A high heat-resistant bio-based polyamide material and its preparation method

Abstract

The present invention relates to the technical field of polyamide materials, and particularly relates to a high heat-resistant bio-based polyamide material and a preparation method thereof, which comprise the following raw materials in parts by weight: 45-50 parts of PA56, 7-11 parts of a balanced multi-effect agent doped with a filler modifier, 5-8 parts of a flame retardant, 4-7 parts of a silane coupling agent, 3-5 parts of an antioxidant, and 2-4 parts of a lubricant. The bio-based polyamide material of the present invention uses bio-based PA56 as the matrix, and at the same time adds a flame retardant, a silane coupling agent, an antioxidant and a lubricant as functional aids, and a balanced multi-effect agent doped with a filler modifier and a stability-enhancing agent are added. Through the coordination of the raw materials, the bio-based polyamide material obtained has coordinated improvements in dielectric loss, flame retardancy and wear resistance, and at the same time, the product has remarkable weather resistance and high heat stability effects.

Description

Technical Field

[0001] The present invention relates to the technical field of polyamide materials, and particularly relates to a high heat-resistant bio-based polyamide material and a preparation method thereof. Background Art

[0002] As a special engineering plastic, polyamide has both the excellent properties of aromatic polyamide and the processing properties of aliphatic polyamide. It is a kind of material with excellent properties and has been widely used in the fields of electronic appliances, LED lighting, automotive industry, etc., and has gradually developed into the main product of special engineering plastics.

[0003] The existing bio-based polyamide material (PA56) has poor flame retardancy. In order to enhance the flame retardancy, flame retardants such as inorganic magnesium hydroxide are added. The binding force between the flame retardant and the product raw materials is poor and it is easy to agglomerate, which instead affects the dielectric loss and wear resistance of the product. It is difficult to balance and improve the product performance, and the product has poor weather resistance and high heat stability, which further limits the use efficiency of the product. Summary of the Invention

[0004] Aiming at the defects of the prior art, the purpose of the present invention is to provide a high heat-resistant bio-based polyamide material and a preparation method thereof to solve the problems mentioned in the above background art.

[0005] The present invention solves the technical problems by adopting the following technical solutions:

[0006] The present invention provides a high heat-resistant bio-based polyamide material, and the bio-based polyamide material comprises the following raw materials in parts by weight:

[0007] 45-50 parts of PA56, 7-11 parts of a balanced multi-effect agent doped with a filler modifier, 5-8 parts of a flame retardant, 4-7 parts of a silane coupling agent, 3-5 parts of an antioxidant, and 2-4 parts of a lubricant;

[0008] Among them, the preparation method of the balanced multi-effect agent doped with a filler modifier is as follows:

[0009] A first modification liquid and a second modification liquid are uniformly mixed to obtain a modified compounding liquid, and then a balanced agent is prepared by mixing and stirring a pretreated zinc oxide whisker, glass fiber, cerium oxide and dopamine hydrochloride solution. Finally, a balanced multi-effect agent doped with a filler modifier is obtained by mixing and ball milling the modified compounding liquid and the balanced agent doped with a filler.

[0010] Preferably, the high heat-resistant bio-based polyamide material comprises the following raw materials in parts by weight:

[0011] 47.5 parts of PA56, 9 parts of a balanced multi-effect agent doped with a filler modifier, 6.5 parts of a flame retardant, 5.5 parts of a silane coupling agent, 4 parts of an antioxidant, and 3 parts of a lubricant.

[0012] Preferably, the relative viscosity number of the PA56 is 2.8; the flame retardant is magnesium hydroxide;

[0013] the silane coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 168; the lubricant is polyethylene wax.

[0014] Preferably, the preparation method of the balanced multi-effect agent doped with a filler modifier is as follows:

[0015] S01: Mix 3 parts by weight of silane coupling agent KH560, 5 parts by weight of a 3% chitosan solution by mass fraction, and 1 part by weight of an ethanol solvent at a mixing temperature of 40 °C for 1 h to obtain a silane coupling solution;

[0016] Mix 3 - 5 parts of alumina powder, 1 - 3 parts of boron nitride, and 4 - 7 parts of the silane coupling solution thoroughly to obtain a first modified solution;

[0017] S02: Mix 2 - 4 parts of barium titanate, 1 - 2 parts of barium nitrate solution, and 2 - 3 parts of sodium silicate solution thoroughly to obtain a second modified solution;

[0018] Mix the first modified solution and the second modified solution thoroughly in a weight ratio of (5 - 8):3 to obtain a modified compounding solution;

[0019] S03: Preparation of the doped balancing agent:

[0020] Mix zinc oxide whiskers thoroughly in a sufficient amount of a 5% potassium permanganate solution by mass fraction, and then wash with boiling water 2 - 3 times to obtain pretreated zinc oxide whiskers;

[0021] Mix 4 - 6 parts of pretreated zinc oxide whiskers, 3 - 4 parts of glass fiber, 1 - 3 parts of cerium oxide, and 5 - 8 parts of a 5% hydrochloric acid dopamine solution by mass fraction by stirring. After stirring, filter by suction and dry to obtain a doped balancing agent;

[0022] S04: Mix and ball-mill the modified compounding solution and the doped balancing agent in a weight ratio of 5:(2 - 3) at a ball-milling speed of 1000 - 1500 r / min for 1 h. After ball-milling, filter by suction and dry to obtain the balanced multi-effect agent of the doped filler modifier.

[0023] Preferably, the alumina powder is spherical alumina particles with a particle size of 2 - 5 µm; the mass fraction of the barium nitrate solution is 3 - 5%; the mass fraction of the sodium silicate solution is 4 - 7%.

[0024] Preferably, the stirring speed of the mixing and stirring treatment is 400 - 450 r / min, stirring for 20 - 30 min, and the stirring temperature is 52 - 56 °C.

[0025] Preferably, 5-8 parts of a stability-resistant improver are further added to the bio-based polyamide material, and the preparation method of the stability-resistant improver is as follows:

[0026] S11: Preheat cordierite at 60-65 °C for 1 h, and add the preheated cordierite to a 5% sodium alginate solution according to a weight ratio of 3:5 and disperse evenly to obtain a cordierite solution;

[0027] S12: Add 3-5 parts of nano-silica sol and 1-2 parts of sodium carboxymethylcellulose to 5-8 parts of Tris-HCl buffer solution, and then add 2-3 parts of yttrium nitrate solution and stir well to obtain a modified silica sol;

[0028] S13: Blend and ball-mill 3-5 parts of cordierite solution, 2-3 parts of zirconia and 5-8 parts of modified silica sol, with a ball-milling speed of 1500 r / min and ball-mill for 1 h. After the ball-milling is completed, filter and dry to obtain the stability-resistant improver.

[0029] Preferably, the pH value of the Tris-HCl buffer solution is 8-9; the mass fraction of the yttrium nitrate solution is 3-5%.

[0030] The present invention also provides a preparation method of a high heat-resistant bio-based polyamide material, including the following steps:

[0031] Weigh the raw materials according to parts by weight, add the raw materials to a twin-screw extruder for extrusion in sequence, and finally draw, cool and pelletize to obtain a high heat-resistant bio-based polyamide material.

[0032] Preferably, the melting and plasticizing temperature in the extruder is 300-330 °C, and the rotation speed of the extrusion screw is 500 rpm / min.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The bio-based polyamide material of the present invention uses bio-based PA56 as the matrix, and at the same time adds a flame retardant, a silane coupling agent, an antioxidant and a lubricant as functional aids, and the balanced multi-effect agent of the added blending filler modifier is combined with the stability-resistant improver. Through the coordination and cooperation of the raw materials, the bio-based polyamide material obtained has coordinated improvements in dielectric loss, flame retardancy and wear resistance, and at the same time, the product has remarkable weather resistance and high heat stability effects;

[0035] 2. The balanced multi-effect agent doped with a filler modifier uses alumina powder, boron nitride, and a silane coupling solution as the first modifier, and barium titanate, barium nitrate solution, and sodium silicate solution as the second modifier. Through the coordination of the first modifier and the second modifier, with alumina powder, boron nitride, and barium titanate as the matrix, and then blending with raw materials such as barium nitrate solution and sodium silicate solution, the obtained modified compounding liquid can better coordinate the doped balancing agent, thereby enhancing the performance effect of the product system;

[0036] 3. The doped balancing agent is optimized by potassium permanganate solution for zinc oxide whiskers, and then improved by blending and stirring with glass fiber, cerium oxide, and 5% by mass of dopamine hydrochloride solution. The whisker-shaped zinc oxide whiskers are combined with needle-shaped glass fibers and then incorporated into the system to enhance the interfacial property between the systems. At the same time, it is further blended with raw materials such as alumina powder and boron nitride in the modified compounding liquid into the system to further enhance the coordination of the dielectric loss, flame retardancy, and wear resistance of the system. Meanwhile, the product has remarkable weather resistance and high heat stability effects;

[0037] 4. The heat-resistant supplement agent uses cordierite after preheating, and is then improved by dispersion with sodium alginate solution, and a modified nano-silica sol is obtained by co-blending nano-silica sol, sodium carboxymethylcellulose, Tris-HCl buffer solution, and yttrium nitrate solution. By improving the nano-silica sol, cordierite and zirconia raw materials can be better incorporated into the product system, and the obtained heat-resistant supplement agent can further coordinate the balanced multi-effect agent of the doped filler modifier, and thus the performance of the product is further improved. Specific embodiments

[0038] The following combines specific embodiments to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0039] A high heat-resistant bio-based polyamide material in this embodiment, the bio-based polyamide material includes the following raw materials in parts by weight:

[0040] 45 - 50 parts of PA56, 7 - 11 parts of the balanced multi-effect agent doped with a filler modifier, 5 - 8 parts of a flame retardant, 4 - 7 parts of a silane coupling agent, 3 - 5 parts of an antioxidant, and 2 - 4 parts of a lubricant; wherein the preparation method of the balanced multi-effect agent doped with a filler modifier is:

[0041] The first modification liquid and the second modification liquid are mixed evenly to obtain a modified compounding liquid, and then a blended balance agent is prepared by mixing and stirring a pretreated zinc oxide whisker, glass fiber, cerium oxide and a hydrochloric acid dopamine solution. Finally, a balanced multi-effect agent filled with a modified filler modifier is obtained by mixing and ball milling the modified compounding liquid and the blended balance agent.

[0042] The high heat-resistant bio-based polyamide material of this embodiment comprises the following raw materials in parts by weight:

[0043] 47.5 parts of PA56, 9 parts of a balanced multi-effect agent filled with a modified filler modifier, 6.5 parts of a flame retardant, 5.5 parts of a silane coupling agent, 4 parts of an antioxidant, and 3 parts of a lubricant.

[0044] The relative viscosity number of PA56 in this embodiment is 2.8; the flame retardant is magnesium hydroxide;

[0045] The silane coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 168; the lubricant is polyethylene wax.

[0046] The preparation method of the balanced multi-effect agent filled with a modified filler modifier in this embodiment is as follows:

[0047] S01: Mix 3 parts by weight of silane coupling agent KH560, a 3% chitosan solution by mass fraction and an ethanol solvent in a weight ratio of 3:5:1, and mix at a temperature of 40 °C for 1 h to obtain a silane coupling liquid;

[0048] Mix 3 - 5 parts of alumina powder, 1 - 3 parts of boron nitride and 4 - 7 parts of the silane coupling liquid evenly to obtain the first modification liquid;

[0049] S02: Mix 2 - 4 parts of barium titanate, 1 - 2 parts of barium nitrate solution and 2 - 3 parts of sodium silicate solution evenly to obtain the second modification liquid;

[0050] Mix the first modification liquid and the second modification liquid evenly in a weight ratio of (5 - 8):3 to obtain a modified compounding liquid;

[0051] S03: Preparation of the blended balance agent:

[0052] Mix the zinc oxide whisker evenly in a sufficient amount of a 5% potassium permanganate solution by mass fraction, and then wash it with boiling water 2 - 3 times to obtain a pretreated zinc oxide whisker;

[0053] Mix 4 - 6 parts of the pretreated zinc oxide whisker, 3 - 4 parts of glass fiber, 1 - 3 parts of cerium oxide and 5 - 8 parts of a 5% hydrochloric acid dopamine solution by mass fraction, stir and process, and after stirring ends, filter and dry to obtain the blended balance agent;

[0054] S04: The modified compounding liquid and the added balancing agent are mixed and ball-milled in a weight ratio of 5:(2~3) at a ball-milling speed of 1000~1500r / min for 1h. After the ball-milling is completed, the mixture is filtered and dried to obtain a balancing multi-effect agent added with a filler modifier.

[0055] The alumina powder of this embodiment is spherical alumina particles with a particle size of 2-5 μm; the mass fraction of the barium nitrate solution is 3-5%; and the mass fraction of the sodium silicate solution is 4-7%.

[0056] The stirring speed of the blending and stirring process in this embodiment is 400-450 r / min, stirring is 20-30 min, and the stirring temperature is 52-56°C.

[0057] The bio-based polyamide material of this embodiment further comprises 5 to 8 parts of a stable supplementing agent, wherein the preparation method of the stable supplementing agent is as follows:

[0058] S11: preheating the cordierite at 60-65° C. for 1 h, adding the preheated cordierite into a 5% by mass sodium alginate solution at a weight ratio of 3:5 and dispersing the mixture evenly to obtain a cordierite liquid;

[0059] S12: adding 3-5 parts of nano-silica sol and 1-2 parts of sodium carboxymethyl cellulose to 5-8 parts of Tris-HCl buffer solution, and then adding 2-3 parts of yttrium nitrate solution, stirring sufficiently, to obtain modified silica sol;

[0060] S13: 3-5 parts of cordierite liquid, 2-3 parts of zirconium oxide and 5-8 parts of modified silica sol are mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball-milling is completed, the mixture is filtered and dried to obtain a stable replenisher.

[0061] The pH value of the Tris-HCl buffer solution in this embodiment is 8-9; the mass fraction of the yttrium nitrate solution is 3-5%.

[0062] A method for preparing a highly heat-resistant bio-based polyamide material in this embodiment comprises the following steps:

[0063] The raw materials are weighed according to weight, and are sequentially added into a twin-screw extruder for extrusion, and finally are drawn, cooled, and pelletized to obtain a highly heat-resistant bio-based polyamide material.

[0064] In the extruder of this embodiment, the melt plasticization temperature is 300-330° C., and the extrusion screw speed is 500 rpm / min.

[0065] Example 1.

[0066] A highly heat-resistant bio-based polyamide material according to this embodiment includes the following raw materials in parts by weight:

[0067] 45 parts of PA56, 7 parts of balanced multi-effect agent with blended filler modifier, 5 parts of flame retardant, 4 parts of silane coupling agent, 3 parts of antioxidant, 2 parts of lubricant.

[0068] The relative viscosity number of PA56 in this example is 2.8; the flame retardant is magnesium hydroxide;

[0069] The silane coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 168; the lubricant is polyethylene wax.

[0070] The preparation method of the balanced multi-effect agent with blended filler modifier in this example is as follows:

[0071] S01: Mix 3 parts of silane coupling agent KH560, 5 parts of chitosan solution with a mass fraction of 3%, and ethanol solvent in a weight ratio of 3:5:1, with a mixing temperature of 40 °C for 1 h to obtain a silane coupling solution;

[0072] Mix 3 parts of alumina powder, 1 part of boron nitride, and 4 parts of silane coupling solution thoroughly to obtain a first modified solution;

[0073] S02: Mix 2 parts of barium titanate, 1 part of barium nitrate solution, and 2 parts of sodium silicate solution thoroughly to obtain a second modified solution;

[0074] Mix the first modified solution and the second modified solution thoroughly in a weight ratio of 5:3 to obtain a modified compounding solution;

[0075] S03: Preparation of the blended balance agent:

[0076] Mix zinc oxide whiskers thoroughly in a sufficient amount of potassium permanganate solution with a mass fraction of 5%, and then wash with boiling water 2 times to obtain pretreated zinc oxide whiskers;

[0077] Mix 4 parts of pretreated zinc oxide whiskers, 3 parts of glass fiber, 1 part of cerium oxide, and 5 parts of hydrochloric acid dopamine solution with a mass fraction of 5% by stirring. After stirring, filter and dry to obtain the blended balance agent;

[0078] S04: Blend and ball-mill the modified compounding solution and the blended balance agent in a weight ratio of 5:2, with a ball-milling speed of 1000 r / min for 1 h. After ball-milling, filter and dry to obtain the balanced multi-effect agent with blended filler modifier.

[0079] The alumina powder in this example is spherical alumina particles with a particle size of 2 µm; the mass fraction of the barium nitrate solution is 3%; the mass fraction of the sodium silicate solution is 4%.

[0080] The stirring speed of the blending and stirring treatment in this example is 400 r / min, stirring for 20 min, and the stirring temperature is 52 °C.

[0081] The bio-based polyamide material of this embodiment further adds 5 parts of a stable improver, and the preparation method of the stable improver is as follows:

[0082] S11: Preheat cordierite at 60 °C for 1 h, and add the preheated cordierite to a 5% sodium alginate solution according to a weight ratio of 3:5 and disperse evenly to obtain a cordierite solution;

[0083] S12: Add 3 parts of nano-silica sol and 1 part of sodium carboxymethylcellulose to 5 parts of Tris-HCl buffer solution, and then add 2 parts of yttrium nitrate solution and stir well to obtain a modified silica sol;

[0084] S13: Blend and ball-mill 3 parts of cordierite solution, 2 parts of zirconia and 5 parts of modified silica sol, with a ball-mill speed of 1500 r / min for 1 h. After the ball-milling is completed, filter and dry to obtain a stable improver.

[0085] The pH value of the Tris-HCl buffer solution in this embodiment is 8; the mass fraction of the yttrium nitrate solution is 3%.

[0086] The preparation method of a high heat-resistant bio-based polyamide material in this embodiment includes the following steps:

[0087] Weigh the raw materials according to parts by weight, add the raw materials to a twin-screw extruder for extrusion in sequence, and finally draw, cool and pelletize to obtain a high heat-resistant bio-based polyamide material.

[0088] The melting and plasticizing temperature in the extruder of this embodiment is 300 °C, and the rotation speed of the extrusion screw is 500 rpm / min.

[0089] Example 2.

[0090] A high heat-resistant bio-based polyamide material in this embodiment, and the bio-based polyamide material includes the following raw materials in parts by weight:

[0091] 50 parts of PA56, 11 parts of a balanced multi-effect agent doped with a filler modifier, 8 parts of a flame retardant, 7 parts of a silane coupling agent, 5 parts of an antioxidant, and 4 parts of a lubricant.

[0092] The relative viscosity number of PA56 in this embodiment is 2.8; the flame retardant is magnesium hydroxide;

[0093] The silane coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 168; the lubricant is polyethylene wax.

[0094] The preparation method of the balanced multi-effect agent doped with a filler modifier in this embodiment is as follows:

[0095] S01: Mix 3 parts by weight of silane coupling agent KH560, 5 parts by weight of a 3% chitosan solution by mass fraction, and 1 part by weight of ethanol solvent at 40°C for 1 hour to obtain a silane coupling solution;

[0096] Mix 5 parts of alumina powder, 3 parts of boron nitride, and 7 parts of the silane coupling solution thoroughly to obtain a first modified solution;

[0097] S02: Mix 4 parts of barium titanate, 2 parts of barium nitrate solution, and 3 parts of sodium silicate solution thoroughly to obtain a second modified solution;

[0098] Mix the first modified solution and the second modified solution thoroughly at a weight ratio of 8:3 to obtain a modified compounding solution;

[0099] S03: Preparation of the blended balance agent:

[0100] Mix zinc oxide whiskers thoroughly in a sufficient amount of 5% potassium permanganate solution by mass fraction, and then wash with boiling water 3 times to obtain pretreated zinc oxide whiskers;

[0101] Mix 6 parts of pretreated zinc oxide whiskers, 4 parts of glass fiber, 3 parts of cerium oxide, and 8 parts of 5% hydrochloric acid dopamine solution by mass fraction by stirring. After stirring, filter by suction and dry to obtain the blended balance agent;

[0102] S04: Blend and ball-mill the modified compounding solution and the blended balance agent at a weight ratio of 5:3. The ball-milling speed is 1500 r / min, and ball-mill for 1 hour. After ball-milling, filter by suction and dry to obtain a balanced multi-effect agent doped with a filler modifier.

[0103] In this example, the alumina powder is spherical alumina particles with a particle size of 5 µm; the mass fraction of the barium nitrate solution is 5%; the mass fraction of the sodium silicate solution is 7%.

[0104] In this example, the stirring speed of the blending and stirring treatment is 450 r / min, stir for 30 min, and the stirring temperature is 56°C.

[0105] In the bio-based polyamide material of this example, 8 parts of a stable supplement agent are also added. The preparation method of the stable supplement agent is as follows:

[0106] S11: Preheat cordierite at 65°C for 1 hour, and add the preheated cordierite to a 5% sodium alginate solution by mass fraction at a weight ratio of 3:5 and disperse evenly to obtain a cordierite solution;

[0107] S12: Add 5 parts of nano-silica sol and 2 parts of sodium carboxymethylcellulose to 8 parts of Tris-HCl buffer solution, and then add 3 parts of yttrium nitrate solution and stir thoroughly to obtain a modified silica sol;

[0108] S13: 5 parts of cordierite liquid, 3 parts of zirconium oxide and 8 parts of modified silica sol were mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball-milling was completed, the mixture was filtered and dried to obtain a stable replenisher.

[0109] The pH value of the Tris-HCl buffer solution in this embodiment is 9; the mass fraction of the yttrium nitrate solution is 5%.

[0110] A method for preparing a highly heat-resistant bio-based polyamide material in this embodiment comprises the following steps:

[0111] The raw materials are weighed according to weight, and are sequentially added into a twin-screw extruder for extrusion, and finally are drawn, cooled, and pelletized to obtain a highly heat-resistant bio-based polyamide material.

[0112] In the extruder of this embodiment, the melt plasticization temperature is 330° C. and the extrusion screw speed is 500 rpm / min.

[0113] Example 3.

[0114] A highly heat-resistant bio-based polyamide material according to this embodiment includes the following raw materials in parts by weight:

[0115] PA56 47.5 parts, balanced multi-effect agent for filler modifier 9 parts, flame retardant 6.5 parts, silane coupling agent 5.5 parts, antioxidant 4 parts, lubricant 3 parts.

[0116] The relative viscosity of PA56 in this embodiment is 2.8; the flame retardant is magnesium hydroxide;

[0117] The silane coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 168; and the lubricant is polyethylene wax.

[0118] The preparation method of the balanced multi-effect agent mixed with the filler modifier of this embodiment is:

[0119] S01: Silane coupling agent KH560, 3% chitosan solution and ethanol solvent were mixed in a weight ratio of 3:5:1 at a mixing temperature of 40°C for 1 hour to obtain a silane coupling liquid;

[0120] 4 parts of aluminum oxide powder, 2 parts of boron nitride and 5.5 parts of silane coupling liquid are fully mixed to obtain a first modified liquid;

[0121] S02: 3 parts of barium titanate, 1.5 parts of barium nitrate solution and 2.5 parts of sodium silicate solution are fully mixed to obtain a second modified solution;

[0122] The first modified liquid and the second modified liquid were mixed thoroughly at a weight ratio of 6.5:3 to obtain a modified compounding liquid;

[0123] S03: Preparation of the blended balance agent:

[0124] Mix zinc oxide whiskers thoroughly in a sufficient amount of 5% potassium permanganate solution by mass fraction, and then wash them with boiling water 3 times to obtain pretreated zinc oxide whiskers;

[0125] Blend and stir 5 parts of pretreated zinc oxide whiskers, 3.5 parts of glass fiber, 2 parts of cerium oxide and 6.5 parts of 5% hydrochloric acid dopamine solution by mass fraction. After stirring, filter by suction and dry to obtain the blended balance agent;

[0126] Blend and ball-mill the modified compounding liquid and the blended balance agent at a weight ratio of 5:2.5. The ball-milling speed is 1250 r / min, and ball-mill for 1 h. After ball-milling, filter by suction and dry to obtain the balanced multi-effect agent filled with the blended filler modifier.

[0127] The alumina powder in this example is spherical alumina particles with a particle size of 3.5 µm; the mass fraction of the barium nitrate solution is 4%; the mass fraction of the sodium silicate solution is 5.5%.

[0128] The stirring speed of the blending and stirring treatment in this example is 420 r / min, stir for 25 min, and the stirring temperature is 54 °C.

[0129] 6.5 parts of a stable supplement agent are also added to the bio-based polyamide material in this example. The preparation method of the stable supplement agent is as follows:

[0130] Preheat cordierite at 62 °C for 1 h first, and add the preheated cordierite to a 5% sodium alginate solution by weight ratio of 3:5 and disperse it evenly to obtain cordierite liquid;

[0131] Add 4 parts of nano-silica sol and 1.5 parts of sodium carboxymethylcellulose to 6.5 parts of Tris-HCl buffer solution, and then add 2.5 parts of yttrium nitrate solution, and stir thoroughly to obtain modified silica sol;

[0132] Blend and ball-mill 4 parts of cordierite liquid, 2.5 parts of zirconia and 6.5 parts of modified silica sol. The ball-milling speed is 1500 r / min, and ball-mill for 1 h. After ball-milling, filter by suction and dry to obtain the stable supplement agent.

[0133] The pH value of the Tris-HCl buffer solution in this example is 8.5; the mass fraction of the yttrium nitrate solution is 4%.

[0134] The preparation method of a high heat-resistant bio-based polyamide material in this example includes the following steps:

[0135] Weigh the raw materials by weight parts, add the raw materials to a twin-screw extruder in sequence for extrusion, and finally carry out strand pelletizing, cooling, and cutting to obtain a high heat-resistant bio-based polyamide material.

[0136] In the extruder of this example, the melting and plasticizing temperature is 315 °C, and the rotational speed of the extrusion screw is 500 rpm / min.

[0137] Comparative Example 1.

[0138] It is different from Example 3 in that the balanced multi-effect agent of the blending filler modifier is not added.

[0139] Comparative Example 2.

[0140] It is different from Example 3 in that the modified compounding liquid is not added in the preparation of the balanced multi-effect agent of the blending filler modifier.

[0141] Comparative Example 3.

[0142] It is different from Example 3 in that the first modification liquid is not added to the modified compounding liquid.

[0143] Comparative Example 4.

[0144] It is different from Example 3 in that alumina powder and boron nitride are not added to the first modification liquid.

[0145] Comparative Example 5.

[0146] It is different from Example 3 in that the second modification liquid is not added to the modified compounding liquid.

[0147] Comparative Example 6.

[0148] It is different from Example 3 in that barium titanate and barium nitrate solution are not added to the second modification liquid.

[0149] Comparative Example 7.

[0150] It is different from Example 3 in that the blended balance agent is not added in the preparation of the balanced multi-effect agent of the blending filler modifier.

[0151] Comparative Example 8.

[0152] It is different from Example 3 in that the pretreated zinc oxide whiskers and glass fibers are not added in the preparation of the blended balance agent.

[0153] Comparative Example 9.

[0154] It is different from Example 3 in that cerium oxide and dopamine hydrochloride solution are not added in the preparation of the blended balance agent, and water is used instead.

[0155] Comparative Example 10.

[0156] It is different from Example 3 in that the heat-resistant supplement agent is not added.

[0157] Conventional tests were conducted on the flame retardancy, dielectric loss, and abrasion resistance of Examples 1 to 3 and Comparative Examples 1 to 10, as well as the weather resistance and high heat stability of the test products (the products were placed at 75 °C for 24 h and then irradiated under ultraviolet conditions for 24 h, with an irradiation intensity of 100 W / m 2 , and the above was taken as one cycle, and the cycle test was carried out 10 times);

[0158]

[0159] It can be seen from Comparative Examples 1 to 10 and Examples 1 to 3;

[0160] The product of Example 3 has excellent limiting oxygen index, dielectric loss, and abrasion loss. The wear resistance, dielectric loss, and flame retardancy of the product can be coordinately improved. At the same time, the product has excellent stability under weather and high heat conditions;

[0161] It can be seen from Comparative Examples 1 to 10 and Example 3 that when one of the balanced multi-effect agent of the blending filler modifier and the stabilizing improver is not added to the product, the performance of the product deteriorates significantly. By using the two in coordination, the performance effect of the product is the most significant;

[0162] When the modified compounding liquid is not added in the preparation of the balanced multi-effect agent of the blending filler modifier, the first modified liquid is not added to the modified compounding liquid, alumina powder and boron nitride are not added to the first modified liquid, the second modified liquid is not added to the modified compounding liquid, and barium titanate and barium nitrate solution are not added to the second modified liquid, the performance of the product shows a deteriorating trend to varying degrees. By using the modified compounding liquid prepared by combining the specific first modified liquid and second modified liquid of the present invention, the performance effect of the product is the most significant;

[0163] When the blended balance agent is not added in the preparation of the balanced multi-effect agent of the blending filler modifier, the pretreated zinc oxide whiskers and glass fibers are not added in the preparation of the blended balance agent, and cerium oxide and dopamine hydrochloride solution are replaced by water in the preparation of the blended balance agent, the performance of the product shows a deteriorating trend to varying degrees. The performance effect of the blended balance agent obtained by the method of the present invention is the most excellent, and the performance effect of the balanced multi-effect agent of the blending filler modifier prepared by combining the blended balance agent obtained by the specific method of the present invention with the modified compounding liquid is the most significant; at the same time, the inventors of the present invention also found that when the stabilizing improver is not added to the product, the performance of the product also shows an obvious deteriorating trend.

[0164] Based on the above tests, the stabilizing improver of the present invention has a great influence on the product performance. Based on this, the present invention further explores it:

[0165] Experimental Example 1.

[0166] The difference from Example 3 is that cordierite liquid is not added in the preparation of the stabilizing improver.

[0167] Experimental Example 2

[0168] Different from Example 3, zirconia was not added in the preparation of the stability-resistant improver.

[0169] Experimental Example 3

[0170] Different from Example 3, modified silica sol was not added in the preparation of the stability-resistant improver.

[0171] Experimental Example 4

[0172] Different from Example 3, nano-silica sol and sodium carboxymethylcellulose were not added to the modified silica sol.

[0173] Experimental Example 5

[0174] Different from Example 3, yttrium nitrate solution was not added to the modified silica sol, and water was used instead of Tris-HCl buffer solution.

[0175]

[0176] It can be seen from Experimental Examples 1-5 that when cordierite liquid is not added in the preparation of the stability-resistant improver, the performance of the product deteriorates significantly. At the same time, when zirconia or modified silica sol is not added in the preparation of the stability-resistant improver, the performance effect of the product is poor. Therefore, when using zirconia and modified silica sol in combination with the cordierite liquid of the present invention, the product raw materials are proprietary. When using other raw materials in combination, the effect is not obvious. At the same time, when nano-silica sol and sodium carboxymethylcellulose are not added to the modified silica sol, or when yttrium nitrate solution is not added to the modified silica sol and water is used instead of Tris-HCl buffer solution, the performance of the product shows a deteriorating trend. The performance effect of the product is the most significant when using the modified silica sol obtained by the method of the present invention. Only when using the raw materials of the present invention in combination, the performance effect of the product is the most significant.

[0177] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0178] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A highly heat-resistant bio-based polyamide material, characterized in that: The bio-based polyamide material comprises the following raw materials in parts by weight: PA56 45-50 parts, balanced multi-effect agent for filler modifier 7-11 parts, flame retardant 5-8 parts, silane coupling agent 4-7 parts, antioxidant 3-5 parts, lubricant 2-4 parts and 5-8 parts of stable replenisher; The preparation method of the balanced multi-effect agent mixed with the filler modifier is as follows: S01: Silane coupling agent KH560, 3% chitosan solution and ethanol solvent were mixed in a weight ratio of 3:5:1 at a mixing temperature of 40°C for 1 hour to obtain a silane coupling liquid; 3-5 parts of aluminum oxide powder, 1-3 parts of boron nitride and 4-7 parts of silane coupling liquid are fully mixed to obtain a first modified liquid; S02: 2-4 parts of barium titanate, 1-2 parts of barium nitrate solution and 2-3 parts of sodium silicate solution are fully mixed to obtain a second modified solution; The first modified liquid and the second modified liquid are mixed thoroughly in a weight ratio of (5-8):3 to obtain a modified compounding liquid; S03: Preparation of balancing agent for blending: The zinc oxide whiskers are mixed with a sufficient amount of a 5% by mass potassium permanganate solution, and then washed with boiling water for 2 to 3 times to obtain pretreated zinc oxide whiskers; 4-6 parts of pretreated zinc oxide whiskers, 3-4 parts of glass fibers, 1-3 parts of cerium oxide and 5-8 parts of 5% by mass dopamine hydrochloride solution are mixed and stirred, and after the stirring is completed, the mixture is filtered and dried to obtain a mixed balancing agent; S04: The modified compounding liquid and the added balancing agent are mixed and ball-milled in a weight ratio of 5:(2~3), with a ball-milling speed of 1000~1500r / min for 1h. After the ball-milling is completed, the mixture is filtered and dried to obtain a balancing multi-effect agent mixed with a filler modifier; The preparation method of the stable supplement is as follows: S11: preheating the cordierite at 60-65° C. for 1 h, adding the preheated cordierite into a 5% by mass sodium alginate solution at a weight ratio of 3:5 and dispersing the mixture evenly to obtain a cordierite liquid; S12: adding 3-5 parts of nano-silica sol and 1-2 parts of sodium carboxymethyl cellulose to 5-8 parts of Tris-HCl buffer solution, and then adding 2-3 parts of yttrium nitrate solution, stirring sufficiently, to obtain modified silica sol; S13: 3-5 parts of cordierite liquid, 2-3 parts of zirconium oxide and 5-8 parts of modified silica sol are mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball-milling is completed, the mixture is filtered and dried to obtain a stable replenisher.

2. A highly heat-resistant bio-based polyamide material according to claim 1, characterized in that: The highly heat-resistant bio-based polyamide material also includes the following raw materials in parts by weight: PA56 47.5 parts, balanced multi-effect agent for blending filler modifier 9 parts, flame retardant 6.5 parts, silane coupling agent 5.5 parts, antioxidant 4 parts, lubricant 3 parts.

3. The highly heat-resistant bio-based polyamide material according to claim 1, characterized in that: The relative viscosity of the PA56 is 2.8; the flame retardant is magnesium hydroxide; The silane coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 168; and the lubricant is polyethylene wax.

4. The highly heat-resistant bio-based polyamide material according to claim 1, characterized in that: The alumina powder is spherical alumina particles with a particle size of 2 to 5 μm; The mass fraction of the barium nitrate solution is 3-5%; the mass fraction of the sodium silicate solution is 4-7%.

5. The highly heat-resistant bio-based polyamide material according to claim 1, characterized in that: The mixing and stirring process has a stirring speed of 400-450 r / min, a stirring time of 20-30 min, and a stirring temperature of 52-56° C.

6. The highly heat-resistant bio-based polyamide material according to claim 1, characterized in that: The pH value of the Tris-HCl buffer solution is 8-9; the mass fraction of the yttrium nitrate solution is 3-5%.

7. The method for preparing a highly heat-resistant bio-based polyamide material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The raw materials are weighed according to weight, and are sequentially added into a twin-screw extruder for extrusion, and finally are drawn, cooled, and pelletized to obtain a highly heat-resistant bio-based polyamide material.

8. The method for preparing a highly heat-resistant bio-based polyamide material according to claim 7, characterized in that: The melt plasticizing temperature in the extruder is 300-330° C., and the extrusion screw speed is 500 rpm / min.

Images