Halogen-free flame-retardant reinforced polyamide material with corrosion resistance and preparation method thereof

Abstract

The invention discloses a corrosion-resistant halogen-free flame-retardant reinforced polyamide material and a preparation method thereof. The material is prepared from the following components in parts by weight: 70-90 parts of polyamide modified resin, 10-40 parts of glass fibers, 3-10 parts of an impact modifier, 5-10 parts of a flame retardant and a flame-retardant synergist, 0.5-3.0 parts of a corrosion-resistant improver, 0.1-0.3 part of an antioxidant and 0.3-1.0 part of a lubricant. Maleic anhydride or acrylic acid grafted POE, EPDM and PE all belong to elastomer materials, POE, EPDM and PE are short names of ethylene and butylene high polymers, ethylene propylene diene monomer and polyethylene respectively, and the toughness and impact resistance of a matrix material can be improved by mixing the elastomer materials with a polymer modified matrix. In addition, glass fibers, a flame retardant, a flame-retardant synergist, a corrosion-resistant improver, an antioxidant and a lubricant are added into a polymer modified matrix, so that the flame retardance, corrosion resistance, toughness and impact resistance of the material are further improved, and the corrosion resistance of a mold is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a halogen-free flame-retardant reinforced polyamide material with corrosion resistance and a preparation method thereof. Background Art

[0002] Polyamide composites, also known as nylon engineering plastics, are widely used in automobile manufacturing, electronic and electrical, aerospace and other industries. With the continuous development and progress of technology, the service environment faced by engineering plastics will become more and more demanding. Especially in the field of electronic and electrical appliances, higher requirements are put forward for aspects such as strength, flame retardancy efficiency, and withstand voltage. When plastic materials are used in electrical current-carrying components, they must have certain flame retardant properties. Although many polyamide resin varieties have self-extinguishing properties, when used as electrical structural parts, they generally need to be reinforced and modified to improve their heat distortion temperature and mechanical properties. However, the fiber-reinforced polyamide no longer has the self-extinguishing property, and additional flame retardants must be added to meet the flame retardant requirements of electrical current-carrying parts.

[0003] Currently, there are three major methods for flame-retarding polyamide materials: ① nitrogen-based flame-retardant system - melamine hydrogen urate flame-retards polyamide, and the common problem is the deterioration of mechanical properties; ② halogen-based flame-retardant system, which will generate a large amount of toxic hydrogen halide gas and thick smoke in a fire, affecting rescue, and has gradually been phased out by the market; ③ phosphonate system, the polyamide composite manufactured has good mechanical properties and excellent flame retardant properties, and is also currently evaluated as a very environmentally friendly flame retardant method, with good development prospects.

[0004] In view of the above problems, in the current existing technology, blending modification is an effective method to improve the performance defects of nylon. For many years, researchers have been conducting research in this area. There are nylon alloys such as reinforced nylon, PA / PE, PA / ABS, PA / PPO, etc. Some improve the impact strength of nylon at low temperature and in the dry state and reduce the moisture absorption, and some improve the heat resistance of nylon and improve the comprehensive performance. Summary of the Invention

[0005] Object of the Invention: The object of the present invention is to provide a flame-retardant reinforced nylon composition with high corrosion resistance and high impact resistance. This composition has characteristics such as high impact resistance, high heat resistance, high stability, good processability, and good flame retardancy, and can be used as a material for electronic and electrical component products such as low-voltage electrical appliance casings, junction boxes, connectors, switches, etc.

[0006] Technical solution: A halogen-free flame-retardant reinforced polyamide material with corrosion resistance, characterized in that it comprises the following components by weight: 70-90 parts of polyamide modified resin, 10-40 parts of glass fiber, 3-10 parts of impact modifier, 5-10 parts of flame retardant and flame retardant synergist, 0.5-3.0 parts of corrosion resistance improver, 0.1-0.3 parts of antioxidant, and 0.3-1.0 parts of lubricant; Among them, the preparation method of the polyamide modified resin is: N-methylbenzenesulfonamide, nano-montmorillonite, PA6, and ethylene-octene copolymer (EOR) are blended, melted at 200 °C and reacted at 240 °C for 1 h, and vacuum is drawn for 4 h to complete the polymerization reaction to obtain the polyamide modified resin; The flame retardant and flame retardant synergist is {((6-oxo-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)methyl)succinic acid (DDP) reacts with ethylene glycol to obtain ethylene glycol-terminated DDP, which is blended with melamine cyanurate (MCA); The corrosion resistance improver is obtained by adding nano-zinc oxide, EDTA, and boric acid to ethanol for heating and dissolution, then adding nano-magnesium powder and triethylamine for heating and mechanical stirring for 4 h of metal ion exchange reaction, and evaporating ethanol under reduced pressure.

[0007] Preferably, the particle size of the nano-montmorillonite is 20-100 nm, and the addition amount is 4% of PA6.

[0008] Preferably, the impact modifier is one or more of elastomers such as POE, EPDM, and PE grafted with maleic anhydride or acrylic acid.

[0009] Preferably, the blending ratio of ethylene glycol-terminated DDP to melamine cyanurate (MCA) is 1:2.

[0010] Preferably, the particle sizes of nano-zinc oxide and nano-magnesium powder are 50-200 nm.

[0011] Preferably, the antioxidant is an antioxidant such as organic hindered phenols, amines, phosphites, and thioesters, and can be a mixture of one or two, and the mixing ratio is 1:1.

[0012] Preferably, the lubricant is one or more of fatty acids, metal stearates, and fatty acid amides.

[0013] A preparation method of a halogen-free flame-retardant reinforced polyamide material with corrosion resistance, comprising the following steps: S1. Weigh the polyamide modified resin, glass fiber, impact modifier, flame retardant and flame retardant synergist, corrosion resistance improver, antioxidant, and lubricant according to the above weight ratio, put them into a high-speed mixer for mixing, and obtain a mixture of the above components; S2. Add the component mixture obtained by high-speed mixing in step (1) to a twin-screw extruder and granulate at 230-280 °C to obtain a halogen-free flame-retardant reinforced polyamide material with corrosion resistance. Beneficial effects

[0014] (1) In the present invention, through the blending and polymerization reaction of modified polyamide resin, N-methylbenzenesulfonamide, nano-montmorillonite, PA6, and ethylene-octene copolymer (EOR), the montmorillonite is uniformly dispersed in the matrix, generating strong ionic bonds, thereby achieving a toughening effect.

[0015] (2) For the flame retardant and flame retardant synergist in the present invention, react DDP with ethylene glycol to obtain ethylene glycol-terminated DDP, blend it with melamine cyanurate (MCA), and mix them with the polymer-modified matrix to further improve the tensile strength and flame retardant performance.

[0016] (3) By adding the corrosion-resistant improver nano-zinc borate to the polymer-modified matrix in the present invention, the corrosion resistance of the material can be enhanced, and the corrosion of the polyamide material mold can be reduced. Description of the drawings

[0017] Figure 1 It is a graph showing the performance test comparison results between the examples and the comparative examples. Detailed implementation manners

[0018] To make the technical solution of the present invention clearer, the following further describes the present invention in detail with reference to the drawings and specific embodiments. Examples

[0019] A halogen-free flame-retardant reinforced polyamide material with corrosion resistance is obtained by the following preparation method: (1) Preparation of polyamide modified resin: Blend 100 g of N-methylbenzenesulfonamide, 50 g of nano-montmorillonite, 600 g of PA6, and 150 g of ethylene-octene copolymer (EOR), melt at 200 °C and react at 240 °C for 1 h, and evacuate for 4 h to complete the polymerization reaction to obtain polyamide modified resin; (2) Preparation of flame retardant and flame retardant synergist: React 100 g of {(6-oxo-6H-dibenzo[c,e][1,2]oxaphosphorin-6-yl)methyl} succinic acid (DDP) with 100 g of ethylene glycol, wash with water and dry to obtain ethylene glycol-terminated DDP, and blend 100 g of ethylene glycol-terminated DDP with 200 g of melamine cyanurate (MCA); (3) Preparation of corrosion-resistant improver: Add 20 g of nano-zinc oxide, 20 g of EDTA, and 30 g of boric acid to ethanol, heat and dissolve, then add 35 g of nano-magnesium powder and 5 g of triethylamine, keep warm at 75 °C and stir and react for 4 h, and evaporate ethanol under a vacuum degree of -0.09 MPa to obtain it; (4) Put 350 g of polyamide modified resin, 50 g of glass fiber, 15 g of acrylic acid grafted POE, 25 g of flame retardant and flame retardant synergist in step (2), 2.5 g of corrosion resistance improver in step (3), 0.5 g of 1:1 mixture of organic hindered phenol and phosphite antioxidants, and 1.5 g of fatty acid into a high-speed mixer and mix for 20 min to obtain a premix; (5) Add the premix in step (4) to a twin-screw extruder and extrude and pelletize at 230 °C to obtain a halogen-free flame-retardant reinforced polyamide material with corrosion resistance. Example

[0020] A halogen-free flame-retardant reinforced polyamide material with corrosion resistance is obtained by the following preparation method: (1) Preparation of polyamide modified resin: Blend 100 g of N-methylbenzenesulfonamide, 50 g of nano-montmorillonite, 600 g of PA6, and 150 g of ethylene-octene copolymer (EOR), melt at 200 °C and react at 240 °C for 1 h, and evacuate for 4 h to complete the polymerization reaction to obtain polyamide modified resin; (2) Preparation of flame retardant and flame retardant synergist: React 100 g of { (6-oxo-6H-dibenzo[c,e][1,2]oxaphosphorin-6-yl)methyl} succinic acid (DDP) with 100 g of ethylene glycol, wash with water and dry to obtain ethylene glycol-terminated DDP, and blend 100 g of ethylene glycol-terminated DDP with 200 g of melamine cyanurate (MCA); (3) Preparation of corrosion resistance improver: Add 20 g of nano-zinc oxide, 20 g of EDTA, and 30 g of boric acid to ethanol, heat and dissolve, then add 35 g of nano-magnesium powder and 5 g of triethylamine, keep the temperature at 75 °C and stir and react for 4 h, and evaporate ethanol under reduced pressure at a vacuum degree of -0.09 MPa to obtain it; (4) Put 450 g of polyamide modified resin, 200 g of glass fiber, 50 g of maleic anhydride grafted EPDM, 50 g of flame retardant and flame retardant synergist in step (2), 15 g of corrosion resistance improver in step (3), 1.5 g of 1:1 mixture of organic hindered phenol and amine antioxidants, and 5 g of fatty amide in step (1) into a high-speed mixer and mix for 20 min to obtain a premix; (5) Add the premix in step (4) to a twin-screw extruder and extrude and pelletize at 280 °C to obtain a halogen-free flame-retardant reinforced polyamide material with corrosion resistance. Example

[0021] A halogen-free flame-retardant reinforced polyamide material with corrosion resistance is obtained by the following preparation method: (1)Preparation of polyamide modified resin: 100 g of N-methylbenzenesulfonamide, 50 g of nano-montmorillonite, 600 g of PA6, and 150 g of ethylene-octene copolymer (EOR) were blended. After melting at 200 °C, the reaction was carried out at 240 °C for 1 h, and then vacuum was applied for 4 h to complete the polymerization reaction, obtaining the polyamide modified resin; (2)Preparation of flame retardant and flame retardant synergist: 100 g of { (6-oxo-6H-dibenzo[c,e][1,2]oxaphosphorin-6-yl)methyl} succinic acid (DDP) was reacted with 100 g of ethylene glycol, washed with water and dried to obtain ethylene glycol-terminated DDP. 100 g of ethylene glycol-terminated DDP was blended with 200 g of melamine cyanurate (MCA); (3)Preparation of corrosion resistance improver: 20 g of nano-zinc oxide, 20 g of EDTA, and 30 g of boric acid were added to ethanol and heated to dissolve. Then 35 g of nano-magnesium powder and 5 g of triethylamine were added, and the mixture was stirred and reacted at 75 °C for 4 h. Ethanol was removed by vacuum distillation under a vacuum of -0.09 MPa to obtain the product; (4)400 g of the polyamide modified resin in step (1), 125 g of glass fiber, 32.5 g of acrylic acid grafted PE, 37.5 g of the flame retardant and flame retardant synergist in step (2), 8.7 g of the corrosion resistance improver in step (3), 1 g of a 1:1 mixture of organic hindered phenols and thioesters antioxidants, and 3.2 g of fatty acid calcium salt were put into a high-speed mixer and mixed for 20 min to obtain a premix; (5)The premix in step (4) was added to a twin-screw extruder and extruded and pelletized at 255 °C to obtain a halogen-free flame retardant reinforced polyamide material with corrosion resistance.

[0022] A halogen-free flame retardant reinforced polyamide material with corrosion resistance is obtained by the following preparation method: (1)Preparation of flame retardant and flame retardant synergist: 100 g of { (6-oxo-6H-dibenzo[c,e][1,2]oxaphosphorin-6-yl)methyl} succinic acid (DDP) was reacted with 100 g of ethylene glycol, washed with water and dried to obtain ethylene glycol-terminated DDP. 100 g of ethylene glycol-terminated DDP was blended with 200 g of melamine cyanurate (MCA); (2)Preparation of corrosion resistance improver: 20 g of nano-zinc oxide, 20 g of EDTA, and 30 g of boric acid were added to ethanol and heated to dissolve. Then 35 g of nano-magnesium powder and 5 g of triethylamine were added, and the mixture was stirred and reacted at 75 °C for 4 h. Ethanol was removed by vacuum distillation under a vacuum of -0.09 MPa to obtain the product; (3) Put 400 g of polyamide resin (PA6), 125 g of glass fiber, 32.5 g of acrylic-grafted POE, 37.5 g of the flame retardant and flame retardant synergist in step (1), 8.7 g of the corrosion-resistant improver in step (2), 1 g of a 1:1 mixture of organic hindered phenol and phosphite antioxidants, and 3.2 g of fatty acid into a high-speed mixer and mix for 20 min to obtain a premix; (4) Add the premix in step (3) to a twin-screw extruder and extrude and pelletize at 255 °C to obtain a polyamide material.

[0023] A halogen-free flame-retardant reinforced polyamide material with corrosion resistance is obtained by the following preparation method: (1) Preparation of polyamide modified resin: Blend 100 g of N-methylbenzenesulfonamide, 50 g of nano-montmorillonite, 600 g of PA6, and 150 g of ethylene-octene copolymer (EOR), melt at 200 °C and react at 240 °C for 1 h, and evacuate for 4 h to complete the polymerization reaction to obtain a polyamide modified resin; (2) Preparation of corrosion-resistant improver: Add 20 g of nano-zinc oxide, 20 g of EDTA, and 30 g of boric acid to ethanol and heat to dissolve, then add 35 g of nano-magnesium powder and 5 g of triethylamine, keep warm at 75 °C and stir and react for 4 h, and evaporate ethanol under reduced pressure with a vacuum degree of -0.09 MPa to obtain it; (3) Put 400 g of the polyamide modified resin in step (1), 125 g of glass fiber, 32.5 g of acrylic-grafted POE, 37.5 g of MAC, 8.7 g of the corrosion-resistant improver in step (2), 1 g of a 1:1 mixture of organic hindered phenol and phosphite antioxidants, and 3.2 g of fatty acid into a high-speed mixer and mix for 20 min to obtain a premix; (4) Add the premix in step (3) to a twin-screw extruder and extrude and pelletize at 255 °C to obtain a polyamide material.

[0024] A halogen-free flame-retardant reinforced polyamide material is obtained by the following preparation method: (1) Preparation of polyamide modified resin: Blend 100 g of N-methylbenzenesulfonamide, 50 g of nano-montmorillonite, 600 g of PA6, and 150 g of ethylene-octene copolymer (EOR), melt at 200 °C and react at 240 °C for 1 h, and evacuate for 4 h to complete the polymerization reaction to obtain a polyamide modified resin; (2) Preparation of flame retardant and flame retardant synergist: React 100 g of {6-oxo-6H-dibenzo[c,e][1,2]oxaphosphorin-6-yl}methyl succinic acid (DDP) with 100 g of ethylene glycol, wash with water and dry to obtain ethylene glycol-terminated DDP, and blend 100 g of ethylene glycol-terminated DDP with 200 g of melamine cyanurate (MCA); (3) Put 400 g of polyamide modified resin, 125 g of glass fiber, 32.5 g of acrylic grafted POE, 37.5 g of flame retardant and flame retardant synergist in step (2), 1 g of a 1:1 mixture of organic hindered phenol and phosphite antioxidants, and 3.2 g of fatty acid into a high-speed mixer and mix for 20 min to obtain a premix; (4) Add the premix in step (3) to a twin-screw extruder and extrude and pelletize at 255 °C to obtain a polyamide material.

[0025] The compositions and preparation processes of the corrosion-resistant halogen-free flame-retardant reinforced polyamide materials described in Examples 1, 2, and 3 correspond to those of Comparative Examples 1, 2, and 3 respectively, and their composition formulas and preparation methods are basically the same. The main differences are as follows: (1) The polyamide modified resin in Comparative Example 1 is PA6; (2) The flame retardant and flame retardant synergist in Comparative Example 2 is MAC; (3) The corrosion-resistant improver is not added in Comparative Example 3.

[0026] (1) Tensile strength: Tested according to the ISO 527 standard method; (2) Flexural strength: Tested according to the ISO 178 standard method; (3) Impact strength: Tested according to the ISO 179 / 1eU standard method; (4) Flame retardant performance: The flame retardant grade is tested according to the UL-94 standard; (5) High temperature and high humidity treatment: The condition is to place it at 90 °C and 95% humidity for 168 h, and observe whether there is any precipitate on the surface; (6) Continuous processability: Under the injection molding temperature condition of 230 °C to 280 °C, after the composite material is continuously processed for 14 days, observe whether there is mold scale or corrosion on the mold surface.

[0027] The performance test comparison results of the above-mentioned examples and comparative examples are as Figure 1 shown. The results show that the corrosion-resistant halogen-free flame-retardant reinforced polyamide material provided by the present invention has excellent tensile strength, toughness, corrosion resistance, and flame retardant performance. From Examples 1 to 3 and Comparative Examples 1 to 3, it can be seen that: (1) Polyamide modified resin, glass fiber, impact modifier, flame retardant and flame retardant synergist, corrosion-resistant improver, antioxidant, and lubricant, they improve the mechanical properties and flame retardant performance of the composite wire and its printed parts through synergistic interaction, especially the toughness and impact resistance are greatly enhanced, and the precipitation of the flame retardant is greatly reduced; (2) The addition of the corrosion-resistant improver component can slow down the corrosion of the mold, which is beneficial to obtaining improved continuous processability.

[0028] The above-described embodiments merely represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the patent for the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be subject to the appended claims.

Claims

1. A corrosion-resistant halogen-free flame-retardant reinforced polyamide material, characterized in that: The invention comprises the following components by weight: 70-90 parts of polyamide modified resin, 10-40 parts of glass fiber, 3-10 parts of impact modifier, 5-10 parts of flame retardant and flame retardant synergist, 0.5-3.0 parts of corrosion resistance improver, 0.1-0.3 parts of antioxidant, and 0.3-1.0 parts of lubricant; The preparation method of the polyamide modified resin is as follows: N-methylbenzenesulfonamide, nano-montmorillonite, PA6, and ethylene-octene copolymer (EOR) are blended, melted at 200°C, reacted at 240°C for 1 hour, and vacuumed for 4 hours to complete the polymerization reaction, thereby obtaining the polyamide modified resin; The flame retardant and flame retardant synergist are {(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphorin-6-yl)methyl}succinic acid (DDP) and ethylene glycol to obtain ethylene glycol-terminated DDP, which is mixed with melamine cyanuric acid (MCA); The corrosion resistance improver is nano zinc oxide, EDTA, and boric acid, which are added to ethanol and heated to dissolve, and then nano magnesium powder and triethylamine are added and heated with mechanical stirring to carry out metal ion exchange reaction for 4 hours, and the ethanol is evaporated under reduced pressure to obtain the corrosion resistance improver.

2. The corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to claim 1, characterized in that: The particle size of nano-montmorillonite is 20~100nm, and the added amount is 4% of PA6.

3. The corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to claim 1, characterized in that: The impact modifier is one or more of POE, EPDM, and PE elastomers grafted with maleic anhydride or acrylic acid.

4. The corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to claim 1, characterized in that: The blending ratio of ethylene glycol-terminated DDP and melamine cyanuric acid (MCA) is 1:

2.

5. The corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to claim 1, characterized in that: The particle size of nano zinc oxide and nano magnesium powder is 50~200nm.

6. The corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to claim 1, characterized in that: The antioxidant is an organic hindered phenol, amine, phosphite, or thioester antioxidant, and may be a mixture of one or two of them, with a mixing ratio of 1:

1.

7. The corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to claim 1, characterized in that: The lubricant is one or more of fatty acids, stearates, and fatty amides.

8. A method for preparing the corrosion-resistant halogen-free flame-retardant reinforced polyamide material according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. Weigh the polyamide modified resin, glass fiber, impact modifier, flame retardant and flame retardant synergist, corrosion resistance improver, antioxidant, and lubricant according to the above weight ratio, put them into a high-speed mixer and mix them to obtain a mixture of the above components; S2, adding the component mixture mixed at high speed in step S1 into a twin screw, and extruding and granulating at 230-280° C. to obtain a corrosion-resistant halogen-free flame-retardant reinforced polyamide material.

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