PVC (polyvinyl chloride) stabilizer for ultrathin-wall automobile wire and preparation method of PVC stabilizer

Abstract

The invention provides a PVC (polyvinyl chloride) stabilizer for ultrathin-wall automobile wires and a preparation method of the PVC stabilizer. The PVC stabilizer for the ultrathin-wall automobile wire comprises the following components in parts by weight: 15-25 parts of calcium-zinc composite metal soap, 5-10 parts of hydrotalcite, 3-8 parts of a beta-diketone compound, 2-5 parts of a hindered phenol antioxidant, 1-3 parts of a phosphite ester antioxidant, 2-5 parts of a lubricant, 1-3 parts of an ultraviolet light absorber, 0.5-2 parts of a coupling agent, 4-5 parts of calcined clay and 5-15 parts of filler. According to the PVC stabilizer for the ultrathin-wall automobile wire and the preparation method of the PVC stabilizer, the calcium-zinc composite metal soap, the hydrotalcite, the beta-diketone compound and other stabilizers have a synergistic effect, so that the PVC stabilizer has excellent thermal stability; according to the present invention, the material can effectively inhibit the oxidative degradation of the PVC during the processing and using process, can prolong the service life of the wire, and can provide the good insulation stability through the minimum addition proportion of the calcined clay so as to ensure the thermal stability and the mechanical physical property of the material.

Description

Technical Field

[0001] The present invention relates to the field of polymer material additives, and particularly to a PVC stabilizer for ultra-thin wall automotive wires and a preparation method thereof. Background Art

[0002] Polyvinyl chloride (PVC), as a widely used polymer material, has important applications in the field of automotive wires. With the development of the automotive industry towards lightweight and miniaturization, the requirements for automotive wires are also getting higher and higher. Ultra-thin wall automotive wires, due to their advantages such as light weight and small space occupation, have gradually become the trend of automotive wire development. However, during the processing and use of PVC materials, they are easily affected by factors such as heat, light, and oxygen and degrade, resulting in a decline in the physical and electrical properties of the wires and shortening the service life of the wires. Therefore, it is necessary to add stabilizers to improve the stability of PVC.

[0003] Currently, the commonly used PVC stabilizers on the market mainly include lead salts, metal soaps, organotin compounds, etc. Although lead salt stabilizers have good stabilizing effects, they are highly toxic and do not meet environmental protection requirements; the stability of metal soap stabilizers is relatively weak, and blooming is likely to occur; organotin stabilizers are relatively expensive, which limits their wide application.

[0004] For ultra-thin wall automotive wires, due to their thin wall thickness, the performance requirements for PVC stabilizers are more stringent. They not only require good thermal stability, insulation, and mechanical physical properties, but also require the stabilizers to have excellent processing performance and compatibility to ensure the quality and performance of the wires. Existing PVC stabilizers are difficult to meet the comprehensive performance requirements of ultra-thin wall automotive wires.

[0005] Therefore, it is necessary to provide a PVC stabilizer for ultra-thin wall automotive wires and a preparation method thereof to solve the above technical problems. Summary of the Invention

[0006] The present invention provides a PVC stabilizer for ultra-thin wall automotive wires and a preparation method thereof, which solves the problems in the background art.

[0007] To solve the above technical problems, the PVC stabilizer for ultra-thin wall automotive wires provided by the present invention includes the following weight groups:

[0008] 15 - 25 parts of calcium-zinc composite metal soap, 5 - 10 parts of hydrotalcite, 3 - 8 parts of β-diketone compound, 2 - 5 parts of hindered phenol antioxidant, 1 - 3 parts of phosphite antioxidant, 2 - 5 parts of lubricant, 1 - 3 parts of ultraviolet absorber, 0.5 - 2 parts of coupling agent, 4 - 5 parts of calcined clay, 5 - 15 parts of filler.

[0009] Preferably, it includes the following weight groups: 20 parts of calcium-zinc composite metal soap, 8 parts of hydrotalcite, 3 parts of β-diketone compound, 3 parts of hindered phenol antioxidant, 2 parts of phosphite antioxidant, 5 parts of lubricant, 3 parts of ultraviolet absorber, 1 part of coupling agent, 4.5 parts of calcined clay, and 10 parts of filler.

[0010] Preferably, the calcium-zinc composite metal soap is compounded from calcium stearate and zinc stearate in a mass ratio of 2:1 - 3:1.

[0011] Preferably, the hydrotalcite is layered double metal hydroxide, and the molar ratio of magnesium to aluminum is 2 - 4:1.

[0012] Preferably, the β-diketone compound is calcium acetylacetonate, and the hindered phenol antioxidant is pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

[0013] Preferably, the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite, and the ultraviolet absorber is 2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol.

[0014] Preferably, the lubricant is stearic acid, the coupling agent is γ-aminopropyltriethoxysilane; and the filler is nano calcium carbonate.

[0015] Preferably, the mesh number of the calcined clay is 500 - 2500 mesh.

[0016] A preparation method of a PVC stabilizer for ultra-thin wall automotive wires, which is used to prepare the PVC stabilizer for ultra-thin wall automotive wires, includes the following steps:

[0017] S1. Weigh each component according to the weight groups.

[0018] S2. Add the calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, hindered phenol antioxidant, phosphite antioxidant, lubricant, ultraviolet absorber, coupling agent, calcined clay and filler into a high-speed mixer, and mix each component evenly.

[0019] S3. Transfer the mixed material to a twin-screw extruder for extrusion granulation, and then the PVC stabilizer for ultra-thin wall automotive wires is obtained.

[0020] Preferably, the temperature of the high-speed mixer is 80 - 100 °C, and the mixing time is 10 - 20 min; the temperature of the twin-screw extruder is 120 - 160 °C, and the screw speed is 150 - 250 r / min.

[0021] Compared with the related technology, the PVC stabilizer for ultra-thin wall automotive wires and its preparation method provided by the present invention have the following beneficial effects:

[0022] The present invention provides a PVC stabilizer for ultra-thin wall automotive wires and a preparation method thereof. The present invention uses a variety of stabilizers such as calcium-zinc composite metal soap, hydrotalcite, and β-diketone compounds to act synergistically, having excellent thermal stability. The calcium-zinc composite metal soap can absorb hydrogen chloride generated by the degradation of PVC, hydrotalcite can neutralize hydrogen chloride and inhibit its catalytic degradation of PVC, and the β-diketone compound can form a stable complex with metal ions, further improving the stabilizing effect of the stabilizer. At the same time, the addition of hindered phenol antioxidants and phosphite antioxidants can effectively inhibit the oxidative degradation of PVC during processing and use, and extend the service life of the wires. Lubricants and coupling agents are added. The lubricant can reduce the friction and energy consumption of PVC during processing and improve the processing performance; the coupling agent can enhance the compatibility between the stabilizer and the PVC matrix, make the stabilizer uniformly dispersed in PVC, avoid phenomena such as blooming, and improve the appearance quality and performance of the wires. By calcining clay, better insulation stability is given to the material with the smallest addition ratio, thereby ensuring the thermal stability and mechanical and physical properties of the material. Nano calcium carbonate is selected as the filler. Nano calcium carbonate has the characteristics of large specific surface area and high activity, can improve the mechanical properties and dimensional stability of PVC, and does not affect the processing performance and electrical properties of PVC. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic flow chart of a preferred embodiment of the preparation method of the PVC stabilizer for ultra-thin wall automotive wires provided by the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] The present invention will be further described below in conjunction with the drawings and embodiments.

[0025] Please refer to Figure 1 , wherein, Figure 1 It is a schematic flow chart of a preferred embodiment of the preparation method of the PVC stabilizer for ultra-thin wall automotive wires provided by the present invention.

[0026] Example 1

[0027] A PVC stabilizer for ultra-thin wall automotive wires, comprising the following weight groups:

[0028] 15 parts of calcium-zinc composite metal soap (calcium stearate and zinc stearate are compounded at a mass ratio of 2:1), 5 parts of hydrotalcite (magnesium-aluminum molar ratio is 2:1), 3 parts of β-diketone compound (calcium acetylacetonate), 2 parts of hindered phenol antioxidant (pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), 1 part of phosphite antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), 2 parts of lubricant (stearic acid), 1 part of ultraviolet absorber (2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol), 0.5 part of coupling agent (γ-aminopropyltriethoxysilane), 4 parts of calcined clay, 5 parts of filler (nano calcium carbonate).

[0029] A preparation method of a PVC stabilizer for ultra-thin wall automotive wires, which is used to prepare the PVC stabilizer for ultra-thin wall automotive wires, includes the following steps:

[0030] S1. Weigh each component according to the weight group;

[0031] S2. Add the calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, hindered phenol antioxidant, phosphite antioxidant, lubricant, ultraviolet absorber, coupling agent, calcined clay and filler into a high-speed mixer, and mix at 80 °C for 10 min to make each component fully and evenly mixed;

[0032] S3. Transfer the mixed material to a twin-screw extruder, and carry out extrusion granulation at 120 °C. The screw speed of the twin-screw extruder is 150 r / min, and thus the PVC stabilizer for ultra-thin wall automotive wires is obtained.

[0033] Example 2

[0034] A PVC stabilizer for ultra-thin wall automotive wires, including the following weight groups:

[0035] 20 parts of calcium-zinc composite metal soap (calcium stearate and zinc stearate are compounded at a mass ratio of 2:1), 7 parts of hydrotalcite (magnesium-aluminum molar ratio is 2:1), 5 parts of β-diketone compound (calcium acetylacetonate), 3 parts of hindered phenol antioxidant (pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), 2 parts of phosphite antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), 3 parts of lubricant (stearic acid), 2 parts of ultraviolet absorber (2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol), 1 part of coupling agent (γ-aminopropyltriethoxysilane), 4 parts of calcined clay, 8 parts of filler (nano calcium carbonate).

[0036] A preparation method of a PVC stabilizer for ultra-thin wall automotive wires, which is used to prepare the PVC stabilizer for ultra-thin wall automotive wires, includes the following steps:

[0037] S1. Weigh each component according to the weight group;

[0038] S2. Add calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, hindered phenol antioxidant, phosphite antioxidant, lubricant, ultraviolet absorber, coupling agent, calcined clay and filler into a high-speed mixer, and mix at 80 °C for 15 min to make each component fully and evenly mixed;

[0039] S3. Transfer the mixed material to a twin-screw extruder and carry out extrusion granulation at 140 °C. The screw speed of the twin-screw extruder is 200 r / min, and the PVC stabilizer for ultra-thin wall automotive wires is obtained.

[0040] Example 3

[0041] A PVC stabilizer for ultra-thin wall automotive wires, comprising the following weight groups:

[0042] 20 parts of calcium-zinc composite metal soap (calcium stearate and zinc stearate are compounded according to a mass ratio of 3:1), 10 parts of hydrotalcite (magnesium-aluminum molar ratio is 3:1), 8 parts of β-diketone compound (calcium acetylacetonate), 5 parts of hindered phenol antioxidant (pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 3 parts of phosphite antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), 4 parts of lubricant (stearic acid), 2 parts of ultraviolet absorber (2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol), 1.5 parts of coupling agent (γ-aminopropyltriethoxysilane), 4.5 parts of calcined clay, 12 parts of filler (nano calcium carbonate).

[0043] A preparation method of a PVC stabilizer for ultra-thin wall automotive wires, used to prepare the PVC stabilizer for ultra-thin wall automotive wires, comprising the following steps:

[0044] S1. Weigh each component according to the weight group;

[0045] S2. Add calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, hindered phenol antioxidant, phosphite antioxidant, lubricant, ultraviolet absorber, coupling agent, calcined clay and filler into a high-speed mixer, and mix at 90 °C for 15 min to make each component fully and evenly mixed;

[0046] S3. Transfer the mixed material to a twin-screw extruder and carry out extrusion granulation at 140 °C. The screw speed of the twin-screw extruder is 200 r / min, and the PVC stabilizer for ultra-thin wall automotive wires is obtained.

[0047] Example 4

[0048] A PVC stabilizer for ultra-thin wall automotive wires, comprising the following weight groups:

[0049] 25 parts of calcium-zinc composite metal soap (calcium stearate and zinc stearate are compounded at a mass ratio of 3:1), 10 parts of hydrotalcite (magnesium-aluminum molar ratio is 4:1), 8 parts of β-diketone compound (calcium acetylacetonate), 5 parts of hindered phenol antioxidant (pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 3 parts of phosphite antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), 5 parts of lubricant (stearic acid), 3 parts of ultraviolet absorber (2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol), 2 parts of coupling agent (γ-aminopropyltriethoxysilane), 5 parts of calcined clay, 15 parts of filler (nano calcium carbonate).

[0050] A preparation method of a PVC stabilizer for ultra-thin wall automotive wires, used to prepare the PVC stabilizer for ultra-thin wall automotive wires, includes the following steps:

[0051] S1. Weigh each component according to the weight group;

[0052] S2. Add the calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, hindered phenol antioxidant, phosphite antioxidant, lubricant, ultraviolet absorber, coupling agent, calcined clay and filler into a high-speed mixer, and mix at 100 °C for 120 min to make each component fully mixed and uniform;

[0053] S3. Transfer the mixed material to a twin-screw extruder and carry out extrusion granulation at 160 °C. The screw speed of the twin-screw extruder is 250 r / min, and thus the PVC stabilizer for ultra-thin wall automotive wires is obtained.

[0054] Comparative Example 1

[0055] A PVC stabilizer, by weight, consists of the following components: 15 parts of calcium-zinc composite metal soap (calcium stearate and zinc stearate are compounded at a mass ratio of 2:1), 2 parts of hindered phenol antioxidant (pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 1 part of phosphite antioxidant (tris(2,4-di-tert-butylphenyl) phosphite), 2 parts of lubricant (stearic acid), 1 part of ultraviolet absorber (2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol), 0.5 part of coupling agent (γ-aminopropyltriethoxysilane), 5 parts of filler (nano calcium carbonate). The preparation method is the same as that of Example 1.

[0056] Performance Test

[0057] The PVC stabilizers prepared in Examples 1-4 and Comparative Example 1 were respectively mixed with PVC resin at a mass ratio of 1:100, kneaded on a two-roll mill at 160-170 °C for 10-15 minutes, and then molded by compression molding on a flat vulcanizer at 170-180 °C to make test specimens. The following performance tests were carried out on the test specimens:

[0058] Thermal stability test: Using the Congo red method, the test specimens were placed in a hot air aging oven at 180 °C, and the discoloration time of the Congo red test paper was recorded. The longer the discoloration time, the better the thermal stability.

[0059] Processing performance test: The processing performance was evaluated by observing the fluidity, plasticization of the material during kneading and compression molding, and the surface quality of the product.

[0060] Mechanical property test: The tensile strength and elongation at break of the test specimens were tested according to the standard of GB / T1040.3-2006.

[0061] The test results are shown in the following table:

[0062]

[0063]

[0064] As can be seen from the above table, the PVC stabilizers prepared in Examples 1-4 of the present invention are significantly superior to Comparative Example 1 in terms of thermal stability, processing performance and mechanical properties, indicating that there is a good synergistic effect among the components of the PVC stabilizer of the present invention, which can effectively improve the comprehensive performance of PVC and is suitable for ultra-thin wall automotive wires.

[0065] Compared with the related technology, the PVC stabilizer for ultra-thin wall automotive wires and its preparation method provided by the present invention have the following beneficial effects:

[0066] The present invention uses a variety of stabilizers such as calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, etc. to act synergistically, having excellent thermal stability. The calcium-zinc composite metal soap can absorb hydrogen chloride generated by the degradation of PVC. Hydrotalcite can neutralize hydrogen chloride and inhibit its catalytic degradation of PVC. The β-diketone compound can form a stable complex with metal ions, further improving the stabilizing effect of the stabilizer. At the same time, the addition of hindered phenol antioxidants and phosphite antioxidants can effectively inhibit the oxidative degradation of PVC during processing and use, extending the service life of the wire. Lubricants and coupling agents are added. The lubricant can reduce the friction and energy consumption of PVC during processing, improving the processing performance. The coupling agent can enhance the compatibility between the stabilizer and the PVC matrix, making the stabilizer evenly dispersed in PVC, avoiding phenomena such as blooming, and improving the appearance quality and performance of the wire. By calcining kaolin clay, better insulation stability is imparted to the material with the smallest addition ratio, thus ensuring the thermal stability and mechanical and physical properties of the material. Nano calcium carbonate is selected as the filler. Nano calcium carbonate has the characteristics of a large specific surface area and high activity, which can improve the mechanical properties and dimensional stability of PVC, while not affecting the processing performance and electrical properties of PVC.

[0067] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structure or equivalent process transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in other related technical fields, shall be equally included in the patent protection scope of the present invention.

Claims

1. A PVC stabilizer for ultra-thin-wall automotive wires, characterized in that, It includes the following weight groups: 15 - 25 parts of calcium-zinc composite metal soap, 5 - 10 parts of hydrotalcite, 3 - 8 parts of β-diketone compound, 2 - 5 parts of hindered phenol antioxidant, 1 - 3 parts of phosphite antioxidant, 2 - 5 parts of lubricant, 1 - 3 parts of ultraviolet absorber, 0.5 - 2 parts of coupling agent, 4 - 5 parts of calcined clay, and 5 - 15 parts of filler.

2. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, wherein It includes the following weight groups: 20 parts of calcium-zinc composite metal soap, 8 parts of hydrotalcite, 3 parts of β-diketone compound, 3 parts of hindered phenol antioxidant, 2 parts of phosphite antioxidant, 5 parts of lubricant, 3 parts of ultraviolet absorber, 1 part of coupling agent, 4.5 parts of calcined clay, and 10 parts of filler.

3. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, characterized in that, The calcium-zinc composite metal soap is prepared by compounding calcium stearate and zinc stearate at a mass ratio of 2:1 - 3:

1.

4. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, characterized in that, The hydrotalcite is a layered double metal hydroxide with a molar ratio of magnesium to aluminum of 2 - 4:

1.

5. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, characterized in that, The β-diketone compound is calcium acetylacetonate, and the hindered phenol antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

6. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, characterized in that, The phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite, and the ultraviolet absorber is 2-(2H-benzotriazol-2-yl)-4,6-di-tert-amylphenol.

7. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, characterized in that, The lubricant is stearic acid, the coupling agent is γ-aminopropyltriethoxysilane; and the filler is nano calcium carbonate.

8. The PVC stabilizer for ultra-thin wall automotive wires according to claim 1, characterized in that, The mesh number of the calcined clay is 500 - 2500 meshes.

9. A preparation method of a PVC stabilizer for ultra-thin wall automotive wires, which is used to prepare the PVC stabilizer for ultra-thin wall automotive wires as described in any one of claims 1-8, characterized in that, It includes the following steps: S1. Weigh each component according to the weight groups. S2. Add the calcium-zinc composite metal soap, hydrotalcite, β-diketone compound, hindered phenol antioxidant, phosphite antioxidant, lubricant, ultraviolet absorber, coupling agent, calcined clay and filler into a high-speed mixer, and mix all components evenly. S3. Transfer the mixed material to a twin-screw extruder for extrusion granulation to obtain the PVC stabilizer for ultra-thin wall automotive wires.

10. The PVC stabilizer for ultra-thin wall automotive wires according to claim 9 and its preparation method are characterized in that, The temperature of the high-speed mixer is 80 - 100 °C, and the mixing time is 10 - 20 min; the temperature of the twin-screw extruder is 120 - 160 °C, and the screw speed is 150 - 250 r / min.

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