Modified alloy material, preparation method thereof and electric appliance shell

Abstract

The invention provides a modified alloy material, a preparation method thereof and an electric appliance shell, and belongs to the technical field of high polymer material modification. According to the invention, the polyphenyl ether and the polyamide 6 are respectively added and blended by the horizontal screw extruder and the vertical screw extruder of the vertical double-screw extruder, so that the mixing uniformity of the polyphenyl ether and the polyamide 6 is improved; meanwhile, in the process of modifying the alloy material, the polyphenyl ether, the polyamide 66, the viscosity-reducing compatible master batch, the flame retardant and the like are blended step by step, and then the glass fibers are added through the rear half section of a specific vertical double-screw extruder, so that the situation that the glass fibers are sheared is reduced, and the mechanical property, the shrinkage rate and the like of the modified alloy material are greatly improved; and the viscosity-reducing compatible master batch also improves the compatibility among the polyphenyl ether, the polyamide 66 and the glass fiber, reduces the floating fiber phenomenon of the glass fiber and greatly improves the flatness of a molded part.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material modification, and particularly relates to a modified alloy material, a preparation method thereof, and an electrical appliance housing. Background Art

[0002] Polyphenylene oxide (PPO) is one of the high-temperature resistant plastics. Its molecular chain contains a large number of benzene rings, and there are no strong polar groups in the molecular structure, belonging to a non-crystalline material. Therefore, it has good water resistance, and the performance decay is small after long-term immersion in water. It has strong molecular rigidity, high mechanical strength, good dimensional stability, good heat resistance, and is not easily decomposed during processing. However, the disadvantages are poor melt fluidity, high melt viscosity, poor solvent resistance, difficult processing and forming, and the impact resistance and heat resistance will decrease over time. Therefore, most of the polyphenylene oxide in the market is modified polyphenylene oxide, and the modification method usually uses blending modification to improve the processing fluidity of polyphenylene oxide.

[0003] Polyamide 66 (PA66), as a high-performance engineering plastic with high crystallinity, wear resistance, and solvent resistance, can resist corrosion by acids, alkalis, most inorganic salt aqueous solutions, halogenated alkanes, hydrocarbons, esters, ketones, etc., and has excellent wear resistance, self-lubrication, and relatively high mechanical strength. However, it has a large water absorption, so its dimensional stability is poor. Therefore, blending and modifying polyamide 66 with polyphenylene oxide can make the properties complementary to obtain a high-strength, acid and alkali resistant, and dimensionally stable alloy material.

[0004] CN111793355B discloses a wear-resistant PPO / PA66 alloy material for an automobile wiper shaft sleeve and a preparation method thereof. The wear-resistant PPO / PA66 alloy material for the automobile wiper shaft sleeve is composed of the following components by weight percentage: 30-40% of PPO resin, 30-47% of PA66 resin, 15-20% of wear-resistant agent A, 1-3% of wear-resistant agent B, 5-10% of compatibilizer, 0.2-0.5% of antioxidant, and 1.5-1.8% of lubricant. After weighing the respective components and adding them to a high-speed mixer for mixing, they are melt-extruded and pelletized by a twin-screw extruder.

[0005] CN111961342B discloses a method for preparing a flame-retardant and high-tough nylon 66 / polyphenylene oxide (PA66 / PPO) plastic alloy. The method is as follows: maleic anhydride (MAH) and high-impact polystyrene (HIPS) are melt-mixed together and extruded into pellets; then the pellets are placed in a gamma-ray radiation field for irradiation, and the absorbed dose is 1 kGy - 100 kGy. The irradiated pellets are mixed with PA66, PPO, a flame retardant, and other additives; finally, the above mixture is extruded and pelletized on an extruder to obtain a flame-retardant and high-tough PA66 / PPO plastic alloy.

[0006] CN110938298A discloses a PA66 / PPO composite material, which is made of the following raw material components in parts by weight: PA66: 30 - 70 parts; PPO: 30 - 70 parts; compatibilizer: 8 - 20 parts; antioxidant: 0.2 - 1 part; lubricant: 0.2 - 1 part. For the PA66 / PPO product prepared by this technical solution, the tensile strength, flexural strength, impact strength, etc. are basically equivalent to those of the products in the prior art. However, the product prepared by the present invention has good processing fluidity, can prepare thin-walled and large-sized products, and has a wider application range.

[0007] However, polyphenylene oxide and polyamide 66 are thermally incompatible. The product obtained by simple blending has a high viscosity, obvious phase separation, poor brittleness and other disadvantages, and it is difficult to achieve complementary advantages. To solve the above problems, glass fiber is usually added to improve the mechanical properties of the material, and a halogen-free flame retardant is added to improve the heat resistance and flame retardant properties of the material.

[0008] CN101875776B discloses a high-strength PPO / PA66 alloy material and its preparation method. The high-strength PPO / PA66 alloy material is composed of the following components in weight percentage: polyphenylene oxide resin 20 - 40%; nylon 66 resin 20 - 40%; compatibilizer 5 - 10%; toughening agent 5 - 10%; glass fiber 5 - 15%; glass microbead 5 - 15%; mica powder 5 - 15%; antioxidant 0.2 - 0.4%; other auxiliaries 0.5 - 1%. By using glass fiber to compound with glass microbeads and mica powder to reinforce the PPO / PA66 alloy, the material prepared by the present invention has excellent comprehensive properties, not only high strength, good heat resistance, easy to spray, but also excellent dimensional stability and low warpage rate.

[0009] CN102732020A discloses a flame-retardant glass fiber-reinforced PA66 / PPO alloy composition and its preparation method. The composition includes the following components in weight percentage: PA66 20 - 41%, PPO 20 - 41%, compatibilizer 0 - 10%, compound flame retardant masterbatch 0 - 15%, glass fiber 20 - 40%, antioxidant 0.1 - 1%, lubricating dispersant 0.1 - 1%. The preparation method of the composition includes the following steps: weighing each component according to the weight ratio, putting them into a high-speed mixer and mixing for 2 - 5 minutes, discharging, and then extruding and pelletizing with a twin-screw extruder. The processing temperature is 245 - 270 °C, and the screw rotation speed is 30 - 40 HZ. Compared with the prior art, the composition of the present invention has the advantages of high CTI value, low flame retardant exudation, halogen-free environmental protection, and balanced comprehensive performance.

[0010] In summary, by adding a flame retardant or glass fiber to modify polyphenylene ether and polyamide 66, the mechanical properties of the alloy material can be improved. However, after adding the flame retardant and glass fiber, the viscosity of the alloy material increases, resulting in worse processing fluidity, serious surface fiber floating, and difficult molding. These are still technical problems that need to be urgently solved. Summary of the Invention

[0011] In view of the above problems, the present invention provides a modified alloy material, its preparation method, and an electrical appliance housing. By blending polyphenylene ether, polyamide 66, and other additives, the mechanical properties and processing performance of the modified alloy material are improved.

[0012] The present invention provides a modified alloy material, which is prepared by blending polyphenylene ether (PPO), polyamide 66 (PA66), a viscosity-reducing compatibilizing masterbatch, glass fiber, a flame retardant, a lubricant, and an antioxidant. The tensile strength of the modified alloy material is 150 - 180 MPa, the flexural strength is 210 - 230 MPa, the flexural modulus is 9 - 12 GPa, and the notched Izod impact strength at 23 °C is 13 - 15 kJ / m 2 ; the density of the modified alloy material is 1.3 - 1.4 g / cm 3 , and the melt index at 280 °C / 5 kg is 10 - 50 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 190 - 220 °C, and the shrinkage rate (MD / TD) is (0.15 - 0.3) / (0.25 - 0.3); the flame retardancy of the 1.5 mm modified alloy material is V0; The viscosity-reducing compatibilizing masterbatch is prepared by blending polyphenylene ether, polyamide 6, an activator, a coupling agent, and an initiator in a vertical twin-screw extruder.

[0013] Further, in the shrinkage rate (MD / TD), MD is the shrinkage rate of the modified alloy material in the material flow direction between 0.15% and 0.3%, and TD is the shrinkage rate of the modified alloy material perpendicular to the material flow direction between 0.25% and 0.3%.

[0014] Further, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 10 - 30 parts by weight; The polyamide 66 is 10 - 25 parts by weight; The viscosity-reducing compatibilizing masterbatch is 10 - 30 parts by weight; The glass fiber is 20 - 40 parts by weight; The flame retardant is 10 - 20 parts by weight; The lubricant is 0.5 - 1 part by weight; The antioxidant is 0.3 - 0.5 part by weight.

[0015] Further, the components and their contents in the viscosity-reducing compatibilizing masterbatch are as follows: Polyphenylene ether: 30 - 80 parts by weight; Polyamide 6: 30 - 80 parts by weight; Activator: 0.1 - 1 part by weight; Coupling agent: 0.1 - 1 part by weight; Initiator: 0.1 - 1 part by weight.

[0016] Further, the vertical twin-screw extruder is composed of a horizontal screw extruder and a vertical screw extruder; the horizontal screw extruder is evenly divided into thirteen sections of barrels in sequence according to the material moving direction, where the first section of the barrel is the feeding barrel, and the second to the thirteenth sections of the barrels are evenly divided into twelve temperature zones; the vertical screw extruder is evenly divided into five sections of barrels in sequence according to the material moving direction, where the first section of the barrel is the feeding barrel, and the second to the fifth sections of the barrels are evenly divided into four temperature zones; The tail end of the fifth section of the barrel of the vertical screw extruder is vertically and sealingly connected to the side feeding port of the fifth section of the barrel of the horizontal screw extruder, so that the horizontal screw extruder and the vertical screw extruder are vertically arranged.

[0017] Further, an extruder head is also provided at the tail end of the thirteenth section of the barrel of the horizontal screw extruder.

[0018] Further, the vertical twin-screw extruder is provided with a main feeding port one, a main feeding port two, and a side feeding port three. Among them, the main feeding port one is arranged at the first section of the barrel of the horizontal screw extruder, the main feeding port two is arranged at the first section of the barrel of the vertical screw extruder, and the side feeding port three is arranged at the eighth section of the barrel of the horizontal screw extruder.

[0019] Further, the structure of the screw in both the horizontal screw extruder and the vertical screw extruder is a twin-screw; the length-diameter ratio of the horizontal screw extruder is (48 - 52):1, and the length-diameter ratio of the vertical screw extruder is 16:1.

[0020] Further, the materials enter the vertical twin-screw extruder through the horizontal screw extruder and the vertical screw extruder respectively, and are mixed together at the fifth section of the barrel of the horizontal screw extruder.

[0021] The present invention also provides a method for preparing the modified alloy material by using the vertical twin-screw extruder. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Heat and stir poly(phenylene ether) and an active agent at high speed in a high-speed mixer. While stirring, spray a coupling agent for blending. After the blending is completed, cool to room temperature and then add an initiator and continue stirring to obtain a first premix. Step 2: Heat and stir polyamide 6 and an active agent at high speed in a high-speed mixer. While stirring, spray a coupling agent for blending. After the blending is completed, cool to room temperature to obtain a second premix. Step 3: Feed the first premix into a vertical twin-screw twin-extruder through the first main feed port, and feed the second premix into the vertical twin-screw twin-extruder through the second main feed port. After melting and blending, extrude and pelletize to obtain a viscosity-reducing compatibilizing masterbatch. Step 4: Stir and blend poly(phenylene ether), the viscosity-reducing compatibilizing masterbatch, a lubricant, and an antioxidant in a high-speed mixer to obtain a first mixture. Step 5: Add polyamide 66 and a flame retardant to a high-speed mixer and stir and blend to obtain a second mixture. Step 6: Feed the first mixture into the vertical twin-screw twin-extruder through the first main feed port, feed the second mixture into the vertical twin-screw twin-extruder through the second main feed port, and feed glass fiber into the vertical twin-screw twin-extruder through the third side feed port. After melting and extruding, pelletize to obtain the modified alloy material.

[0022] Further, in Step 1, the mass ratio of the poly(phenylene ether), the active agent, the coupling agent, and the initiator is (30 - 80):(0.05 - 0.95):(0.05 - 0.95):(0.1 - 1).

[0023] Further, in Step 1, the intrinsic viscosity of the poly(phenylene ether) is 0.30 - 0.45 dL / g.

[0024] Further, in Step 1, the active agent is one or both of maleic anhydride (MAH) and glycidyl methacrylate (GMA).

[0025] Further, in Step 1, the coupling agent is one or more of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-glycidyletheroxypropyltrimethoxysilane, and 3-(methacryloyloxy)propyltrimethoxysilane.

[0026] Further, in Step 1, the initiator is dicumyl peroxide (DCP).

[0027] Further, in Step 1, the heating temperature is 80 - 120 °C.

[0028] Further, in Step 1, the speed of the high-speed stirring is 300 - 800 rpm.

[0029] Further, the blending time in the step 1 is 3 - 10 min.

[0030] Further, the speed of the continued stirring in the step 1 is 300 - 800 rpm, and the time of the continued stirring is 30 - 60 s.

[0031] Further, the mass ratio of polyamide 6, the active agent and the coupling agent in the step 2 is (30 - 80):(0.05 - 0.95):(0.05 - 0.95).

[0032] Further, the intrinsic viscosity of the polyamide 6 in the step 2 is 2.52 dL / g.

[0033] Further, the active agent in the step 2 is one or two of maleic anhydride (MAH) or glycidyl methacrylate (GMA).

[0034] Further, the coupling agent in the step 2 is one or several of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-glycidyletheroxypropyltrimethoxysilane and 3-(methacryloyloxy)propyltrimethoxysilane.

[0035] Further, the heating temperature in the step 2 is 80 - 120 °C.

[0036] Further, the speed of the high-speed stirring in the step 2 is 300 - 800 rpm.

[0037] Further, the blending time in the step 2 is 3 - 10 min.

[0038] Further, the working temperature of the horizontal screw extruder of the vertical twin-screw double extruder in the step 3 is 260 - 310 °C. Among them, the temperatures of the twelve temperature zones are respectively: the temperature of the first temperature zone is 280 - 290 °C, the temperature of the second temperature zone is 290 - 300 °C, the temperature of the third temperature zone is 300 - 310 °C, the temperature of the fourth temperature zone is 290 - 300 °C, the temperature of the fifth temperature zone is 280 - 290 °C, the temperature of the sixth temperature zone is 270 - 280 °C, the temperature of the seventh temperature zone is 270 - 280 °C, the temperature of the eighth temperature zone is 270 - 280 °C, the temperature of the ninth temperature zone is 260 - 270 °C, the temperature of the tenth temperature zone is 260 - 270 °C, the temperature of the eleventh temperature zone is 260 - 270 °C, and the temperature of the twelfth temperature zone is 260 - 270 °C.

[0039] Further, the main machine current of the horizontal screw extruder in the step 3 is 80 - 100 A.

[0040] Further, the length-diameter ratio of the horizontal screw extruder in step 3 is (48 - 52):1.

[0041] Further, the screw rotation speed of the horizontal screw extruder in step 3 is 300 - 500 rpm.

[0042] Further, the melt temperature of the horizontal screw extruder in step 3 is 270 - 300 °C.

[0043] Further, the temperature of the extruder head of the horizontal screw extruder in step 3 is 280 - 310 °C.

[0044] Further, the vacuum degree of the horizontal screw extruder in step 3 is 0.05 to 0.08 MPa.

[0045] Further, the torque of the horizontal screw extruder in step 3 is 270 - 290 N•m.

[0046] Further, the feeding speed of the main feeding port 1 of the horizontal screw extruder in step 3 is 30 - 60 kg / h.

[0047] Further, the working temperature of the vertical screw extruder of the vertical twin-screw double extruder in step 3 is 250 - 270 °C, wherein the temperatures of the four temperature zones are: the first temperature zone is 250 - 260 °C, the second temperature zone is 260 - 270 °C, the third temperature zone is 260 - 270 °C, and the fourth temperature zone is 260 - 270 °C.

[0048] Further, the length-diameter ratio of the vertical screw extruder in step 3 is 16:1.

[0049] Further, the screw rotation speed of the vertical screw extruder in step 3 is 300 - 500 rpm.

[0050] Further, the feeding speed of the main feeding port 2 of the vertical screw extruder in step 3 is 30 - 60 kg / h.

[0051] Further, in the horizontal screw extruder, the initiator in the premix 1 will generate free radicals under high temperature and shear action. The free radicals will capture the H on the polyphenylene ether molecular chain, forming free radical active sites on the polyphenylene ether molecular chain. The active agent has a highly reactive carbon-carbon double bond structure. At this time, the active sites on the polyphenylene ether molecular chain will undergo an addition reaction with the carbon-carbon double bond structure, thereby grafting the active agent onto the molecular chain of the polyphenylene ether. At the same time, the functional groups in the coupling agent will also undergo a chemical reaction or hydrogen bond interaction with the long chain of the polyphenylene ether, forming a crosslinked structure.

[0052] Furthermore, under the high temperature and shearing action of the vertical screw extruder, the active end groups in the active agent in the second premix will ring open under the action of the amino groups (-NH2) on the molecular chain of the polyamide 6, and amide groups and carboxyl groups are obtained through reaction to form a stable structure. Meanwhile, the coupling agent will also undergo a chemical reaction or hydrogen bonding with the polyamide 6 to form a crosslinked structure.

[0053] Furthermore, in the vertical twin-screw extruder, the first premix and the second premix are blended in the latter half of the horizontal screw extruder. The compatibility between the polyphenylene ether and the polyamide 6 modified by the active agent and the coupling agent is improved, and the system viscosity is reduced.

[0054] Furthermore, in step 4, the mass ratio of the polyphenylene ether, the viscosity-reducing compatibilizing masterbatch, the lubricant, and the antioxidant is (10 - 30):(10 - 30):(0.5 - 1):(0.3 - 0.5).

[0055] Furthermore, in step 4, the intrinsic viscosity of the polyphenylene ether is 0.30 - 0.45 dL / g.

[0056] Furthermore, in step 4, the lubricant is one or more of polyethylene wax (PE wax), silicone powder, pentaerythritol stearate (PETS), and montan wax.

[0057] Furthermore, in step 4, the antioxidant is one or more of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0058] Furthermore, in step 4, the stirring speed is 300 - 800 rpm, and the blending time is 0.5 - 1 min.

[0059] Furthermore, in step 5, the mass ratio of the polyamide 66 and the flame retardant is (10 - 25):(10 - 20).

[0060] Furthermore, in step 5, the intrinsic viscosity of the polyamide 66 is 2.4 - 3.2 dL / g.

[0061] Furthermore, in step 5, the flame retardant is one or more of bisphenol A-bis(diphenyl phosphate) (BDP), aluminum diethyl phosphinate (ADP), and red phosphorus masterbatch.

[0062] Further, the stirring speed in step 5 is 300 - 800 rpm, and the blending time is 0.5 - 1 min.

[0063] Further, the mass ratio of the glass fiber to the polyamide 66 in step 6 is (20 - 40) : (10 - 25).

[0064] Further, the average diameter of the glass fiber in step 6 is 10 - 15 μm, and the aspect ratio is 3 - 4.

[0065] Further, the shape of the glass fiber in step 6 is one or both of round fiber and flat fiber.

[0066] Further, the operating temperature of the horizontal screw extruder of the vertical twin - screw twin - extruder in step 6 is 240 - 280 °C. Among them, the temperatures of the twelve temperature zones are respectively: the first temperature zone is 240 - 250 °C, the second temperature zone is 270 - 280 °C, the third temperature zone is 270 - 280 °C, the fourth temperature zone is 260 - 270 °C, the fifth temperature zone is 250 - 260 °C, the sixth temperature zone is 250 - 260 °C, the seventh temperature zone is 250 - 260 °C, the eighth temperature zone is 240 - 250 °C, the ninth temperature zone is 240 - 250 °C, the tenth temperature zone is 240 - 250 °C, the eleventh temperature zone is 240 - 250 °C, and the twelfth temperature zone is 250 - 260 °C.

[0067] Further, the main machine current of the horizontal screw extruder in step 6 is 80 - 100 A.

[0068] Further, the length - diameter ratio of the horizontal screw extruder in step 6 is (48 - 52) : 1.

[0069] Further, the screw rotation speed of the horizontal screw extruder in step 6 is 300 - 500 rpm.

[0070] Further, the melt temperature of the horizontal screw extruder in step 6 is 255 - 275 °C.

[0071] Further, the temperature of the extruder head of the horizontal screw extruder in step 6 is 250 - 280 °C.

[0072] Further, the vacuum degree of the horizontal screw extruder in step 6 is 0.05 to 0.08 MPa.

[0073] Further, the torque of the horizontal screw extruder in step 6 is 270 - 290 N•m.

[0074] Further, in the step 6, the feeding speed of the main feeding port 1 of the horizontal screw extruder is 30 - 60 kg / h, and the feeding speed of the side feeding port 3 is 40 - 50 kg / h.

[0075] Further, in the step 6, the working temperature of the vertical screw extruder of the vertical twin-screw double extruder is 220 - 250 °C. Among them, the temperatures of the four temperature zones are: the first temperature zone is 220 - 230 °C, the second temperature zone is 240 - 250 °C, the third temperature zone is 240 - 250 °C, and the fourth temperature zone is 240 - 250 °C.

[0076] Further, in the step 6, the length-diameter ratio of the vertical screw extruder is 16:1.

[0077] Further, in the step 6, the screw rotation speed of the vertical screw extruder is 300 - 500 rpm.

[0078] Further, in the step 6, the feeding speed of the main feeding port 2 of the vertical screw extruder is 30 - 60 kg / h.

[0079] Further, in the modified alloy material, the viscosity-reducing compatibilizing masterbatch contains polyphenylene ether and polyamide 6, has good compatibility with the polyphenylene ether and the polyamide 66, and the active agent in the viscosity-reducing compatibilizing masterbatch can form chemical bonds with the polyphenylene ether and the polyamide 66, further improving the compatibility of the polyphenylene ether and the polyamide 66. At the same time, the coupling agent in the viscosity-reducing compatibilizing masterbatch has hydrophilicity and hydrophobicity. After being mixed with the glass fiber, the hydrophilic group interacts with the sizing agent on the surface of the glass fiber, and the hydrophobic group forms an interaction force with the polyphenylene ether, polyamide 66, and polyamide 6. In addition, the flame retardant will decompose to generate phosphoric acid or polyphosphoric acid during the combustion process of the modified alloy material, forming a highly viscous molten vitreous or dense carbon layer in a solid form to isolate the material from heat and oxygen, preventing the material from further pyrolysis and the internal pyrolysis products from entering the gas phase to participate in the combustion process. And the flame retardant will decompose to generate free radicals such as PO or HPO during combustion, capturing active H free radicals or OH free radicals in the gas phase state, thereby delaying the combustion chain reaction.

[0080] The present invention also provides an electrical appliance housing, which is prepared from the modified alloy material.

[0081] The beneficial effects of the present invention: 1. In the present invention, the viscosity-reducing compatibilizing masterbatch is prepared by adding polyphenylene ether and polyamide 6 through different feeding ports of a vertical twin-screw extruder, avoiding the violent reaction of polyamide 6 caused by the higher melting point temperature of polyphenylene ether than that of polyamide 6 and the lower reaction activity of polyphenylene ether than that of polyamide 6. In the horizontal screw part, polyphenylene ether and an active agent react and graft under the participation of an initiator first. After a period of time, polyamide 6 and an active agent fed laterally by the vertical screw part continue to participate in the reaction, obtaining the viscosity-reducing compatibilizing masterbatch. In addition, in the modified alloy material of the present invention, polyphenylene ether and polyamide 66 are also added to the vertical twin-screw extruder in the same manner, improving the mixing uniformity of polyphenylene ether and polyamide 66. The addition of the viscosity-reducing compatibilizing masterbatch reduces the viscosity of the system and improves the compatibility between raw materials. 2. In the present invention, glass fiber is added to the vertical twin-screw extruder through the side feeding port of the horizontal screw extruder, so that the glass fiber will not be overly sheared. The inherent stability of the glass fiber also increases the heat distortion temperature of the material, reduces the shrinkage rate, and the viscosity-reducing compatibilizing masterbatch improves the compatibility between polyphenylene ether, polyamide 66 and glass fiber after being mixed with the system, reducing the fiber floating and poor flatness of the material, making the mixing of glass fiber better, and improving the mechanical properties of the material. The addition of the flame retardant effectively improves the flame retardancy of the material on the basis of environmental protection and no generation of harmful halogen gases. 3. The preparation process of the modified alloy material in the present invention is simple, does not involve dangerous operations during the material mixing process, has a short synthesis time and high efficiency. At the same time, the raw materials in the synthesis process of the present invention are green, environmentally friendly, non-toxic and harmless, and are suitable for industrial production. Description of the Drawings

[0082] Figure 1 It is a comparison diagram of the flatness of the injection-molded samples of the modified alloy materials described in Examples 2 and 3; Figure 2 It is a scanning electron microscope image of the modified alloy material described in Example 3 after being brittle fractured by liquid nitrogen; Figure 3 It is a comparison diagram of the rheological tests of the modified alloy materials described in Example 1 and Comparative Example 1; Figure 4 It is a comparison diagram of the flatness of the injection-molded samples of the modified alloy materials described in Comparative Examples 1 and 2 of the present invention; Figure 5 It is a scanning electron microscope image of the modified alloy material described in Comparative Example 1 of the present invention after being brittle fractured by liquid nitrogen; Figure 6 It is a scanning electron microscope image of the modified alloy material described in Comparative Example 2 of the present invention after being brittle fractured by liquid nitrogen; Figure 7 It is a schematic structural diagram of the vertical twin-screw extruder described in the present invention; The names of the labels in the figure are as follows: 1. Horizontal screw extruder; 2. Vertical screw extruder; 11. Main feeding port 1; 12. Side feeding port 3; 21. Main feeding port 2. Detailed implementation mode

[0083] The following is a detailed description of the invention in combination with embodiments: The present invention provides a modified alloy material, its preparation method and an electrical appliance housing. Specifically, by preparing a viscosity-reducing compatibilizing masterbatch, mixing it with polyphenylene ether and polyamide 66, and adding additives, the modified alloy material is prepared. During the preparation process, through a specific vertical twin-screw extruder, polyphenylene ether and polyamide 6 in the viscosity-reducing compatibilizing masterbatch, as well as polyphenylene ether and polyamide 66 in the modified alloy material, are added into the vertical twin-screw extruder by the horizontal screw extruder and the vertical screw extruder in the vertical twin-screw extruder. Thus, the prepared modified alloy material has good compatibility, does not show phenomena such as floating fibers, and has excellent mechanical properties and good processing performance, etc.

[0084] Example 1 This example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, viscosity-reducing compatibilizing masterbatch, glass fiber, flame retardant, lubricant and antioxidant; the tensile strength of the modified alloy material is 168 MPa, the flexural strength is 228 MPa, the flexural modulus is 10 GPa, and the notched impact strength of the simply supported beam at 23 °C is 13.8 kJ / m 2 ; the density of the modified alloy material is 1.37 g / cm 3 , and the melt index at 280 °C / 5 kg is 19 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 211 °C, and the shrinkage rate (MD / TD) is 0.15 / 0.25; the flame retardancy of the 1.5 mm modified alloy material is V0; The viscosity-reducing compatibilizing masterbatch is prepared by blending polyphenylene ether, polyamide 6, active agent, coupling agent and initiator in a vertical twin-screw extruder.

[0085] In this example, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 26 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 20 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The viscosity-reducing compatibilizing masterbatch is 10 parts by weight; The glass fiber is 30 parts by weight, and the glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethyl phosphinate; The lubricant is 0.6 parts by weight of silicone powder; The antioxidant is 0.2 parts by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 parts by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0086] In this example, the components and their contents in the viscosity-reducing compatibilizing masterbatch are as follows: The polyphenylene ether is 50 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 6 is 50 parts by weight, and the intrinsic viscosity of the polyamide 6 is 2.52 dL / g; The active agent is 0.6 parts by weight of maleic anhydride; The coupling agent is 0.6 parts by weight of γ-glycidoxypropyltrimethoxysilane; The initiator is 0.5 parts by weight of dicumyl peroxide.

[0087] This example also provides a method for preparing the modified alloy material with the vertical twin-screw extruder. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Add the polyphenylene ether and 0.3 parts by weight of the active agent to a high-speed mixer, stir at a high speed at 100 °C and 500 rpm, while stirring, spray 0.3 parts by weight of the coupling agent and blend for 5 min. After the blending is completed, cool to room temperature, then add the initiator and continue to stir at 500 rpm for 60 s to obtain premix one; Step 2: Add the polyamide 6 and 0.3 parts by weight of the active agent to a high-speed mixer, stir at a high speed at 100 °C and 500 rpm, while stirring, spray 0.3 parts by weight of the coupling agent and blend for 5 min. After the blending is completed, cool to room temperature to obtain premix two; Step 3: Feed premix one into the vertical twin-screw extruder through the first main feeding port 11, and feed premix two into the vertical twin-screw extruder through the second main feeding port 21. After melting and blending, extrude and pelletize to obtain the viscosity-reducing compatibilizing masterbatch; Step 4: Add the polyphenylene ether, the viscosity-reducing compatibilizing masterbatch, the lubricant and the antioxidant to a high-speed mixer, stir and blend at 300 r / min for 1 min to obtain blend one; Step 5: Add polyamide 66 and the flame retardant to a high-speed mixer, stir and blend at 300 r / min for 1 min to obtain blend two; Step 6: Feed the first mixture into the vertical twin-screw double extruder through the first main feeding port 11, feed the second mixture into the vertical twin-screw double extruder through the second main feeding port 21, and laterally feed glass fibers into the vertical twin-screw double extruder through the third side feeding port 12. After melting and extrusion, pelletize to obtain the modified alloy material.

[0088] Example 2 This example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, viscosity-reducing compatibilizing masterbatch, glass fibers, flame retardant, lubricant and antioxidant; the tensile strength of the modified alloy material is 170 MPa, the flexural strength is 226 MPa, the flexural modulus is 9.9 GPa, and the notched Izod impact strength at 23 °C is 13.4 kJ / m 2 ; the density of the modified alloy material is 1.36 g / cm 3 , and the melt index at 280 °C / 5 kg is 26 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 209 °C, and the shrinkage rate (MD / TD) is 0.15 / 0.25; the flame retardancy of the 1.5 mm modified alloy material is V0; The viscosity-reducing compatibilizing masterbatch is prepared by blending polyphenylene ether, polyamide 6, activator, coupling agent and initiator in a vertical twin-screw extruder.

[0089] In this example, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 21 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 15 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The viscosity-reducing compatibilizing masterbatch is 20 parts by weight; The glass fibers are 30 parts by weight, the glass fibers are round fibers, and the average diameter of the round fibers is 10 μm; The flame retardant is 13 parts by weight of aluminum diethylphosphinate; The lubricant is 0.6 parts by weight of silicone powder; The antioxidant is 0.2 parts by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 parts by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0090] In this example, the components and their contents in the viscosity-reducing compatibilizing masterbatch are as follows: The polyphenylene ether is 55 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 6 is 45 parts by weight, and the intrinsic viscosity of the polyamide 6 is 2.52 dL / g; The active agent is 0.6 parts by weight of maleic anhydride; The coupling agent is 0.6 parts by weight of γ-glycidoxypropyltrimethoxysilane; The initiator is 0.5 parts by weight of dicumyl peroxide.

[0091] This embodiment also provides a method for preparing the modified alloy material with the vertical twin-screw extruder. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Add polyphenylene ether and 0.3 parts by weight of the active agent into a high-speed mixer, stir at a high speed at 100 °C and 300 rpm, spray 0.3 parts by weight of the coupling agent while stirring and blend for 8 min. After the blending is completed, cool to room temperature, then add the initiator and continue to stir at 300 rpm for 60 s to obtain premix one; Step 2: Add polyamide 6 and 0.3 parts by weight of the active agent into a high-speed mixer, stir at a high speed at 100 °C and 500 rpm, spray 0.3 parts by weight of the coupling agent while stirring and blend for 5 min. After the blending is completed, cool to room temperature to obtain premix two; Step 3: Feed premix one into the vertical twin-screw extruder through main feeding port one 11, and feed premix two into the vertical twin-screw extruder through main feeding port two 21. After melting and blending, extrude and pelletize to obtain a viscosity-reducing and compatibility-improving masterbatch; Step 4: Add polyphenylene ether, the viscosity-reducing and compatibility-improving masterbatch, lubricant and antioxidant into a high-speed mixer, stir and blend at 500 r / min for 0.5 min to obtain blend one; Step 5: Add polyamide 66 and flame retardant into a high-speed mixer, stir and blend at 500 r / min for 0.5 min to obtain blend two; Step 6: Feed blend one into the vertical twin-screw extruder through main feeding port one 11, feed blend two into the vertical twin-screw extruder through main feeding port two 21, and feed glass fiber into the vertical twin-screw extruder through side feeding port three 12 on the side. After melting and extruding, pelletize to obtain the modified alloy material.

[0092] Example 3 This embodiment provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, viscosity-reducing and compatibility-improving masterbatch, glass fiber, flame retardant, lubricant and antioxidant; the tensile strength of the modified alloy material is 162 MPa, the flexural strength is 220 MPa, the flexural modulus is 9.7 GPa, and the notched Izod impact strength at 23 °C is 14 kJ / m 2 ; the density of the modified alloy material is 1.33 g / cm 3, the melt index at 280 °C / 5 kg is 40 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 199 °C, and the shrinkage rate (MD / TD) is 0.25 / 0.3; the flame retardancy of the 1.5 mm modified alloy material is V0; The viscosity-reducing compatibilizing masterbatch is prepared by blending polyphenylene ether, polyamide 6, an activator, a coupling agent, and an initiator in a vertical twin-screw extruder.

[0093] In this embodiment, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 16 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 10 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The viscosity-reducing compatibilizing masterbatch is 30 parts by weight; The glass fiber is 30 parts by weight. The glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethylphosphinate; The lubricant is 0.6 part by weight of silicone powder; The antioxidant is 0.2 part by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and 0.2 part by weight of tris[2,4-di-tert-butylphenyl] phosphite.

[0094] In this embodiment, the components and their contents in the viscosity-reducing compatibilizing masterbatch are as follows: The polyphenylene ether is 50 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 6 is 50 parts by weight, and the intrinsic viscosity of the polyamide 6 is 2.52 dL / g; The activator is 0.6 part by weight of maleic anhydride; The coupling agent is 0.6 part by weight of γ-glycidoxypropyltrimethoxysilane; The initiator is 0.5 part by weight of dicumyl peroxide.

[0095] This embodiment also provides a method for preparing the modified alloy material by using the vertical twin-screw extruder. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Add polyphenylene ether and 0.3 part by weight of the activator to a high-speed mixer, stir at high speed at 100 °C and 800 rpm, spray 0.3 part by weight of the coupling agent while stirring, blend for 3 min, after the blending is completed, cool to room temperature, and then add the initiator and continue to stir at 800 rpm for 30 s to obtain premix one; Step 2: Add polyamide 6 and 0.3 parts by weight of an active agent into a high-speed mixer, and stir at 80°C and 800 rpm at high speed. While stirring, spray 0.3 parts by weight of a coupling agent and blend for 3 minutes. After the blending is completed, cool to room temperature to obtain premix two. Step 3: Feed the premix one into a vertical twin-screw extruder through the first main feeding port 11, and feed the premix two into the vertical twin-screw extruder through the second main feeding port 21. After melt blending, extrude and pelletize to obtain a viscosity-reducing and compatibility-improving masterbatch. Step 4: Add polyphenylene ether, the viscosity-reducing and compatibility-improving masterbatch, a lubricant, and an antioxidant into a high-speed mixer, and stir and blend for 0.5 minutes under the condition of 800 r / min to obtain blend one. Step 5: Add polyamide 66 and a flame retardant into a high-speed mixer, and stir and blend for 0.5 minutes under the condition of 800 r / min to obtain blend two. Step 6: Feed the blend one into the vertical twin-screw extruder through the first main feeding port 11, feed the blend two into the vertical twin-screw extruder through the second main feeding port 21, and feed glass fiber into the vertical twin-screw extruder through the third side feeding port 12 on the side. After melt extrusion, pelletize to obtain the modified alloy material.

[0096] As Figure 1 This is a comparison chart of the flatness of the injection-molded samples of the modified alloy materials described in Example 2 and 3. As can be seen from the figure, under the action of raw materials such as the viscosity-reducing and compatibility-improving masterbatch and polyamide 66, the surface flatness of the modified alloy materials described in Example 2 and 3 is excellent.

[0097] As Figure 2 This is a scanning electron microscope image of the modified alloy material described in Example 3 after being brittle fractured by liquid nitrogen. As can be seen from the figure, the coating resin of the glass fiber in the modified alloy material described in Example 3 is relatively thick.

[0098] Comparative Example 1 This comparative example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, glass fiber, a flame retardant, a coupling agent, a lubricant, and an antioxidant; the tensile strength of the modified alloy material is 90 MPa, the flexural strength is 140 MPa, the flexural modulus is 8.8 GPa, and the notched izod impact strength at 23°C is 7.2 kJ / m 2 ; the density of the modified alloy material is 1.37 g / cm 3 , and the melt index at 280°C / 5 kg is 16 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 175°C, and the shrinkage rate (MD / TD) is 0.3 / 0.4; the flame retardancy of the 1.5-mm modified alloy material is V0.

[0099] In this comparative example, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 31 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 25 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The glass fiber is 30 parts by weight. The glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethylphosphinate; The coupling agent is 0.5 part by weight of γ-glycidoxypropyltrimethoxysilane; The lubricant is 0.6 part by weight of silicone powder; The antioxidant is 0.2 part by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 part by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0100] This comparative example also provides a method for preparing the modified alloy material using the vertical twin-screw extruder. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Add the polyphenylene ether, coupling agent, lubricant and antioxidant into a high-speed mixer, stir at 300 r / min for 1 min to obtain a first blended material; Step 2: Add the polyamide 66 and flame retardant into a high-speed mixer, stir at 300 r / min for 1 min to obtain a second blended material; Step 3: Feed the first blended material into the vertical twin-screw extruder through the first main feeding port 11, feed the second blended material into the vertical twin-screw extruder through the second main feeding port 21, and feed the glass fiber into the vertical twin-screw extruder through the third side feeding port 12. After melting and extrusion, pelletize to obtain the modified alloy material.

[0101] As Figure 3 This is the rheological test comparison chart of the modified alloy materials in Example 1 and Comparative Example 1. It can be seen from the figure that in Example 1, the viscosity-reducing compatibilizing masterbatch is added, and the viscosity of the material is moderate. While in Comparative Example 1, the viscosity-reducing compatibilizing masterbatch is not added, and its viscosity is relatively large. The trend of the material viscosity in the figure is consistent with the melt index test data. It can be seen that the introduction of the viscosity-reducing compatibilizing masterbatch significantly improves the viscosity and fluidity of the material.

[0102] Comparative Example 2 This comparative example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, glass fiber, flame retardant, coupling agent, compatibilizer, lubricant and antioxidant; the tensile strength of the modified alloy material is 105 MPa, the flexural strength is 146 MPa, the flexural modulus is 9.1 GPa, and the notched Izod impact strength at 23 °C is 8.5 kJ / m 2 ; the density of the modified alloy material is 1.37 g / cm 3 , and the melt index at 280 °C / 5 kg is 12 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 186 °C, and the shrinkage rate (MD / TD) is 0.3 / 0.35; the flame retardant property of the 1.5 mm modified alloy material is V0.

[0103] In this comparative example, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 26 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 25 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The glass fiber is 30 parts by weight, and the glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethylphosphinate; The coupling agent is 0.5 part by weight of γ-glycidoxypropyltrimethoxysilane; The compatibilizer is 5 parts by weight of polyphenylene ether grafted maleic anhydride; The lubricant is 0.6 part by weight of silicone powder; The antioxidant is 0.2 part by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 part by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0104] This comparative example also provides a method for preparing the modified alloy material by using the vertical twin-screw extruder. Each component is taken according to the content of each component. The preparation method includes the following steps: Step 1: Add polyphenylene ether, coupling agent, compatibilizer, lubricant and antioxidant into a high-speed mixer, and stir at 300 r / min for 1 min to obtain a first mixture; Step 2: Add polyamide 66 and flame retardant into a high-speed mixer, and stir at 300 r / min for 1 min to obtain a second mixture; Step 3: Feed the first mixture into the vertical double-screw double-extruder through the first main feeding port 11, feed the second mixture into the vertical double-screw double-extruder through the second main feeding port 21, and laterally feed glass fiber into the vertical double-screw double-extruder through the third side feeding port 12. After melting and extrusion, pelletize to obtain the modified alloy material.

[0105] Such as Figure 4 This is the flatness comparison diagram of the injection-molded samples of the modified alloy materials in Comparative Examples 1 and 2 of the present invention. As can be seen from the figure, in Comparative Examples 1 and 2, simply increasing the dosage of the compatibilizer increases the system viscosity and worsens the processability, without improving the surface flatness after processing and forming the material.

[0106] Such as Figure 5 And 6 And this is the scanning electron microscope image of the modified alloy materials in Comparative Examples 1 and 2 of the present invention after being brittle fractured by liquid nitrogen. As can be seen from the figure, compared with Comparative Example 2, in Comparative Example 1, the addition of the coupling agent makes more resin wrap on the surface of the glass fiber, and the bonding effect with the resin is better. Compared with Figure 2 Example 3 in, in Example 3, the viscosity reduction and compatibilization effects of the viscosity-reducing compatibilizing masterbatch are better, the compatibility is better, and the resin coating on the glass fiber is thicker.

[0107] Comparative Example 3 This comparative example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, glass fiber, flame retardant, coupling agent, compatibilizer, lubricant and antioxidant; the tensile strength of the modified alloy material is 138 MPa, the flexural strength is 187 MPa, the flexural modulus is 9.6 GPa, and the notched Izod impact strength at 23 °C is 10.3 kJ / m 2 ; the density of the modified alloy material is 1.35 g / cm 3 , and the melt index at 280 °C / 5 kg is 10 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 194 °C, and the shrinkage rate (MD / TD) is 0.2 / 0.3; the flame retardancy of the 1.5 mm modified alloy material is V0.

[0108] The components and their contents in the modified alloy material in this comparative example are as follows: The polyphenylene ether is 21 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 25 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The glass fiber is 30 parts by weight, and the glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethylphosphinate; The coupling agent is 0.5 parts by weight of γ-glycidoxypropyltrimethoxysilane; The compatibilizer is 10 parts by weight of polyphenylene ether grafted maleic anhydride; The lubricant is 0.6 parts by weight of silicone powder; The antioxidant is 0.2 parts by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 parts by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0109] This comparative example also provides a method for preparing the modified alloy material using the vertical twin-screw extruder. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Add polyphenylene ether, coupling agent, compatibilizer, lubricant and antioxidant into a high-speed mixer, stir at 300 r / min for 1 min to obtain a first mixture; Step 2: Add polyamide 66 and flame retardant into a high-speed mixer, stir at 300 r / min for 1 min to obtain a second mixture; Step 3: Feed the first mixture into the vertical twin-screw double extruder through the first main feeding port 11, feed the second mixture into the vertical twin-screw double extruder through the second main feeding port 21, and feed glass fiber into the vertical twin-screw double extruder through the third side feeding port 12. After melting and extrusion, pelletize to obtain the modified alloy material.

[0110] Comparative Example 4 This comparative example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, viscosity-reducing compatibilizing masterbatch, glass fiber, flame retardant, lubricant and antioxidant; the tensile strength of the modified alloy material is 155 MPa, the flexural strength is 218 MPa, the flexural modulus is 9.7 GPa, and the notched impact strength of the simply supported beam at 23 °C is 12 kJ / m 2 ; the density of the modified alloy material is 1.33 g / cm 3 , and the melt index at 280 °C / 5 kg is 37 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 197 °C, and the shrinkage rate (MD / TD) is 0.3 / 0.3; the flame retardancy of the 1.5 mm modified alloy material is V0.

[0111] In this comparative example, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 16 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 10 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The viscosity-reducing compatibilizing masterbatch is 30 parts by weight; The glass fiber is 30 parts by weight. The glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethylphosphinate; The lubricant is 0.6 parts by weight of silicone powder; The antioxidant is 0.2 parts by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 parts by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0112] In this comparative example, the components and their contents in the viscosity-reducing compatibilizing masterbatch are as follows: The polyphenylene ether is 50 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 6 is 50 parts by weight, and the intrinsic viscosity of the polyamide 6 is 2.52 dL / g; The activator is 0.6 parts by weight of maleic anhydride; The coupling agent is 0.6 parts by weight of γ-glycidoxypropyltrimethoxysilane; The initiator is 0.5 parts by weight of dicumyl peroxide.

[0113] This comparative example also provides a method for modifying the alloy material. Each component is taken according to the content of each component. The preparation method includes the following steps: Step 1: Add the polyphenylene ether and 0.3 parts by weight of the activator into a high-speed mixer, stir at 100 °C and 800 rpm at high speed, spray 0.3 parts by weight of the coupling agent while stirring for 3 min, after the blending is completed, cool to room temperature, and then add the initiator and continue to stir at 800 rpm for 30 s to obtain the first premix; Step 2: Add the polyamide 6 and 0.3 parts by weight of the activator into a high-speed mixer, stir at 80 °C and 800 rpm at high speed, spray 0.3 parts by weight of the coupling agent while stirring for 3 min, after the blending is completed, cool to room temperature to obtain the second premix; Step 3: Feed the first premix into a vertical twin-screw twin-extruder through the first main feeding port 11, and feed the second premix into the vertical twin-screw twin-extruder through the second main feeding port 21. After melting and blending, extrude and pelletize to obtain the viscosity-reducing compatibilizing masterbatch; Step 4: Add the polyphenylene ether, polyamide 66, viscosity-reducing compatibilizing masterbatch, lubricant, antioxidant, and flame retardant into a high-speed mixer, stir at 300 r / min for 3 min to obtain a blended mixture; Step 5: Feed the mixture into the main feeding port of a conventional twin-screw extruder, and add glass fiber into the conventional twin-screw extruder through the side feeding port, melt, extrude and pelletize to obtain the modified alloy material.

[0114] Comparative Example 5 This comparative example provides a modified alloy material, which is prepared by blending polyphenylene ether, polyamide 66, viscosity-reducing compatibilizing masterbatch, glass fiber, flame retardant, lubricant and antioxidant; the tensile strength of the modified alloy material is 130 MPa, the flexural strength is 185 MPa, the flexural modulus is 9.6 GPa, and the notched Izod impact strength at 23 °C is 9 kJ / m 2 ; the density of the modified alloy material is 1.35 g / cm 3 , and the melt index at 280 °C / 5 kg is 9 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 190 °C, and the shrinkage rate (MD / TD) is 0.3 / 0.35; the flame retardancy of the 1.5 mm modified alloy material is V0.

[0115] In this comparative example, the components and their contents in the modified alloy material are as follows: The polyphenylene ether is 21 parts by weight, and the intrinsic viscosity of the polyphenylene ether is 0.40 dL / g; The polyamide 66 is 25 parts by weight, and the intrinsic viscosity of the polyamide 66 is 2.7 dL / g; The glass fiber is 30 parts by weight, the glass fiber is round fiber, and the average diameter of the round fiber is 10 μm; The flame retardant is 13 parts by weight of aluminum diethyl phosphinate; The coupling agent is 0.5 part by weight of γ-glycidoxypropyltrimethoxysilane; The compatibilizer is 10 parts by weight of polyphenylene ether grafted maleic anhydride; The lubricant is 0.6 part by weight of silicone powder; The antioxidant is 0.2 part by weight of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and 0.2 part by weight of tris[2,4-di-tert-butylphenyl]phosphite.

[0116] This comparative example also provides a method for the modified alloy material. Take each component according to the content of each component. The preparation method includes the following steps: Step 1: Add polyphenylene ether, polyamide 66, flame retardant, coupling agent, compatibilizer, lubricant and antioxidant into a high-speed mixer, stir at 300 r / min for 3 min, and blend to obtain a mixture; Step 2: Feed the mixture into the main feeding port of a conventional twin-screw extruder, and add glass fiber into the conventional twin-screw extruder through the side feeding port of the conventional twin-screw extruder, melt and extrude, and pelletize to obtain the modified alloy material.

[0117] In Comparative Example 4-5, the conventional twin-screw extruder only includes a feeding barrel, a screw, and an extruder head. The conventional twin-screw extruder is divided into twelve temperature zones. Among them, the first temperature zone is 240°C, the second temperature zone is 280°C, the third temperature zone is 280°C, the fourth temperature zone is 270°C, the fifth temperature zone is 260°C, the sixth temperature zone is 260°C, the seventh temperature zone is 250°C, the eighth temperature zone is 240°C, the ninth temperature zone is 240°C, the tenth temperature zone is 240°C, the eleventh temperature zone is 250°C, and the twelfth temperature zone is 260°C.

[0118] In Examples 1-3 and Comparative Examples 1-4 of the present invention, the vertical twin-screw extruder is composed of a horizontal screw extruder 1 and a vertical screw extruder 2; The horizontal screw extruder 1 is evenly divided into thirteen sections of barrels according to the material moving direction. Among them, the first section of the barrel is the feeding barrel, and the second section of the barrel to the thirteenth section of the barrel are evenly divided into twelve temperature zones; the vertical screw extruder 2 is evenly divided into five sections of barrels according to the material moving direction. Among them, the first section of the barrel is the feeding barrel, and the second section of the barrel to the fifth section of the barrel are evenly divided into four temperature zones; The tail end of the fifth section of the barrel of the vertical screw extruder 2 is vertically and hermetically connected to the side feeding port of the fifth section of the barrel of the horizontal screw extruder 1, so that the horizontal screw extruder 1 and the vertical screw extruder 2 are vertically arranged; An extruder head is also provided at the tail end of the thirteenth section of the barrel of the horizontal screw extruder 1; The vertical twin-screw extruder is provided with a main feeding port 11, a main feeding port 21, and a side feeding port 12. Among them, the main feeding port 11 is provided at the first section of the barrel of the horizontal screw extruder 1, the main feeding port 21 is provided at the first section of the barrel of the vertical screw extruder 2, and the side feeding port 12 is provided at the eighth section of the barrel of the horizontal screw extruder 1; The structure of the screw in both the horizontal screw extruder 1 and the vertical screw extruder 2 is a twin-screw; the length-diameter ratio of the horizontal screw extruder 1 is 52:1, and the length-diameter ratio of the vertical screw extruder 2 is 16:1; Materials enter the vertical twin-screw extruder through the horizontal screw extruder 1 and the vertical screw extruder 2 respectively, and are mixed together at the fifth section of the barrel of the horizontal screw extruder 1.

[0119] In Examples 1-3 and Comparative Examples 1-4, the operating temperature of the horizontal screw extruder 1 of the vertical twin-screw twin extruder in Step 3 is 260-310 °C. Among them, the temperatures of the twelve temperature zones are as follows: the temperature of the first temperature zone is 280 °C, the temperature of the second temperature zone is 300 °C, the temperature of the third temperature zone is 310 °C, the temperature of the fourth temperature zone is 300 °C, the temperature of the fifth temperature zone is 280 °C, the temperature of the sixth temperature zone is 270 °C, the temperature of the seventh temperature zone is 270 °C, the temperature of the eighth temperature zone is 270 °C, the temperature of the ninth temperature zone is 260 °C, the temperature of the tenth temperature zone is 260 °C, the temperature of the eleventh temperature zone is 260 °C, and the temperature of the twelfth temperature zone is 260 °C; The main motor current of the horizontal screw extruder 1 is 95 A, the screw speed is 350 rpm, the melt temperature is 285 °C, the temperature of the extruder head is 290 °C, the vacuum degree is 0.05 MPa, the torque is 270 N•m, and the feeding speed of the main feeding port 11 is 50 kg / h; In Step 3, the operating temperature of the vertical screw extruder 2 of the vertical twin-screw twin extruder is 250-270 °C. Among them, the temperatures of the four temperature zones are as follows: the temperature of the first temperature zone is 250 °C, the temperature of the second temperature zone is 270 °C, the temperature of the third temperature zone is 270 °C, and the temperature of the fourth temperature zone is 270 °C; The screw speed of the vertical screw extruder 2 is 400 rpm, and the feeding speed of the main feeding port 21 is 50 kg / h; In Step 6, the operating temperature of the horizontal screw extruder 1 of the vertical twin-screw twin extruder is 240-280 °C. Among them, the temperatures of the twelve temperature zones are as follows: the temperature of the first temperature zone is 240 °C, the temperature of the second temperature zone is 280 °C, the temperature of the third temperature zone is 280 °C, the temperature of the fourth temperature zone is 270 °C, the temperature of the fifth temperature zone is 260 °C, the temperature of the sixth temperature zone is 260 °C, the temperature of the seventh temperature zone is 250 °C, the temperature of the eighth temperature zone is 240 °C, the temperature of the ninth temperature zone is 240 °C, the temperature of the tenth temperature zone is 240 °C, the temperature of the eleventh temperature zone is 250 °C, and the temperature of the twelfth temperature zone is 260 °C; The main motor current of the horizontal screw extruder 1 is 95 A, the screw speed is 350 rpm, the melt temperature is 260 °C, the temperature of the extruder head is 255 °C, the vacuum degree is 0.05 MPa, the torque is 270 N•m, the feeding speed of the main feeding port 11 is 50 kg / h, and the feeding speed of the side feeding port 12 is 45 kg / h; In Step 6, the operating temperature of the vertical screw extruder 2 of the vertical twin-screw twin extruder is 220-250 °C. Among them, the temperatures of the four temperature zones are as follows: the temperature of the first temperature zone is 220 °C, the temperature of the second temperature zone is 250 °C, the temperature of the third temperature zone is 250 °C, and the temperature of the fourth temperature zone is 250 °C; The screw speed of the vertical screw extruder 2 is 400 rpm, and the feeding speed of the main feeding port 21 is 50 kg / h.

[0120] Table 1 shows the components and contents of the modified alloy materials described in Examples 1-3 and Comparative Examples 1-5.

[0121] Table 2 shows the components and contents of the viscosity-reducing compatibilizing masterbatch described in Examples 1-3 and Comparative Example 4.

[0122] Table 3 shows the properties of the modified alloy materials described in Examples 1-3 and Comparative Examples 1-5.

[0123] As shown in Tables 1-3, in the modified alloy materials described in Examples 1-3, the mixed viscosity-reducing compatibilizing masterbatch has good compatibility with polyphenylene ether and polyamide 66, good processability. The modified alloy materials prepared by mixing with polyphenylene ether, polyamide 66 and other materials have good mechanical properties, moderate melt index, high heat distortion temperature, low shrinkage rate, and high flame retardancy. For the materials in Comparative Examples 1-3, whether a compatibilizer is added or not, their mechanical properties and heat resistance are reduced to varying degrees, and the viscosity of the system increases, making the processing difficult and thus the performance is reduced. In Comparative Example 4, a viscosity-reducing compatibilizing masterbatch was prepared by a vertical twin-screw extruder, and a modified alloy material was prepared by a conventional twin-screw extruder. At the same processing temperature and process conditions, the differences in the melting points and viscosities of PPO, PA66 and the viscosity-reducing compatibilizing masterbatch result in poorer compatibility during main feeding and blending compared to the vertical twin-screw extruder, resulting in poorer material performance. In Comparative Example 5, all materials were prepared by a conventional twin-screw extruder. Similarly, the differences in melting point, viscosity, etc. lead to poor compatibility and poor mechanical properties, and the comprehensive performance is also reduced.

[0124] From the above, it can be seen that the modified alloy material of the present invention has a very wide range of uses, low cost, and extremely high market prospects.

[0125] The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any other form. Any modification or equivalent change made according to the technical essence of the present invention still belongs to the scope protected by the present invention.

Claims

1. A modified alloy material, characterized in that, The modified alloy material is prepared by blending polyphenylene ether, polyamide 66, viscosity-reducing compatibilizing masterbatch, glass fiber, flame retardant, lubricant and antioxidant; the tensile strength of the modified alloy material is 150-180 MPa, the flexural strength is 210-230 MPa, the flexural modulus is 9-12 GPa, and the notched Izod impact strength at 23 °C is 13-15 kJ / m 2 ; the density of the modified alloy material is 1.3-1.4 g / cm 3 , and the melt index at 280 °C / 5 kg is 10-50 g / 10 min; the heat distortion temperature of the modified alloy material under 1.82 MPa is 190-220 °C, and the shrinkage rate is (0.15-0.3) / (0.25-0.3); the flame retardancy of the 1.5 mm modified alloy material is V0; The viscosity-reducing compatibilizing masterbatch is prepared by blending polyphenylene ether, polyamide 6, an active agent, a coupling agent and an initiator in a vertical twin-screw extruder.

2. The modified alloy material according to claim 1, characterized in that The components and their contents in the modified alloy material are as follows: The polyphenylene ether is 10-30 parts by weight; The polyamide 66 is 10-25 parts by weight; The viscosity-reducing compatibilizing masterbatch is 10-30 parts by weight; The glass fiber is 20-40 parts by weight; The flame retardant is 10-20 parts by weight; The lubricant is 0.5-1 part by weight; The antioxidant is 0.3-0.5 part by weight.

3. The modified alloy material according to claim 1, characterized in that, The components and their contents in the viscosity-reducing compatibilizing masterbatch are as follows: Polyphenylene ether: 30-80 parts by weight; Polyamide 6: 30-80 parts by weight; Active agent: 0.1-1 part by weight; Coupling agent: 0.1-1 part by weight; Initiator: 0.1-1 part by weight.

4. The modified alloy material according to claim 1, wherein, The vertical twin-screw extruder is composed of a horizontal screw extruder (1) and a vertical screw extruder (2); the horizontal screw extruder (1) is evenly divided into thirteen sections of barrels according to the material moving direction, wherein the first section of barrel is the feeding barrel, and the second section to the thirteenth section of barrels are evenly divided into twelve temperature zones; the vertical screw extruder (2) is evenly divided into five sections of barrels according to the material moving direction, wherein the first section of barrel is the feeding barrel, and the second section to the fifth section of barrels are evenly divided into four temperature zones; The tail end of the fifth section of barrel of the vertical screw extruder (2) is vertically and hermetically connected to the side feeding port of the fifth section of barrel of the horizontal screw extruder (1), so that the horizontal screw extruder (1) and the vertical screw extruder (2) are vertically arranged.

5. The modified alloy material according to claim 4, wherein The vertical twin-screw extruder is provided with a main feeding port one (11), a main feeding port two (21) and a side feeding port three (12), wherein the main feeding port one (11) is arranged at the first section of barrel of the horizontal screw extruder (1), the main feeding port two (21) is arranged at the first section of barrel of the vertical screw extruder (2), and the side feeding port three (12) is arranged at the eighth section of barrel of the horizontal screw extruder (1).

6. The modified alloy material according to claim 4, wherein The structures of the screws in the horizontal screw extruder (1) and the vertical screw extruder (2) are both twin-screws; the length-diameter ratio of the horizontal screw extruder (1) is (48-52):1, and the length-diameter ratio of the vertical screw extruder (2) is 16:

1.

7. The modified alloy material according to claim 4, characterized in that, Materials enter the vertical twin-screw extruder through the horizontal screw extruder (1) and the vertical screw extruder (2) respectively, and are mixed together at the fifth section of barrel of the horizontal screw extruder (1).

8. A method for preparing the modified alloy material according to any one of claims 1-7, characterized in that, Take each component according to the content of each component, and the preparation method includes the following steps: Step 1: Heat and stir the polyphenylene ether and the active agent at high speed in a high-speed mixer, spray the coupling agent while stirring for blending, after the blending is completed, cool to room temperature, and then add the initiator and continue stirring to obtain premix one; Step 2: Heat and stir the polyamide 6 and the active agent at high speed in a high-speed mixer, spray the coupling agent while stirring for blending, and after the blending is completed, cool to room temperature to obtain premix two; Step 3: Feed the first premix into the vertical twin-screw double extruder through the first main feeding port (11), and feed the second premix into the vertical twin-screw double extruder through the second main feeding port (21). After melting and blending, extrude and pelletize to obtain the viscosity-reducing and compatibility-improving masterbatch. Step 4: Stir and blend polyphenylene ether, the viscosity-reducing and compatibility-improving masterbatch, lubricant, and antioxidant in a high-speed mixer to obtain the first mixture. Step 5: Add polyamide 66 and flame retardant into the high-speed mixer and stir and blend to obtain the second mixture. Step 6: Feed the first mixture into the vertical twin-screw double extruder through the first main feeding port (11), feed the second mixture into the vertical twin-screw double extruder through the second main feeding port (21), and side-feed glass fiber into the vertical twin-screw double extruder through the third side feeding port (12). After melting and extruding, pelletize to obtain the modified alloy material.

9. The preparation method according to claim 8, characterized in that, The initiator in Step 1 is diisopropylbenzene peroxide.

10. An electrical appliance housing, characterized in that, The electrical appliance housing is prepared from the modified alloy material according to any one of claims 1-7.

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