CN110093031B - High-strength high-heat-resistance stable-size electroplated nylon PA6 lamp housing material and preparation method thereof - Google Patents
High-strength high-heat-resistance stable-size electroplated nylon PA6 lamp housing material and preparation method thereof Download PDFInfo
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- CN110093031B CN110093031B CN201910479287.3A CN201910479287A CN110093031B CN 110093031 B CN110093031 B CN 110093031B CN 201910479287 A CN201910479287 A CN 201910479287A CN 110093031 B CN110093031 B CN 110093031B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a high-strength high-heat-resistance dimension-stable electroplated nylon PA6 lamp housing material and a preparation method thereof, talcum powder with high mesh number and high silicon content is selected and compounded with mica powder with high diameter-thickness ratio and small particle size, so that the strength, heat resistance and dimension stability of nylon PA6 are obviously improved; the filler is activated by a coupling agent, and the binding force with nylon is enhanced by adding a compatilizer, so that the strength and heat resistance of the nylon are greatly enhanced, the problems of insufficient strength of some nylon PA6, deformation caused by overhigh temperature during electroplating and the like are solved, and the surface effect of electroplating is improved; the water and volatile matters in the system are optimized and controlled through the formula, and the electroplating surface effect is improved, so that the electroplating nylon PA6 lamp housing material has the following characteristics: 1. the plating solution has the advantages of high mechanical strength, heat resistance and dimensional stability 2, high plating yield, good stability 3, good plating binding force, no obvious shedding in a hundred-grid test 4, no obvious pockmark on the plating surface and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-strength high-heat-resistance dimension-stable electroplated nylon PA6 lamp housing material and a preparation method thereof.
Background
Many types of plastics, but not all plastics, can be plated. Some plastics and metal coatings have too large difference of certain physical properties such as expansion coefficients, and the service performance of the plastics and the metal coatings is difficult to ensure in a high temperature difference environment. The most used for electroplating today is ABS, followed by PP. The unmodified nylon PA6 has poor strength and heat resistance, poor dimensional stability, difficulty in meeting the temperature use condition of the car lamp, unsatisfactory electroplating effect, high electroplating defective rate, and the defects of pockmarks on the electroplating surface, peeling, poor coating bonding force and the like. The modified nylon PA6 has high mechanical strength and heat resistance, and is suitable for being used for electroplated parts such as lamp shells of vehicle lamps, so that the development of a high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp shell material is needed.
Disclosure of Invention
In order to overcome the defects, the invention provides a high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp housing material and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows: a high-strength high-heat-resistance dimensionally stable electro-plated nylon PA6 lamp housing material comprises the following materials in parts by weight:
60-75 parts of PA6 resin, 20-30 parts of talcum powder, 10-20 parts of mica powder, 0.1-0.5 part of coupling agent, 2-5 parts of compatilizer, 0.5-1 part of lubricant A, 0.5-1 part of lubricant B, 0.2-0.5 part of main antioxidant and 0.2-0.5 part of auxiliary antioxidant;
as a further improvement of the invention, the PA6 resin has a viscosity of 0.26-0.28, so that the material has sufficient fluidity.
As a further improvement of the invention, the talcum powder is high-mesh talcum powder with the mesh number of 2000-3000, and has extremely high silicon content of 62%.
As a further improvement of the invention, the mica powder is a high-number high-diameter-thickness ratio muscovite, the particle diameter of the muscovite is 18 mu m, and the diameter-thickness ratio of the muscovite is 80.
As a further improvement of the invention, the coupling agent is a 1:1 compound of a titanate coupling agent and a silane coupling agent, the titanate coupling agent is of a monoalkoxyl type, and the silane coupling agent is N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane.
As a further improvement of the invention, the compatilizer is POE grafted maleic anhydride polymer.
As a further improvement of the invention, the lubricant A is pentaerythritol stearate and the lubricant B is silicone oil. Pentaerythritol stearate has good thermal stability and low volatility at high temperatures. Because of no color development groups such as amide and the like, the product does not yellow or change color, the original color of the product can be kept, and the color of the product can be improved. Good flowing and demoulding characteristics, improves the dispersibility of the filler and is beneficial to improving the electroplating effect.
In a further improvement of the present invention, the primary antioxidant is a hindered phenol antioxidant, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine. The modified nylon has good compatibility with nylon, high heat resistance and low volatility, reduces the performance loss caused by degradation in the PA6 processing process, and reduces the influence on electroplating property.
As a further improvement of the invention, the auxiliary antioxidant is a phosphite antioxidant. The compound has good synergistic effect with hindered phenol antioxidants.
A preparation method of a high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp housing material comprises the following steps:
(1) accurately weighing talcum powder, mica powder and lubricant according to the weight ratio, adding into a high-speed mixer, heating to 100 ℃, weighing the coupling agent in the formula, adding into a stirrer, stirring for 20min, and discharging for later use;
(2) accurately weighing the PA6 raw material, the compatilizer and other granules in the formula, adding the filler which is activated in the step (1), and stirring for 10 min;
(3) adding the mixed material obtained in the step (2) into a double-screw extruder hopper, setting the temperature of a screw cylinder at 230-250 ℃, and enabling a machine head to be 250 ℃;
(4) the high-strength high-heat-resistance dimensionally stable electroplating nylon PA6 material is prepared by extrusion, water cooling, air drying and grain cutting.
According to the invention, the talcum powder with high mesh number and high silicon content is selected and compounded with the mica powder with high diameter-thickness ratio and small particle size, so that the strength, heat resistance and size stability of the nylon PA6 are obviously improved; the filler is activated by a coupling agent, and the binding force with nylon is enhanced by adding a compatilizer, so that the strength and heat resistance of the nylon are greatly enhanced, the problems of insufficient strength of some nylon PA6, deformation caused by overhigh temperature during electroplating and the like are solved, and the surface effect of electroplating is improved; the water and volatile matters in the system are optimized and controlled through the formula, and the surface effect of electroplating is improved.
The electroplated nylon PA6 lamp housing material has the following characteristics: 1. the plating solution has the advantages of high mechanical strength, heat resistance and dimensional stability 2, high plating yield, good stability 3, good plating binding force, no obvious shedding in a hundred-grid test 4, no obvious pockmark on the plating surface and the like.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example one
A high-strength high-heat-resistance dimensionally stable electroplating nylon PA6 material comprises the following materials in parts by weight:
72 parts of PA6 resin, 20 parts of talcum powder, 5 parts of mica powder, 0.2 part of coupling agent, 3 parts of compatilizer, 0.3 part of lubricant A, 0.2 part of lubricant B, 0.2 part of main antioxidant and 0.2 part of auxiliary antioxidant.
The PA6 resin has a relative viscosity of 0.27, and ensures that the material has enough fluidity.
The talcum powder is high in mesh number, 2000 meshes and extremely high in silicon content, and the silicon content is 60%.
The mica powder is muscovite with a high number and a high diameter-thickness ratio, the particle diameter of the muscovite is 28 mu m, and the diameter-thickness ratio is 70.
The coupling agent is a 1:1 compound of a titanate coupling agent and a silane coupling agent. The titanate coupling agent is of a single alkoxy type, the silane coupling agent is N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, the reaction activity is high, the combination of the two greatly improves the binding force of resin and the filler, improves the dispersibility of the filler, and obviously improves the mechanical property and the electroplating property of the material.
The compatilizer is POE grafted maleic anhydride polymer
The lubricant A is pentaerythritol stearate.
Pentaerythritol stearate has good thermal stability and low volatility at high temperatures. Because of no color development groups such as amide and the like, the product does not yellow or change color, the original color of the product can be kept, and the color of the product can be improved. Good flowing and demoulding characteristics, improves the dispersibility of the filler and is beneficial to improving the electroplating effect.
And the lubricant B is silicone oil.
The main antioxidant is a hindered phenol antioxidant, and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine has good compatibility with nylon, high heat resistance and low volatility, reduces the performance loss caused by degradation in the PA6 processing process, and reduces the influence on electroplating property.
The auxiliary antioxidant is a phosphite antioxidant and has a good synergistic effect by compounding with a hindered phenol antioxidant.
The preparation method comprises the following steps:
(1) accurately weighing talcum powder, mica powder and lubricant according to the weight ratio, adding into a high-speed mixer, heating to 100 ℃, weighing the coupling agent in the formula, adding into a stirrer, stirring for 20min, and discharging for later use.
(2) Accurately weighing the PA6 raw material, the compatilizer and other granules in the formula, adding the filler which is activated in the step (1), and stirring for 10 min.
(3) And (3) adding the mixed material obtained in the step (2) into a double-screw extruder hopper, setting the temperature of a screw cylinder to be 230-250 ℃, and enabling the temperature of a machine head to be 250 ℃.
(4) The high-strength high-heat-resistance electroplating nylon PA6 material with stable size is prepared by extrusion, water cooling, air drying and grain cutting
The performance test results are as follows:
| performance of | Unit of | Market like product | Example 1 |
| Tensile strength | MPa | 55 | 70 |
| Elongation at break | % | 5 | 10 |
| Bending strength | MPa | 90 | 100 |
| Flexural modulus | MPa | 4500 | 5000 |
| Impact strength of cantilever beam | KJ/M2 | 4.5 | 6 |
| Heat distortion temperature | ℃ | 80 | 100 |
| Plating performance | With falling-off in the hundred-grid test | No obvious drop-off in the test of hundreds of cases |
Example two
A high-strength high-heat-resistance dimensionally stable electroplating nylon PA6 material comprises the following materials in parts by weight:
68 parts of PA6 resin, 20 parts of talcum powder, 8 parts of mica powder, 0.2 part of coupling agent, 4 parts of compatilizer, 0.5 part of lubricant A, 0.2 part of lubricant B, 0.2 part of main antioxidant and 0.2 part of auxiliary antioxidant.
The PA6 resin is polyamide, the relative viscosity is 0.27, and the sufficient fluidity of the material is ensured.
The talcum powder is high in mesh number, 3000 meshes and extremely high in silicon content, and the silicon content is 62%.
The mica powder is muscovite with a high number and a high diameter-thickness ratio, the particle diameter is 18 mu m, and the diameter-thickness ratio is 80.
The coupling agent is a 1:1 compound of a titanate coupling agent and a silane coupling agent. The titanate coupling agent is of a single alkoxy type, the silane coupling agent is N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, the reaction activity is high, the combination of the two greatly improves the binding force of resin and the filler, improves the dispersibility of the filler, and obviously improves the mechanical property and the electroplating property of the material.
The compatilizer is POE grafted maleic anhydride polymer
The lubricant A is pentaerythritol stearate.
Pentaerythritol stearate has good thermal stability and low volatility at high temperatures. Because of no color development groups such as amide and the like, the product does not yellow or change color, the original color of the product can be kept, and the color of the product can be improved. Good flowing and demoulding characteristics, improves the dispersibility of the filler and is beneficial to improving the electroplating effect.
And the lubricant B is silicone oil.
The main antioxidant is a hindered phenol antioxidant, and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine has good compatibility with nylon, high heat resistance and low volatility, reduces the performance loss caused by degradation in the PA6 processing process, and reduces the influence on electroplating property.
The auxiliary antioxidant is a phosphite antioxidant and has a good synergistic effect by compounding with a hindered phenol antioxidant.
The preparation method comprises the following steps:
(1) accurately weighing talcum powder, mica powder and lubricant according to the weight ratio, adding into a high-speed mixer, heating to 100 ℃, weighing the coupling agent in the formula, adding into a stirrer, stirring for 20min, and discharging for later use.
(2) Accurately weighing the PA6 raw material, the compatilizer and other granules in the formula, adding the filler which is activated in the step (1), and stirring for 10 min.
(3) And (3) adding the mixed material obtained in the step (2) into a double-screw extruder hopper, setting the temperature of a screw cylinder to be 230-250 ℃, and enabling the temperature of a machine head to be 250 ℃.
(4) The high-strength high-heat-resistance electroplating nylon PA6 material with stable size is prepared by extrusion, water cooling, air drying and grain cutting
The performance test results are as follows:
| performance of | Unit of | Market like product | Example 2 |
| Tensile strength | MPa | 55 | 72 |
| Elongation at break | % | 5 | 12 |
| Bending strength | MPa | 90 | 105 |
| Flexural modulus | MPa | 4500 | 5200 |
| Impact strength of cantilever beam | KJ/M2 | 4.5 | 6.5 |
| Heat distortion temperature | ℃ | 80 | 105 |
| Plating performance | With falling-off in the hundred-grid test | No obvious drop-off in the test of hundreds of cases |
EXAMPLE III
A high-strength high-heat-resistance dimensionally stable electroplating nylon PA6 material comprises the following materials in parts by weight:
65 parts of PA6 resin, 20 parts of talcum powder, 10 parts of mica powder, 0.3 part of coupling agent, 5 parts of compatilizer, 0.5 part of lubricant A, 0.5 part of lubricant B, 0.2 part of main antioxidant and 0.2 part of auxiliary antioxidant.
The PA6 resin is polyamide, the relative viscosity is 0.27, and the sufficient fluidity of the material is ensured.
The talcum powder is high in mesh number, 3000 meshes and extremely high in silicon content, and the silicon content is 62%.
The mica powder is muscovite with a high number and a high diameter-thickness ratio, the particle diameter is 18 mu m, and the diameter-thickness ratio is 80.
The coupling agent is a 1:1 compound of a titanate coupling agent and a silane coupling agent. The titanate coupling agent is of a single alkoxy type, the silane coupling agent is N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, the reaction activity is high, the combination of the two greatly improves the binding force of resin and the filler, improves the dispersibility of the filler, and obviously improves the mechanical property and the electroplating property of the material.
The compatilizer is POE grafted maleic anhydride polymer
The lubricant A is pentaerythritol stearate.
Pentaerythritol stearate has good thermal stability and low volatility at high temperatures. Because of no color development groups such as amide and the like, the product does not yellow or change color, the original color of the product can be kept, and the color of the product can be improved. Good flowing and demoulding characteristics, improves the dispersibility of the filler and is beneficial to improving the electroplating effect.
And the lubricant B is silicone oil.
The main antioxidant is a hindered phenol antioxidant, and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine has good compatibility with nylon, high heat resistance and low volatility, reduces the performance loss caused by degradation in the PA6 processing process, and reduces the influence on electroplating property.
The auxiliary antioxidant is a phosphite antioxidant and has a good synergistic effect by compounding with a hindered phenol antioxidant.
The preparation method comprises the following steps:
(1) accurately weighing talcum powder, mica powder and lubricant according to the weight ratio, adding into a high-speed mixer, heating to 100 ℃, weighing the coupling agent in the formula, adding into a stirrer, stirring for 20min, and discharging for later use.
(2) Accurately weighing the PA6 raw material, the compatilizer and other granules in the formula, adding the filler which is activated in the step (1), and stirring for 10 min.
(3) And (3) adding the mixed material obtained in the step (2) into a double-screw extruder hopper, setting the temperature of a screw cylinder to be 230-250 ℃, and enabling the temperature of a machine head to be 250 ℃.
(4) The high-strength high-heat-resistance electroplating nylon PA6 material with stable size is prepared by extrusion, water cooling, air drying and grain cutting
The performance test results are as follows:
| performance of | Unit of | Market like product | EXAMPLE III |
| Tensile strength | MPa | 55 | 75 |
| Elongation at break | ％ | 5 | 15 |
| Bending strength | MPa | 90 | 110 |
| Flexural modulus | MPa | 4500 | 5500 |
| Impact strength of cantilever beam | KJ/M2 | 4.5 | 7 |
| Heat distortion temperature | ℃ | 80 | 110 |
| Plating performance | With falling-off in the hundred-grid test | No obvious drop-off in the test of hundreds of cases |
Compared with similar products in the market, the electroplated nylon PA6 lamp housing material prepared by the invention has the following characteristics: 1. the plating solution has the advantages of high mechanical strength, heat resistance and dimensional stability 2, high plating yield, good stability 3, good plating binding force, no obvious shedding in a hundred-grid test 4, no obvious pockmark on the plating surface and the like.
Claims (5)
1. A high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp housing material is characterized in that: the material comprises the following materials in parts by weight:
60-75 parts of PA6 resin, 20-30 parts of talcum powder, 10-20 parts of mica powder, 0.1-0.5 part of coupling agent, 2-5 parts of compatilizer, 0.5-1 part of lubricant A, 0.5-1 part of lubricant B, 0.2-0.5 part of main antioxidant and 0.2-0.5 part of auxiliary antioxidant;
the viscosity of the PA6 resin is 0.26-0.28;
the talcum powder is 2000-3000 meshes, and the silicon content is 62%;
the particle size of the mica powder is 18 mu m, and the diameter-thickness ratio is 80;
the lubricant A is pentaerythritol stearate, and the lubricant B is silicone oil;
the coupling agent is a compound of a titanate coupling agent and a silane coupling agent in a mass ratio of 1:1, the titanate coupling agent is of a monoalkoxyl type, and the silane coupling agent is N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane.
2. A high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp envelope material as claimed in claim 1, wherein: the compatilizer is POE grafted maleic anhydride polymer.
3. A high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp envelope material as claimed in claim 1, wherein: the main antioxidant is hindered phenol antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine.
4. A high-strength high-heat-resistance dimensionally stable electroplated nylon PA6 lamp envelope material as claimed in claim 1, wherein: the auxiliary antioxidant is phosphite antioxidant.
5. A method for preparing the high-strength high-heat-resistance dimension-stable electroplated nylon PA6 lamp housing material as defined in any one of claims 1-4, comprising the following steps:
(1) accurately weighing talcum powder, mica powder and a lubricant according to the weight parts, adding into a high-speed mixer, heating to 100 ℃, weighing a coupling agent in the formula, adding into a stirrer, stirring for 20min, and discharging for later use;
(2) accurately weighing other component granules in the formula, adding the activated component in the step (1), and stirring for 10 min;
(3) adding the mixed material obtained in the step (2) into a double-screw extruder hopper, setting the temperature of a screw cylinder at 230-250 ℃, and enabling a machine head to be 250 ℃;
(4) the high-strength high-heat-resistance and stable-size electroplated nylon PA lamp shell material is prepared by extrusion, water cooling, air drying and grain cutting.
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| CN202210591734.6A CN114891345B (en) | 2019-06-04 | 2019-06-04 | Electroplated nylon PA6 lamp housing material and preparation method thereof |
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| CN111004497B (en) * | 2019-12-24 | 2022-03-29 | 上海中镭新材料科技有限公司 | Electroplating nylon material and preparation method thereof |
| CN111269561A (en) * | 2020-03-26 | 2020-06-12 | 合肥卡洛塑业科技有限公司 | Polyamide 6 composition and application thereof |
| CN113667297B (en) * | 2021-09-03 | 2024-03-26 | 惠州市良化新材料有限公司 | Nylon composite material with low water absorption rate |
| CN115746545A (en) * | 2022-11-08 | 2023-03-07 | 金发科技股份有限公司 | Polyamide composition and preparation method and application thereof |
| CN116218205B (en) * | 2023-03-03 | 2024-03-29 | 金旸（厦门）新材料科技有限公司 | Electroplated heat-conducting nylon composite material and preparation method thereof |
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| CN114891345B (en) | 2024-02-06 |
| CN114891345A (en) | 2022-08-12 |
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