CN109943068B - High-temperature-resistant nylon material, electroplating nylon material, preparation method and application thereof - Google Patents
High-temperature-resistant nylon material, electroplating nylon material, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of high polymer materials, and particularly discloses a high-temperature-resistant nylon material, an electroplating nylon material, and preparation methods and applications thereof. The high-temperature-resistant electroplating nylon material is composed of PA6T, potassium titanate whiskers, minerals and an optional high-temperature-resistant antioxidant, wherein the minerals contain kaolin, and the weight ratio of the PA6T to the potassium titanate whiskers to the minerals is (0.1-30) to (20-50). The nylon material provided by the invention not only has higher thermal deformation temperature and notch impact strength, but also can perfectly solve the problems of high nylon water absorption and difficult electroplating, has good electroplating effect at the high temperature of 170-190 ℃, has smoother surface after electroplating and high product quality, and thus widens the application of the electroplated plastic in high-temperature environment.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly discloses a high-temperature-resistant nylon material, an electroplating nylon material, and preparation methods and applications thereof.
Background
The plastic electroplating product not only can realize good metal texture, but also can reduce the weight of the product, effectively improve the appearance and the decoration of the plastic, and simultaneously improve the performances of the plastic in the aspects of electricity, heat, corrosion resistance and the like, but the selection of the plastic material for electroplating comprehensively considers the factors of the processing performance, the mechanical performance, the material cost, the electroplating cost, the difficulty degree of electroplating, the dimensional precision and the like of the material. At present, ABS and PC/ABS are used as base materials for the mainstream electroplating materials, but with the development of society and the improvement of living standard, the requirements of people on products are higher and more diversified, and the heat distortion temperature of the ABS and PC/ABS electroplating materials is lower, so that the ABS and PC/ABS electroplating materials cannot meet the requirements of some higher-temperature application occasions. The nylon material is one of five engineering materials and has extremely excellent mechanical properties. However, the common nylon has high water absorption rate, but cannot be used for electroplating in large quantity, a special electroplating production line needs to be built, the equipment investment is high, and the electroplating cost is higher than that of electroplating ABS and PC/ABS as base materials.
CN108219450A discloses a nylon material, which comprises the following components in percentage by weight: 23-75% of nylon resin, 55-10% of PA 13355, 0-35% of glass fiber, 20-30% of filling mineral, 0-1% of lubricant and 0-1% of antioxidant. The PA1335 is an amorphous nylon material, has good compatibility with nylon, and aims to reduce the crystallinity of the nylon and increase the dimensional stability of the nylon material, thereby improving the apparent performance of the nylon material and reducing the surface floating fiber. The addition of the glass fiber can improve the strength and modulus of the nylon material, and is beneficial to increasing the application of the nylon material by electroplating. The filler mineral is specially treated MD1250WC10012 with unique size and acid-base property, which can endow nylon with electroplating performance, while the conventional filler mineral which is also used as wollastonite and talcum powder has no electroplating effect (see CN108219450A description paragraph [0090 ]). In addition, although the nylon material provided in CN108219450A has a good electroplating effect at a lower temperature, and the surface of the obtained material has substantially no floating fiber, the thermal deformation temperature still needs to be further increased, and when the electroplating temperature is higher, for example, 170-190 ℃, electroplating is difficult to achieve, and some higher temperature applications cannot be satisfied.
Disclosure of Invention
The invention aims to overcome the defects that the existing nylon material is low in thermal deformation temperature and difficult to realize electroplating at the high temperature of 170-190 ℃, and provides a high-temperature-resistant nylon material which is high in thermal deformation temperature and has a good electroplating effect at the high temperature of 170-190 ℃, a preparation method thereof, an electroplating nylon material obtained by electroplating the high-temperature-resistant nylon material, and a preparation method and application thereof.
The existing nylon material generally needs to be added with glass fiber, and the use of the glass fiber can cause the surface of the obtained nylon material to have floating fiber and not smooth. In this regard, although the prior art teaches that this problem can be improved by introducing amorphous nylon material PA1335, such as CN108219450A, and inorganic whiskers, such as CN10569447A, it is generally an essential component, indispensable or indispensable, of nylon materials in view of the fact that the addition of glass fibers can significantly increase the strength and modulus of nylon materials. However, after intensive research, the inventors of the present invention found that the nylon material containing glass fiber has a plurality of burrs on the surface, and the burrs seriously affect the high temperature plating resistance, and thus the electroplating at a higher temperature of 170-190 ℃ cannot be achieved at all. After intensive research, the inventor of the invention also finds that under the premise of adopting the specific nylon resin such as PA6T, when the glass fiber is completely replaced by potassium titanate whisker, kaolin-containing mineral and optional high-temperature-resistant antioxidant are added, and the weight ratio of PA6T, potassium titanate whisker and mineral is controlled to be 100 (0.1-30) to (20-50), the obtained nylon material has higher thermal deformation temperature and high-temperature-resistant electroplating performance, and can completely bear the higher electroplating temperature of 170-190 ℃. Based on this, the present invention has been completed.
The high-temperature-resistant electroplating nylon material is composed of PA6T, potassium titanate whiskers, minerals and an optional high-temperature-resistant antioxidant, wherein the minerals contain kaolin, and the weight ratio of the PA6T to the potassium titanate whiskers to the minerals is (0.1-30) to (20-50).
Further, the weight ratio of the PA6T, the potassium titanate whisker, the mineral and the high-temperature-resistant antioxidant is 100 (10-15): (30-40): 0-5).
Further, the PA6T is at least one of PA6T/6, PA6T/66 and PA 6T/6I.
Further, the PA6T is a mixture of PA6T/6 and PA6T/66 or a mixture of PA6T/66 and PA 6T/6I.
Further, the weight ratio of PA6T/66 to PA6T/6 in the mixture of PA6T/6 and PA6T/66 is 9: 1-6: 4.
Further, the weight ratio of PA6T/66 to PA6T/6I in the mixture of PA6T/66 and PA6T/6I is 9: 1-6: 4.
Further, the potassium titanate whisker is a potassium hexatitanate whisker.
Furthermore, the diameter of the potassium titanate whisker is 0.2-0.6 μm, and the length of the potassium titanate whisker is 3-20 μm.
Further, the content of kaolin in the mineral is not less than 30 wt%.
Further, the mineral is kaolin or a mixture of kaolin and wollastonite.
Further, the kaolin is calcined kaolin.
Further, the calcination temperature of the calcined kaolin is 500-700 ℃, and the particle size is 2000-5000 meshes.
Further, the high-temperature-resistant antioxidant is selected from at least one of H161, 1098, S9228 and HP-136.
The invention also provides a preparation method of the high-temperature resistant electroplating nylon material, which comprises the step of uniformly mixing all the components.
The invention also provides a preparation method of the electroplating nylon material, wherein the method comprises the step of electroplating the section bar of the high-temperature-resistant electroplating nylon material.
Furthermore, the electroplating temperature is 170-190 ℃.
The invention also provides the electroplating nylon material prepared by the method.
In addition, the invention also provides application of the electroplating nylon material as a bathroom product.
The nylon material provided by the invention not only has higher thermal deformation temperature and notch impact strength, but also can perfectly solve the problems of high nylon water absorption and difficult electroplating, has good electroplating effect at the high temperature of 170-190 ℃, has smoother surface after electroplating and high product quality, and thus widens the application of the electroplated plastic in high-temperature environment.
Detailed Description
The present invention will be described in detail below.
In the invention, the high-temperature resistant electroplating nylon material consists of PA6T, potassium titanate whisker and mineral, or consists of PA6T, potassium titanate whisker, mineral and high-temperature resistant antioxidant. Wherein the weight ratio of the PA6T, the potassium titanate whisker and the mineral is 100 (0.1-30): 20-50), preferably 100 (0.5-25): 25-45), more preferably 100 (5-20): 25-40, and most preferably 100 (10-15): 30-40. The weight ratio of the PA6T to the high-temperature-resistant antioxidant can be 100 (0-5), preferably 100 (0.01-4), more preferably 100 (0.05-3), and most preferably 100 (0.1-1).
In the invention, the PA6T can be at least one of PA6T/6, PA6T/66 and PA6T/6I, preferably a mixture of PA6T/6 and PA6T/66 or a mixture of PA6T/66 and PA6T/6I, and then the corresponding nylon material has more excellent high-temperature plating resistance. When the PA6T is a mixture of PA6T/6 and PA6T/66, the weight ratio of PA6T/66 to PA6T/6 is preferably 9: 1-6: 4, more preferably 8: 2-6: 4, and most preferably 7: 3. When the PA6T is a mixture of PA6T/66 and PA6T/6I, the weight ratio of PA6T/66 to PA6T/6I is preferably 9: 1-6: 4, more preferably 8: 2-6: 4, and most preferably 7: 3. Wherein the relative viscosity of the nylon resins PA6T/6, PA6T/66 and PA6T/6I is preferably 2.0-2.4. In the present invention, the test temperature of the relative viscosity is 25. + -. 0.1 ℃ and the reference medium is 96. + -. 0.15 wt% aqueous sulfuric acid.
In the present invention, the potassium titanate whisker is preferably a potassium hexatitanate whisker. In addition, the diameter of the potassium titanate whisker is preferably 0.2-0.6 μm, and the length of the potassium titanate whisker is preferably 3-20 μm.
In the present invention, the mineral contains kaolin, preferably kaolin, in an amount of not less than 30% by weight, and for example, may be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% by weight. According to a preferred embodiment of the invention, the mineral is kaolin or a mixture of kaolin and wollastonite. When the mineral is a mixture of kaolin and wollastonite, the content of kaolin is not less than 30 wt%, for example, the content may be the above percentage content, which is not described herein again. In addition, the kaolin is preferably calcined kaolin, and the corresponding nylon material has higher heat distortion temperature and more excellent high-temperature plating resistance. The calcination temperature of the calcined kaolin can be 500-700 ℃, and the particle size can be 2000-5000 meshes. In the present invention, the wollastonite may be unmodified wollastonite or wollastonite modified by a conventional method.
Specific examples of the high temperature antioxidant include, but are not limited to: at least one of H161, 1098, S9228 and HP-136.
In addition, the high-temperature resistant electroplating nylon material can be granules and various existing profiles.
The preparation method of the high-temperature-resistant electroplating nylon material provided by the invention comprises the step of uniformly mixing all the components. The mixing may be performed by manually stirring or in various existing mixing apparatuses. The mixing conditions are such that the above components form a homogeneous system. In the mixing process, the above components can be mixed in any order, for example, the above components can be added into a mixing container one by one in any order for mixing, or any two or more of the above components can be uniformly mixed and then the other components can be added for continuous uniform mixing. According to a specific embodiment of the invention, the mixing is carried out in a twin-screw extruder with a double-side feeding system, in the mixing process, the PA6T and the optional high-temperature-resistant antioxidant are added from a main feeding port of the twin-screw extruder, the potassium titanate whiskers and the minerals are added from double-side feeding ports, and the raw materials are subjected to melt extrusion granulation to obtain the nylon material. The length-diameter ratio of the double-screw extruder can be (36-48): 1, the extrusion temperature can be 280-320 ℃, the screw rotating speed can be 260-400 r/min, and the feeding rotating speed can be 15-30 r/min. In addition, the preparation method of the high-temperature resistant electroplated nylon material provided by the invention can also comprise a step of injection molding the granules into a profile product (such as a plate, a column, a profile and the like).
The preparation method of the electroplating nylon material provided by the invention comprises the step of electroplating the section bar of the high-temperature-resistant electroplating nylon material. The electroplating can adopt electroplating process of ABS and PC/ABS, and the electroplating solution can be the same as that in the prior art. In addition, the electroplating temperature can be 170-190 ℃.
In addition, the invention also provides application of the electroplating nylon material as a bathroom product.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following examples and comparative examples, the relative viscosity of PA6T/6 was 2.0, that of PA6T/66 was 2.4 and that of PA6T/6I was 2.2.
Example 1
PA6T (a mixture formed by PA6T/66 and PA6T/6 according to a weight ratio of 7: 3) and H161 are added from a main feeding port of a double-screw extruder, potassium titanate whiskers (with the diameter of 0.2-0.6 mu m and the length of 3-20 mu m) and calcined kaolin (with the calcination temperature of 500 ℃ and the particle size of 2000-5000 meshes) are added from double-side feeding ports, the temperature of the double-screw extruder is set to be 280-320 ℃, the screw rotating speed is set to be 260-400 r/min, and the feeding rotating speed is set to be 15-30 r/min, the raw materials are subjected to melt extrusion, and water-cooling bracing is carried out to obtain the nylon material, wherein the using amount of each component is shown in Table 1.
Example 2
Adding PA6T (a mixture formed by PA6T/66 and PA6T/6I according to a weight ratio of 7: 3) and S9228 from a main feeding port of a double-screw extruder, adding potassium titanate whiskers (with the diameter of 0.2-0.6 mu m and the length of 3-20 mu m) and calcined kaolin (with the calcining temperature of 700 ℃ and the particle size of 2000-5000 meshes) from double-side feeding ports, setting the temperature of the double-screw extruder to be 280-320 ℃, the screw rotating speed to be 260-400 r/min and the feeding rotating speed to be 15-30 r/min, performing melt extrusion on the raw materials, and performing water-cooling, drawing strips and cutting to obtain the nylon material, wherein the using amount of each component is shown in Table 1.
Example 3
PA6T (a mixture formed by PA6T/66 and PA6T/6 according to a weight ratio of 6: 4) and 1098 are added from a main feeding port of a double-screw extruder, potassium titanate whiskers (with the diameter of 0.2-0.6 mu m and the length of 3-20 mu m) and calcined kaolin (with the calcining temperature of 600 ℃ and the particle size of 2000-5000 meshes) are added from a double-side feeding port, the temperature of the double-screw extruder is set to be 280-320 ℃, the screw rotating speed is set to be 260-400 r/min, the feeding rotating speed is set to be 15-30 r/min, the raw materials are subjected to melt extrusion, and water-cooling bracing is carried out to obtain the nylon material, wherein the using amount of each component is shown in Table 1.
Example 4
Nylon material was prepared according to the method of example 1 except that PA6T was all PA6T/66 to give nylon material, wherein the amounts of the components are as shown in table 1.
Example 5
A nylon material was prepared by following the procedure of example 1 except that the calcined kaolin was replaced with the same parts by weight of a mixed mineral (a mixture of kaolin and unmodified wollastonite in a mass ratio of 1: 1) to obtain a nylon material, wherein the amounts of the respective components are shown in Table 1.
Example 6
A nylon material was prepared according to the method of example 5, except that the high temperature antioxidant H161 was not added, to obtain a nylon material, wherein the amounts of the components are shown in Table 1.
Comparative example 1
A nylon material was prepared according to the method of example 6, except that the amounts of the components were outside the scope of the present invention, to give a reference nylon material, wherein the amounts of the components are as shown in table 1.
Comparative example 2
A nylon material was prepared by following the procedure of example 6, except that the potassium titanate whiskers were replaced with the same parts by weight of glass fibers to obtain a reference nylon material, wherein the amounts of the respective components were as shown in table 1.
Comparative example 3
A nylon material was prepared as in example 6, except that nylon PA6 was used in place of nylon PA6T to provide a reference nylon material, wherein the amounts of the components are as shown in table 1.
Comparative example 4
A nylon material was prepared by following the procedure of example 6, except that the mixed mineral obtained from kaolin and unmodified wollastonite in the mass ratio of 1:1 was replaced with the same parts by weight of unmodified wollastonite, to obtain a reference nylon material, wherein the amounts of the respective components are shown in Table 1.
TABLE 1 (amounts of the components, in parts by weight)
| Item | PA6T | Potassium titanate whisker | Mineral substance | High temperature resistant antioxidant |
| Example 1 | 100 | 15 | 30 | 0.5 |
| Example 2 | 100 | 10 | 35 | 0.5 |
| Example 3 | 100 | 12 | 40 | 0.5 |
| Example 4 | 100 | 15 | 30 | 0.5 |
| Example 5 | 100 | 15 | 30 | 0.5 |
| Example 6 | 100 | 15 | 30 | - |
| Comparative example 1 | 100 | 40 | 60 | - |
| Comparative example 2 | 100 | Glass fiber 15 | 30 | - |
| Comparative example 3 | 100 | 15 | 30 | - |
| Comparative example 4 | 100 | 15 | Unmodified wollastonite 30 | - |
Test example
Respectively injection-molding the nylon materials obtained in examples 1 to 6 and the reference nylon materials obtained in comparative examples 1 to 4 into standard sample strips, testing the notch impact strength and the thermal deformation temperature (1.8MPa) of the simply supported beam according to the following methods, simultaneously injection-molding the nylon materials and the reference nylon materials into plastic plates with the thickness of 3mm, sequentially electroplating three layers of coatings of copper, nickel and chromium on the surfaces of the plastic plates at 180 ℃ by adopting the same electroplating process for 5.5 mu m in total to obtain electroplated nylon materials, and then testing the apparent mass and the coating bonding force of the coatings according to the following methods:
(1) notched impact strength: the procedure was carried out according to ISO179-1, the results are shown in Table 2;
(2) heat distortion temperature: the results obtained according to the method disclosed in ISO 75 are shown in Table 2;
(3) apparent mass: the apparent mass of the nylon material before and after electroplating is observed by naked eyes, and the obtained result is shown in table 2;
(4) coating binding force: referring to the method disclosed in GB/T23447, a test sample of an electroplating nylon material is sequentially processed according to the following steps: and (3) drying at 70 ℃ for 30 minutes, drying at 15 ℃ for 15 minutes, drying at-30 ℃ for 30 minutes and drying at 15 ℃ for 15 minutes, repeating the steps in sequence, observing the surface of the sample after circulating for 5 times, and determining that the surface of the sample is qualified without corrosion points, cracks, bubbles, peeling, fading and deformation which can be observed by naked eyes, wherein the obtained results are shown in Table 2.
TABLE 2
From the results in table 2, it can be seen that the nylon material provided by the present invention not only has higher thermal deformation temperature and notch impact strength, but also can perfectly solve the problem of difficult electroplating of nylon by using PA6T, potassium titanate whisker, mineral and optional high temperature resistant antioxidant in a specific ratio, and has very excellent high temperature plating resistance (can resist high temperature of 180 ℃). In addition, the surface of the electroplated nylon material is smooth, the bonding force is good, the product quality is high, and the product has great industrial application prospects. As can be seen from the comparison between example 1 and examples 4-5, when PA6T is preferably a mixture of PA6T/6 and PA6T/66 or a mixture of PA6T/66 and PA6T/6I, or when the mineral is preferably calcined kaolin, the improvement of the high-temperature plating resistance (reflected by the heat distortion temperature) of the obtained nylon material is more facilitated. As can be seen from the comparison between example 1 and example 6, when the nylon material preferably further contains a high-temperature-resistant antioxidant, the material can be prevented from being degraded and yellowing in the extrusion process, and the physical properties of the material can be ensured. As can be seen from comparison between the embodiment 6 and the comparative examples 1-4, the matching use of the PA6T, the potassium titanate whisker, the mineral and the high-temperature-resistant antioxidant in a specific proportion plays a crucial role in improving the high-temperature resistance of the nylon material (the proportion of the components in the comparative example 1 is not within the range of the invention, the notch impact performance is poor, the product is easy to damage in the electroplating process, the requirement of a client cannot be met, and the physical property of a plating layer is unqualified), the comparative example 2 adopts glass fiber which is easy to generate floating fiber and can cause poor electroplating and the electroplating binding force is reduced, the comparative example 3 adopts nylon PA6 to replace nylon PA6T, the thermal deformation temperature is too low to carry out high-temperature electroplating, and the mineral used in the comparative example 4 is different from the invention, and the test of the binding force of the plating layer after electroplating is unqualified).
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (3)
1. The preparation method of the electroplating nylon material is characterized in that the preparation method is used for electroplating the section bar of the high-temperature resistant electroplating nylon material; the electroplating temperature is 170-190 ℃; the high-temperature-resistant electroplating nylon material is composed of PA6T, potassium titanate whiskers, minerals and a high-temperature-resistant antioxidant, wherein the weight parts of the high-temperature-resistant electroplating nylon material PA6T, the potassium titanate whiskers, the minerals and the high-temperature-resistant antioxidant are 100: 15: 30: 0.5, the high-temperature resistant electroplating nylon material PA6T is a PA6T mixture formed by PA6T/66 and PA6T/6, and is prepared by the following steps:
adding a PA6T mixture formed by mixing PA6T/66 and PA6T/6 according to a weight ratio of 7:3 and H161 from a main feeding port of a double-screw extruder, wherein the relative viscosity of PA6T/6 is 2.0, the relative viscosity of PA6T/66 is 2.4, adding potassium titanate whiskers with the diameter of 0.2-0.6 mu m and the length of 3-20 mu m and calcined kaolin with the particle size of 2000-5000 meshes from a double-side feeding port, wherein the temperature of the double-screw extruder is 280-320 ℃, the screw rotating speed is 260-400 r/min, and the feeding rotating speed is 15-30 r/min, and carrying out melt extrusion and water-cooling, drawing and granulating on the raw materials to obtain the nylon material.
2. An electroplated nylon material made by the method of claim 1.
3. Use of the electroplated nylon material of claim 2 as a sanitary product.
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