CN112662173A - PA46 reinforced flame-retardant material with high adhesion and preparation method thereof - Google Patents
PA46 reinforced flame-retardant material with high adhesion and preparation method thereof Download PDFInfo
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- CN112662173A CN112662173A CN202011522777.6A CN202011522777A CN112662173A CN 112662173 A CN112662173 A CN 112662173A CN 202011522777 A CN202011522777 A CN 202011522777A CN 112662173 A CN112662173 A CN 112662173A
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Abstract
The invention relates to the technical field of high polymer materials, and discloses a PA46 reinforced flame retardant material with high adhesion and a preparation method thereof, wherein the material comprises the following raw material components in percentage by mass of 100 percent: 18% -78.8% of PA 46; 10-20% of flame retardant; 10% -55% of a reinforcing component; 0.2 to 1 percent of polarity regulator; 0.5 to 5 percent of metal tackifier; 0.5 to 1 percent of processing aid; the polarity regulator is long carbon chain dibasic acid. Aiming at the nylon material containing the reinforcing component and the flame retardant, the metal tackifier is added into the PA46 matrix and is acted with the polarity regulator, so that the obtained melt of the PA46 material has high adhesive property with metal, and the PA46 material is applied to parts needing to be welded and fixed by plastics and metal.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PA46 reinforced flame retardant material with high adhesion and a preparation method thereof.
Background
Polyamide (PA for short) is one of five major engineering plastics, and is widely used in various industrial fields due to its excellent comprehensive properties, and the types of base materials mainly include PA6, PA66, PA56, PA46, PA6T, PPA, long carbon chain nylon and the like, wherein the maximum dosage of PA6 and PA66 is used. At present, PA materials used for functional parts are basically modified physically or chemically, and are endowed with new functions, such as good flame retardance, heat resistance, excellent mechanical properties and the like. The PA composite materials can be used by injection molding alone, and can also be used with metal inserts in an integrated injection molding mode, so that the whole assembly and use are realized, and particularly, the combination of plastics and metals is very important on products such as precision electronics, low-voltage electrical appliances and the like.
The conventional nylon resin is basically a high molecular weight material, the surface polarity of the nylon resin is not high, and in addition, the nylon material is a semi-crystalline material, partial crystallization and shrinkage can be caused in the cooling process of a melt, so that the bonding strength of metal and plastic is reduced. In order to meet the use requirements, the nylon material is often required to be subjected to flame retardance and enhanced modification, and meanwhile, the material is subjected to internal and external lubrication to solve the processing performance, so that the surface polarity of the nylon material is further reduced, and plastic is difficult to weld to a metal piece or is not firm in welding.
At present, the study on the bonding performance of plastics and metals by scholars at home and abroad is less, and the study mainly focuses on nylon hot melt adhesive, adhesive for bonding plastics and metals and a welding method of plastics and metals. For example, CN109986191A discloses a surface treatment method for metal/polymer connection, in which a metal surface is polished and cleaned, and then soaked in a corrosive liquid to form a reaction layer on the surface, where the reaction layer includes a metal substrate and compound particles dispersed on the metal substrate, and in the process of connecting with a polymer, the molten polymer with improved fluidity at high temperature is fully contacted and wetted with the metal substrate and the compound particles to form a tight micro-occlusion and bonding, so that the metal surface is effectively connected with the polymer.
CN 104804659A discloses a hot melt adhesive film for bonding metal and non-polar material and a preparation method thereof, wherein a specific dimer acid type copolyamide is prepared by corresponding proportion, and the good adhesiveness of the specific dimer acid type copolyamide hot melt adhesive to the metal material and the good adhesiveness of a polyolefin elastomer to the non-polar material are combined, so that the prepared hot melt adhesive and the adhesive film thereof have good compatibility by adding a compatilizer with proper components in a specific proportion, and the bonding strength to the metal and the non-polar material is greatly improved.
However, the modified engineering plastic is required to have better bonding strength with metal after being melted by heat, because the engineering plastic has higher molecular weight and weak polarity, and the processing temperature of the PA46 material is high, a plurality of auxiliaries can not be used, particularly after the glass fiber and the flame retardant are added, the bonding strength between the plastic and the metal is further reduced, and the difficulty in realizing high bonding performance is higher.
Disclosure of Invention
The invention aims to solve the problems that the surface of PA46 added with glass fiber and a flame retardant is weak in polarity and poor in adhesion with metal, and provides a PA46 reinforced flame retardant material with high adhesion, wherein a nylon resin is modified, long carbon chain dibasic acid and a hot melt adhesive are used for improving the polarity of a PA46 material, improving the fluidity and enhancing the adhesion performance of the material and the metal.
In order to achieve the purpose, the invention adopts the technical scheme that:
a PA46 reinforced flame retardant material with high adhesion comprises the following raw material components by mass percent of 100 percent:
the polarity regulator is long carbon chain dibasic acid.
Because the surface polarity of the PA46 matrix material is weak, and in addition, the flame retardant and the mechanical property are enhanced, the addition of the flame retardant and the enhancing component further reduces the polarity of the matrix surface, and the bonding property with metal is very weak. In order to solve the problem, the metal tackifier is added into the formula in the formula, so that the viscosity of the matrix is enhanced, and the matrix, the flame retardant and the enhancing component are mixed together; on the other hand, the polarity of the PA46 matrix can be adjusted by adopting a polarity regulator, and the adopted polarity regulator is long carbon chain dibasic acid, so that the fluidity of the matrix can be enhanced, and the processing of the material is facilitated; the components can mutually generate synergistic action, so that the material has the characteristics of high flame retardance and high modulus, and the bonding property of the melt and the metal is high.
Preferably, the feed comprises the following raw material components in percentage by mass of 100 percent:
the PA46 comprises a PA46 material which can be injection molded, such as a new material, a fake-brand material, a reclaimed material and the like.
The flame retardant comprises one or a mixture of brominated polystyrene, polybrominated styrene, hypophosphite OP1312 and hypophosphite OP 1314.
Preferably, the flame retardant further comprises metal oxide, such as any one of inorganic flame retardants such as antimony trioxide, sodium antimonate and zinc borate, and the flame retardant effect is better when the flame retardant is used together with a halogen-containing flame retardant or a phosphorus flame retardant.
The reinforcing component is alkali-free chopped glass fiber. Preferably, the reinforcing component is selected from one or more of Mount Taishan glass fiber 435N, boulder glass fiber 560A, Chongqing International composite 301HP chopped fiber.
The polarity regulator comprises one or more of sebacic acid, dodecanedioic acid and tridecanedioic acid.
Preferably, the polarity regulator comprises one or two of Wuhan hyperbranched HyPer C181 resin, HyPer C182 resin and HyPer C100 resin, and the polarity regulator has good bonding performance with metal, can improve the flow performance of a PA46 matrix, increase the content of polar functional groups of PA46 and improve the bonding performance with metal.
The metal tackifier comprises one or a mixture of two of polyamide hot melt adhesive, polyester hot melt adhesive and polyurethane hot melt adhesive. The tackifier has good compatibility with polymer, relatively moderate molecular weight, is easy to enrich on the outer surface layer of a plastic part, and has high bonding performance with metal in a molten state due to containing more polar groups.
Preferably, the metal tackifier is selected from any one or more of Anqing Anhuitai New Material, Inc. HY-208E, HY-545, Guangdong Shunhua New Material, Inc. 3150M, 3170M, 8685 BM.
The processing aid comprises one or more of antioxidant N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (antioxidant 1098), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010).
The invention also provides a preparation method of the PA46 reinforced flame-retardant material with high adhesion, which comprises the following steps: uniformly mixing PA46, a flame retardant, a polarity regulator and a processing aid, adding the mixture from the main feed of a double-screw extruder, adding a reinforcing component and a metal tackifier from side materials respectively, and performing melt blending, extrusion and granulation on the materials to obtain the PA46 reinforced flame retardant material with high adhesion.
According to the preparation method, aiming at the difference of heat resistance of different components, the components with poor heat resistance are added at the final stage of the extruder, and through the combination of the specific low-shear and high-dispersion screws, the decomposition of the materials is reduced, and the aim of better dispersion is fulfilled.
The length-diameter ratio of the double-screw extruder is 48-52: 1; the side charges of the reinforcing component and the metal tackifier are separated by at least 3 working stages.
Preferably, the reinforcing component is added through a first side material, the first side material is positioned at the 5 th working section, the metal tackifier is added through a second side material, the second side material is positioned at the 10 th working section, and the vacuum port is positioned at the 9 th working section.
The temperature of the melt blending is 210-295 ℃, and the die head temperature of the double-screw extruder is 270-290 ℃. Preferably, the twin-screw extruder comprises 12 working sections, the temperature of each working section being: 290 ℃ at 295 ℃, 285 ℃ at 290 ℃, 275 ℃ at 280 ℃, 265 ℃ at 270 ℃, 255 ℃ at 260 ℃, 240 ℃ at 245 ℃, 215 ℃ at 220 ℃ and 205 ℃ at 210 ℃; the rotating speed of the auxiliary agent is 300-600 rpm/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the nylon material containing the reinforcing component and the flame retardant, the metal tackifier is added into the PA46 matrix and is acted with the polarity regulator, so that the obtained melt of the PA46 material has high adhesive property with metal, and the PA46 material is applied to parts needing to be welded and fixed by plastics and metal.
(2) According to the preparation method of the nylon 46, aiming at the difference of heat resistance of different components, the components with poor heat resistance are added at the final stage of an extruder, and through the combination of the specific low-shear and high-dispersion screws, the decomposition of the materials is reduced, and the aim of better dispersion is fulfilled.
(3) In the prior art, the research on the fusion bonding performance of high-glass fiber and flame-retardant modified high-temperature plastic and metal is less, the research mainly focuses on nylon hot melt adhesive, adhesive for bonding plastic and metal and a plastic and metal welding method, and the invention improves the nylon resin base material and has new innovation in the method and angle.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
Example 1
Preparing raw materials according to the following parts by weight:
the length-diameter ratio of the double-screw extruder is 48-52: 1; the vacuum forming device comprises two side materials, wherein the first side material is positioned at the section 5, the second side material is positioned at the section 10, and the vacuum port is positioned at the section 9; the temperature of each working section in the double-screw extruder is 295 ℃, 290 ℃, 280 ℃, 270 ℃, 260 ℃, 245 ℃, 220 ℃, 210 ℃, 285 ℃ and 300-600 rpm/min of the main machine.
The PA46, the flame retardant and other additives are uniformly mixed, the mixture is added into a double-screw extruder from a main feed, the glass fiber is added into the double-screw extruder from a first side feed, then the metal tackifier is added into a second side feed, the mixture is combined and mixed by low-shearing and high-dispersity screws, and the PA46 reinforced flame retardant material with high adhesion is prepared after extrusion, strip drawing, cooling, grain cutting and drying.
Example 2
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Example 3
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Example 4
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Example 5
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Example 6
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Comparative example 1
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Comparative example 2
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Comparative example 3
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Comparative example 4
Preparing raw materials according to the following parts by weight:
the preparation process is as in example 1, and the PA46 reinforced flame retardant material with high adhesion is obtained.
Performance testing
The PA46 reinforced flame retardant material with high adhesion prepared in the above examples 1 to 6 and comparative examples 1 to 4 was subjected to fusion riveting by single AC resistance welding with an iron sheet, and the adhesion strength after fusion welding was tested by a pointer type push-pull dynamometer. The flame retardant property is carried out according to GB/T2408, the thickness of a sample strip is 1.6mm, the test condition of the Melt Index (MI) is 300 ℃, and the load is 2.16 Kg. The test results are shown in table 1.
TABLE 1 Properties of PA46 materials prepared in the examples and comparative examples
| Serial number | Flame retardant rating | MI(g/10min) | Fusion welding bonding strength (MPa) |
| Comparative example 1 | V-0 | 14 | 1 |
| Comparative example 2 | V-0 | 25 | 1.4 |
| Comparative example 3 | V-0 | 20 | 1.5 |
| Comparative example 4 | V-0 | 16 | 0.9 |
| Example 1 | V-0 | 17 | 1.8 |
| Example 2 | V-0 | 30 | 2.5 |
| Example 3 | V-0 | 32 | 2.4 |
| Example 4 | V-0 | 30 | 2.3 |
| Example 5 | V-0 | 31 | 2.5 |
| Example 6 | V-0 | 35 | 2 |
As can be seen from Table 1, the PA46 reinforced flame-retardant material with high bonding performance with metal and the preparation method have good flame-retardant performance, flow performance and bonding performance with metal, and the fluidity (MI) of the material is greatly increased and the fusion welding bonding strength is improved by adding the polarity regulator; when the metal tackifier is added, the fusion welding bonding strength of the material and the metal is further greatly improved, and if the polarity regulator and the metal tackifier are not added, the fusion welding bonding strength of the material and the metal is very low, and the material and the metal are easy to peel off under external force. Example 1 and comparative example 3 find that the residence time of high-temperature shearing (added through the second side feeding port) is reduced for the auxiliary agent which is not resistant to high temperature, so that the improvement of the fusion welding bonding strength of the material and the metal is facilitated. In example 1, the effect of melt index and weld bond strength was not optimal because no polarity modifier was added.
Claims (10)
1. The PA46 reinforced flame-retardant material with high adhesion is characterized by comprising the following raw material components in percentage by mass of 100 percent:
the polarity regulator is long carbon chain dibasic acid.
2. The PA46 reinforced flame retardant material with high adhesion according to claim 1, wherein the PA46 reinforced flame retardant material comprises the following raw material components by mass percent of 100 percent:
3. the reinforced flame retardant PA46 material with high adhesion according to claim 1, wherein the flame retardant comprises a mixture of one or more of brominated polystyrene, polybrominated styrene, hypophosphite OP1312 and phosphinate OP 1314.
4. The PA46 reinforced flame retardant material with high adhesion according to claim 1, wherein the reinforcing component is alkali-free chopped glass fiber.
5. The PA46 reinforced flame retardant material with high adhesion according to claim 1, wherein the polarity modifier comprises one or more of sebacic acid, dodecanedioic acid, tridecanedioic acid.
6. The PA46 reinforced flame retardant material with high adhesion according to claim 1 or 5, wherein the polarity modifier comprises one or two of Wuhan hyperbranched HyPer C181 resin, HyPer C182 resin and HyPer C100 resin.
7. The PA46 reinforced flame retardant material with high adhesiveness according to claim 1, wherein the metal tackifier comprises one or a mixture of two of polyamide hot melt adhesive, polyester hot melt adhesive and polyurethane hot melt adhesive.
8. The preparation method of the PA46 reinforced flame retardant material with high adhesion according to any one of claims 1-7, characterized by comprising the following steps: uniformly mixing PA46, a flame retardant, a polarity regulator and a processing aid, adding the mixture from the main feed of a double-screw extruder, adding a reinforcing component and a metal tackifier from side materials respectively, and performing melt blending, extrusion and granulation on the materials to obtain the PA46 reinforced flame retardant material with high adhesion.
9. The method for preparing PA46 reinforced flame-retardant material with high adhesion according to claim 8, wherein the length-diameter ratio of the twin-screw extruder is 48-52: 1; the side charges of glass fibers and metal tackifier are separated by at least 3 working stages.
10. The method for preparing PA46 reinforced flame retardant material with high adhesion as claimed in claim 8, wherein the temperature of melt blending is 210-295 ℃ and the die temperature of the twin-screw extruder is 270-290 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381172A (en) * | 2021-12-31 | 2022-04-22 | 山东东岳未来氢能材料股份有限公司 | Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof |
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| CN104804659A (en) * | 2015-05-11 | 2015-07-29 | 上海天洋热熔粘接材料股份有限公司 | Hot melt rubber film for adhering metal and non-polar material and preparation method of hot melt rubber film |
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| US6670442B1 (en) * | 1998-12-21 | 2003-12-30 | Henkel Kommanditgesellschaft Auf Aktien | Hot melt adhesives based on polyamides |
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| CN114381172A (en) * | 2021-12-31 | 2022-04-22 | 山东东岳未来氢能材料股份有限公司 | Stripping-resistant ethylene-tetrafluoroethylene copolymer powder coating and preparation method thereof |
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