system, trimethylaluminum is added and mixed, stirring is applied at 90 rpm, the temperature is controlled to be 80°C, and the reaction is carried out for 6.5 hours; in the above reaction, the amount ratio of dimethyl alkyl diacid, intermediate, trimethylaluminum and anhydrous toluene is 0.1 mol: 0.1 mol: 0.15 g: 170 mL, and toluene is removed by evaporation under reduced pressure after the reaction is completed, and the substrate is washed with ethanol and water in turn, and dried to obtain a brightener.

[0027] 2. Preparation of high gloss paint-free lamp plastics Ingredients: 32wt% ABS resin, selected from PA-707 resin raw material; 4.8wt% brightener, which is prepared in this embodiment; 2.8wt% compatibilizer, selected from HW-102 maleic anhydride grafted ABS copolymer; 0.18wt% antioxidant, selected from antioxidant 1010 and antioxidant 168 in equal weight ratio; 0.11wt% stabilizer, selected from ultraviolet absorber UV-P and light stabilizer 770 in 2:1 weight ratio; 2.2wt% pigment, selected from SM8802 aluminum pigment; the remainder is PC resin, selected from PC-122 resin raw material.

[0028] Mixing: Add the above raw materials into a high speed mixer and mix at 600 rpm for 10 minutes, add into a twin screw extruder, plasticize and mix at 245±5°C, extrude and pelletize to obtain a high gloss paint-free lamp plastic.

[0029] Example 4, preparation of high gloss paint-free lamp plastic, the specific implementation method is as follows: 1. Preparation of Brightening Agent Step A1: premix triethylamine and tetrahydrofuran to form an alkaline mixed system, then add tetramethylenediamine and trifluoroiodopropane to mix, introduce nitrogen to replace the air in the reaction system, stir at 60rpm, control the temperature to 55°C, and react for 3.2h; in the above reaction, the amount ratio of tetramethylenediamine, trifluoroiodopropane, triethylamine and tetrahydrofuran is 0.1mol:0.2mol:13mL:90mL, and after the reaction is completed, tetrahydrofuran is removed by rotary evaporation, and water is added to the rotary evaporation substrate for washing, and the aqueous phase is separated and dried to obtain an intermediate.

[0030] Step A2: dimethyl alkyl diacid, intermediate and anhydrous toluene are added and mixed, dry air is introduced to replace the air in the reaction system, trimethylaluminum is added and mixed, stirring is applied at 90 rpm, the temperature is controlled to be 75° C., and the reaction is carried out for 6.5 hours; in the above reaction, the amount ratio of dimethyl alkyl diacid, intermediate, trimethylaluminum and anhydrous toluene is 0.1 mol: 0.1 mol: 0.16 g: 160 mL, and toluene is evaporated under reduced pressure after the reaction is completed. The substrate is washed with ethanol and water in turn, and dried to obtain a brightener.

[0031] 2. Preparation of high gloss paint-free lamp plastics Ingredients: 30wt% ABS resin, selected from PA-707 resin raw material; 5wt% brightener, which is prepared in this embodiment; 3wt% compatibilizer, selected from HW-102 maleic anhydride grafted ABS copolymer; 0.17wt% antioxidant, selected from antioxidant 1010 and antioxidant 168 in equal weight ratio; 0.12wt% stabilizer, selected from ultraviolet absorber UV-P and light stabilizer 770 in 2:1 weight ratio; 2.2wt% pigment, selected from SM8802 aluminum pigment; the remainder is PC resin, selected from PC-122 resin raw material.

[0032] Mixing: Add the above raw materials into a high speed mixer and mix at 600 rpm for 10 minutes, add into a twin screw extruder, plasticize and mix at 245±5°C, extrude and pelletize to obtain a high gloss paint-free lamp plastic.

[0033] As a comparative example, referring to Example 4, the brightener was replaced with 2.2 wt % of polytetrafluoroethylene powder and 2.8 wt % of lubricant EBS (ethylene bisstearamide), and the rest of the implementation process was exactly the same.

[0034] The plastic pellets prepared as above were hot pressed into sheets at a temperature of 220°C and a pressure of 10 MPa using a flat vulcanizer, and samples were taken for the following tests: Gloss test: Use a gloss meter to test, the light angle is 60°, the number of samples tested is 5, and the average value is taken; Chroma test: Calibrate the colorimeter with a standard color plate. After the color meets the standard, place the sample on the colorimeter for testing; The specific test results are shown in Table 1 below: Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example Glossiness / % 95.09 96.15 95.92 96.24 90.36 L 81.35 80.69 81.15 81.07 74.92 a -0.04 -0.11 -0.08 -0.06 -0.24 b -0.05 0.03 -0.01 -0.03 0.17 It can be seen from the test results in Table 1 that the plastics prepared in the examples have a high glossiness, all reaching more than 95%, and the plastics have a high brightness, brighter colors, and lower color difference, which is beneficial to improving the aesthetics of the lamps.

[0035] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0036] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A high gloss paint-free lamp plastic, characterized in that: The specific components are: ABS resin 27-35wt%, brightener 4.2-5.5wt%, compatibilizer 2.4-3.2wt%, antioxidant 0.15-0.2wt%, stabilizer 0.1-0.13wt% and pigment 1.9-2.4wt%, and the balance is PC resin; Step A1: premix triethylamine and tetrahydrofuran, add tetramethylenediamine and trifluoroiodopropane and mix well, introduce nitrogen protection, stir and react at 45-55°C for 3-4h, and after the reaction, remove tetrahydrofuran by rotary evaporation, wash the substrate with water, remove the aqueous phase, and dry to obtain an intermediate; Step A2: Alkyl dicarboxylic acid dimethyl ester, intermediate and anhydrous toluene are mixed, dry gas protection is introduced, and trimethylaluminum is added and mixed, and the mixture is stirred at 70-90°C for 5.5-7h. After the reaction is completed, toluene is evaporated under reduced pressure, and the substrate is washed with ethanol and water in turn, and dried to obtain a brightener.

2. The high gloss paint-free lamp plastic according to claim 1, characterized in that: The usage ratio of tetramethylenediamine, trifluoroiodopropane, triethylamine and tetrahydrofuran is 0.1 mol: 0.2 mol: 10-15 mL: 80-110 mL.

3. The high gloss paint-free lamp plastic according to claim 2, characterized in that: The usage ratio of dimethyl alkyl diacid ester, intermediate, trimethylaluminum and anhydrous toluene is 0.1 mol: 0.1 mol: 0.1-0.18 g: 150-200 mL.

4. The high gloss paint-free lamp plastic according to claim 3, characterized in that: The alkyl diacid dimethyl ester is selected from one of dimethyl pimelate, dimethyl sebacate and dimethyl dodecanedioate.

5. The high gloss paint-free lamp plastic according to claim 1, characterized in that: The compatibilizer is maleic anhydride grafted ABS copolymer.

6. The high gloss paint-free lamp plastic according to claim 1, characterized in that: The antioxidant is compounded by antioxidant 1010 and antioxidant 168.

7. The high gloss paint-free lamp plastic according to claim 1, characterized in that: The stabilizer is compounded by ultraviolet absorber UV-P and light stabilizer 770.

8. The high gloss paint-free lamp plastic according to claim 1, characterized in that: The pigment is an aluminum pigment.

9. A method for preparing a high-gloss paint-free lamp plastic according to any one of claims 1 to 8, characterized in that: Specifically, the raw materials of various components are mixed, plasticized and mixed at 245±5°C, and extruded and pelletized to obtain high-gloss paint-free lamp plastic.