High-heat-resistance bio-based polyamide material and preparation method thereof

Abstract

The invention relates to the technical field of polyamide materials, in particular to a high-heat-resistance bio-based polyamide material and a preparation method thereof, and the high-heat-resistance bio-based polyamide material comprises the following raw materials in parts by weight: 45-50 parts of PA56, 7-11 parts of a balance 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. According to the bio-based polyamide material, the bio-based PA56 is adopted as a matrix, meanwhile, the flame retardant, the silane coupling agent, the antioxidant and the lubricant are added to serve as functional auxiliaries, the balance multi-effect agent doped with the filler modifier is added to be matched with the stable supplement agent, and the raw materials are blended, coordinated and jointly synergized, so that the flame retardant property of the bio-based polyamide material is improved, and the flame retardant property of the bio-based polyamide material is improved. The obtained bio-based polyamide material is harmoniously improved in dielectric loss, flame retardance and wear resistance, and meanwhile, the product is remarkable in weather resistance and high heat stability resistance.

Description

Technical Field

[0001] The invention relates to the technical field of polyamide materials, and in particular to a highly 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 performance of aliphatic polyamide. It is a kind of material with excellent performance. It is widely used in electronic appliances, LED lighting, automotive industry and other fields, and has gradually developed into the main product of special engineering plastics.

[0003] Existing bio-based polyamide materials (PA56) have poor flame retardancy. In order to enhance the flame retardancy, flame retardants such as inorganic magnesium hydroxide are added. The flame retardants have poor bonding with the product raw materials and are easy to agglomerate, which in turn affects the dielectric loss and wear resistance of the product. It is difficult to improve the product performance in a balanced manner. In addition, the product has poor weather resistance and high heat stability, which further limits the product's efficiency. Summary of the invention

[0004] In view of the defects of the prior art, the object of the present invention is to provide a highly heat-resistant bio-based polyamide material and a preparation method thereof to solve the problems raised in the above background technology.

[0005] The present invention solves the technical problem by adopting the following technical solution: The present invention provides a highly heat-resistant bio-based polyamide material, wherein 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; The preparation method of the balanced multi-effect agent mixed with the filler modifier is as follows: The first modifying liquid and the second modifying liquid are mixed to obtain a modified compounding liquid, and then the pretreated zinc oxide whisker, glass fiber, cerium oxide and dopamine hydrochloride solution are mixed and stirred to obtain a mixed balancing agent, and finally the modified compounding liquid and the mixed balancing agent are mixed and ball-milled to obtain a balanced multi-effect agent of a mixed filler modifier.

[0006] Preferably, the high heat-resistant bio-based polyamide material comprises the following raw materials in parts by weight: 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.

[0007] Preferably, 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.

[0008] Preferably, the preparation method of the balanced multi-effect agent mixed with the filler modifier is: 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) 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.

[0009] 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%; and the mass fraction of the sodium silicate solution is 4-7%.

[0010] Preferably, the mixing and stirring process has a stirring speed of 400-450 r / min, stirring for 20-30 min, and a stirring temperature of 52-56° C.

[0011] Preferably, 5 to 8 parts of a stable supplementing agent are further added to the bio-based polyamide material, wherein the preparation method of the stable supplementing agent is: 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.

[0012] Preferably, the pH value of the Tris-HCl buffer solution is 8-9; and the mass fraction of the yttrium nitrate solution is 3-5%.

[0013] The present invention also provides a method for preparing a highly heat-resistant bio-based polyamide material, comprising the following steps: 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.

[0014] Preferably, the melt plasticizing temperature in the extruder is 300-330° C., and the extrusion screw speed is 500 rpm / min.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The bio-based polyamide material of the present invention adopts bio-based PA56 as a matrix, and adds flame retardants, silane coupling agents, antioxidants and lubricants as functional additives, as well as a balanced multi-effect agent for adding filler modifiers and a stable supplementing agent. Through the coordination and matching of the raw materials, the obtained bio-based polyamide material has coordinated improvements in dielectric loss, flame retardancy and wear resistance, and the product has significant weather resistance and high heat stability. 2. The balanced multi-effect agent for the filler modifier is prepared by using alumina powder, boron nitride and silane coupling liquid as the first modified liquid, and barium titanate, barium nitrate solution and sodium silicate solution as the second modified liquid. The first modified liquid and the second modified liquid are coordinated and matched, and alumina powder, boron nitride and barium titanate are used as the matrix, and then the raw materials such as barium nitrate solution and sodium silicate solution are matched. The modified compound liquid obtained can better coordinate with the blended balancing agent, thereby enhancing the performance effect of the product system; 3. The balancing agent is improved and optimized with zinc oxide whiskers through potassium permanganate solution, and then improved by mixing and stirring glass fiber, cerium oxide and 5% by mass dopamine hydrochloride solution. The whisker-shaped zinc oxide whiskers are combined with needle-shaped glass fibers to be blended into the system to enhance the interface between the systems. At the same time, the aluminum oxide powder, boron nitride and other raw materials in the modified compounding liquid are blended into the system to further enhance the dielectric loss, flame retardancy and wear resistance of the system. At the same time, the product has significant weather resistance and high heat stability. 4. The stable replenishing agent is made of cordierite which is preheated and then dispersed and improved with sodium alginate solution, and modified nano-silica sol is obtained by co-preparing nano-silica sol, sodium carboxymethyl cellulose, Tris-HCl buffer solution and yttrium nitrate solution. By improving the nano-silica sol, the cordierite and zirconium oxide raw materials can be better incorporated into the product system, and the stable replenishing agent obtained can further coordinate the balanced multi-effect agent of the filler modifier, thereby further improving the performance of the product. DETAILED DESCRIPTION

[0016] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] A highly heat-resistant bio-based polyamide material according to this embodiment includes the following raw materials in parts by weight: PA56 45-50 parts, balanced multi-effect agent blended with filler modifier 7-11 parts, flame retardant 5-8 parts, silane coupling agent 4-7 parts, antioxidant 3-5 parts, lubricant 2-4 parts; wherein the preparation method of the balanced multi-effect agent blended with filler modifier is: The first modifying liquid and the second modifying liquid are mixed to obtain a modified compounding liquid, and then the pretreated zinc oxide whisker, glass fiber, cerium oxide and dopamine hydrochloride solution are mixed and stirred to obtain a mixed balancing agent, and finally the modified compounding liquid and the mixed balancing agent are mixed and ball-milled to obtain a balanced multi-effect agent of a mixed filler modifier.

[0018] The high heat-resistant bio-based polyamide material of this embodiment includes the following raw materials in parts by weight: 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.

[0019] The relative viscosity of PA56 in this embodiment 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.

[0020] The preparation method of the balanced multi-effect agent mixed with the filler modifier of this embodiment is: 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) 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.

[0021] 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%.

[0022] 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.

[0023] The bio-based polyamide material of this embodiment further contains 5 to 8 parts of a stable supplementing agent, wherein the preparation method of the stable supplementing agent 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.

[0024] 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%.

[0025] A method for preparing a highly heat-resistant bio-based polyamide material in this embodiment comprises the following steps: 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.

[0026] In the extruder of this embodiment, the melt plasticization temperature is 300-330° C., and the extrusion screw speed is 500 rpm / min.

[0027] Example 1. A highly heat-resistant bio-based polyamide material according to this embodiment includes the following raw materials in parts by weight: PA56 45 parts, balanced multi-effect agent for filler modifier 7 parts, flame retardant 5 parts, silane coupling agent 4 parts, antioxidant 3 parts, lubricant 2 parts.

[0028] The relative viscosity of PA56 in this embodiment 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.

[0029] The preparation method of the balanced multi-effect agent mixed with the filler modifier of this embodiment is: 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 parts of aluminum oxide powder, 1 part of boron nitride and 4 parts of silane coupling liquid are fully mixed to obtain a first modified liquid; S02: fully blending 2 parts of barium titanate, 1 part of barium nitrate solution and 2 parts of sodium silicate solution to obtain a second modified solution; The first modified liquid and the second modified liquid were mixed thoroughly in a weight ratio of 5:3 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 twice with boiling water to obtain pretreated zinc oxide whiskers; 4 parts of pretreated zinc oxide whiskers, 3 parts of glass fibers, 1 part of cerium oxide and 5 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, with a ball-milling speed of 1000 r / min and ball-milling for 1 hour. After the ball-milling is completed, the mixture is filtered and dried to obtain a balancing multi-effect agent added with a filler modifier.

[0030] The alumina powder of this embodiment is spherical alumina particles with a particle size of 2 µm; the mass fraction of the barium nitrate solution is 3%; and the mass fraction of the sodium silicate solution is 4%.

[0031] The stirring speed of the blending and stirring process in this embodiment is 400 r / min, stirring for 20 min, and stirring temperature is 52°C.

[0032] The bio-based polyamide material of this embodiment further contains 5 parts of a stable supplementing agent, wherein the preparation method of the stable supplementing agent is as follows: S11: preheating the cordierite at 60° 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 parts of nano-silica sol and 1 part of sodium carboxymethyl cellulose to 5 parts of Tris-HCl buffer solution, and then adding 2 parts of yttrium nitrate solution, stirring sufficiently, to obtain modified silica sol; S13: 3 parts of cordierite liquid, 2 parts of zirconium oxide and 5 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.

[0033] The pH value of the Tris-HCl buffer solution in this embodiment is 8; the mass fraction of the yttrium nitrate solution is 3%.

[0034] A method for preparing a highly heat-resistant bio-based polyamide material in this embodiment comprises the following steps: 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.

[0035] In the extruder of this embodiment, the melt plasticization temperature is 300° C. and the extrusion screw speed is 500 rpm / min.

[0036] Example 2. A highly heat-resistant bio-based polyamide material according to this embodiment includes the following raw materials in parts by weight: PA56 50 parts, balanced multi-effect agent for filler modifier 11 parts, flame retardant 8 parts, silane coupling agent 7 parts, antioxidant 5 parts, lubricant 4 parts.

[0037] The relative viscosity of PA56 in this embodiment 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.

[0038] The preparation method of the balanced multi-effect agent mixed with the filler modifier of this embodiment is: 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; 5 parts of aluminum oxide powder, 3 parts of boron nitride and 7 parts of silane coupling liquid are fully mixed to obtain a first modified liquid; S02: 4 parts of barium titanate, 2 parts of barium nitrate solution and 3 parts of sodium silicate solution are fully mixed to obtain a second modified solution; The first modified liquid and the second modified liquid were mixed thoroughly in a weight ratio of 8:3 to obtain a modified compounding liquid; S03: Preparation of balancing agent for blending: The zinc oxide whiskers were mixed with a sufficient amount of a 5% by mass potassium permanganate solution, and then washed with boiling water for 3 times to obtain pretreated zinc oxide whiskers; 6 parts of pretreated zinc oxide whiskers, 4 parts of glass fibers, 3 parts of cerium oxide and 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 5:3, with a ball-milling speed of 1500r / min and ball-milling 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.

[0039] The alumina powder of this embodiment is spherical alumina particles with a particle size of 5 μm; the mass fraction of the barium nitrate solution is 5%; and the mass fraction of the sodium silicate solution is 7%.

[0040] The stirring speed of the blending and stirring process in this embodiment is 450 r / min, stirring is 30 min, and the stirring temperature is 56°C.

[0041] The bio-based polyamide material of this embodiment is further added with 8 parts of a stable supplementing agent, wherein the preparation method of the stable supplementing agent is as follows: S11: preheating the cordierite at 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 5 parts of nano-silica sol and 2 parts of sodium carboxymethyl cellulose to 8 parts of Tris-HCl buffer solution, and then adding 3 parts of yttrium nitrate solution, stirring sufficiently, to obtain modified silica sol; 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.

[0042] The pH value of the Tris-HCl buffer solution in this embodiment is 9; the mass fraction of the yttrium nitrate solution is 5%.

[0043] A method for preparing a highly heat-resistant bio-based polyamide material in this embodiment comprises the following steps: 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.

[0044] In the extruder of this embodiment, the melt plasticization temperature is 330° C. and the extrusion screw speed is 500 rpm / min.

[0045] Example 3. A highly heat-resistant bio-based polyamide material according to this embodiment includes the following raw materials in parts by weight: 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.

[0046] The relative viscosity of PA56 in this embodiment 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.

[0047] The preparation method of the balanced multi-effect agent mixed with the filler modifier of this embodiment is: 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; 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; 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; 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; S03: Preparation of balancing agent for blending: The zinc oxide whiskers were mixed with a sufficient amount of a 5% by mass potassium permanganate solution, and then washed with boiling water for 3 times to obtain pretreated zinc oxide whiskers; 5 parts of pretreated zinc oxide whiskers, 3.5 parts of glass fibers, 2 parts of cerium oxide and 6.5 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 5:2.5, with a ball-milling speed of 1250r / 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.

[0048] The alumina powder of this embodiment is spherical alumina particles with a particle size of 3.5 µm; the mass fraction of the barium nitrate solution is 4%; and the mass fraction of the sodium silicate solution is 5.5%.

[0049] The stirring speed of the blending and stirring process in this embodiment is 420 r / min, the stirring time is 25 min, and the stirring temperature is 54°C.

[0050] The bio-based polyamide material of this embodiment is further added with 6.5 parts of a stable supplementing agent, wherein the preparation method of the stable supplementing agent is as follows: S11: preheating the cordierite at 62° 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 4 parts of nano-silica sol and 1.5 parts of sodium carboxymethyl cellulose to 6.5 parts of Tris-HCl buffer solution, and then adding 2.5 parts of yttrium nitrate solution, stirring sufficiently, to obtain modified silica sol; S13: 4 parts of cordierite liquid, 2.5 parts of zirconium oxide and 6.5 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.

[0051] The pH value of the Tris-HCl buffer solution in this embodiment is 8.5; the mass fraction of the yttrium nitrate solution is 4%.

[0052] A method for preparing a highly heat-resistant bio-based polyamide material in this embodiment comprises the following steps: 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.

[0053] In the extruder of this embodiment, the melt plasticization temperature is 315° C. and the extrusion screw speed is 500 rpm / min.

[0054] Comparative Example 1. The difference from Example 3 is that no balanced multi-effect agent with a filler modifier is added.

[0055] Comparative Example 2. The difference from Example 3 is that no modified compounding liquid is added in the preparation of the balanced multi-effect agent blended with the filler modifier.

[0056] Comparative Example 3. The difference from Example 3 is that the first modifying liquid is not added to the modified compounding liquid.

[0057] Comparative Example 4. The difference from Example 3 is that no alumina powder and boron nitride are added to the first modified liquid.

[0058] Comparative Example 5. The difference from Example 3 is that no second modifying liquid is added to the modified compounding liquid.

[0059] Comparative Example 6. The difference from Example 3 is that no barium titanate or barium nitrate solution is added to the second modified solution.

[0060] Comparative Example 7. The difference from Example 3 is that no balancing agent is added in the preparation of the balancing multi-effect agent blended with the filler modifier.

[0061] Comparative Example 8. The difference from Example 3 is that no pretreated zinc oxide whiskers and glass fibers are added in the preparation of the blended balancing agent.

[0062] Comparative Example 9. The difference from Example 3 is that cerium oxide and dopamine hydrochloride solution are not added in the preparation of the blended balancing agent, and water is used instead.

[0063] Comparative Example 10. The difference from Example 3 is that no stable supplement is added.

[0064] Conventional tests, flame retardancy, dielectric loss and wear resistance of Examples 1-3 and Comparative Examples 1-10, as well as weather resistance and high heat resistance of the tested products (the products were placed at 75°C for 24 hours and then irradiated under UV conditions for 24 hours with an irradiation intensity of 100W / m 2 , the above is a cycle, the cycle test is 10 times);

[0065] It can be seen from Comparative Examples 1 to 10 and Examples 1 to 3 that; The product of Example 3 has excellent limiting oxygen index, dielectric loss and abrasion loss, and the wear resistance, dielectric loss and flame retardancy of the product can be improved in a coordinated manner. At the same time, the product has excellent stability under weather resistance and high heat resistance conditions; From comparative examples 1 to 10 and embodiment 3, it can be seen that the performance of the product deteriorates significantly when the balanced multi-effect agent for adjusting the filler modifier and the stable supplement agent are not added to the product. The performance effect of the product is most significant when the two are coordinated and work together. In the preparation of the balanced multi-effect agent mixed with the filler modifier, no modified compounding liquid was added, no first modified liquid was added to the modified compounding liquid, no aluminum oxide powder and boron nitride were added to the first modified liquid, no second modified liquid was added to the modified compounding liquid, and no barium titanate and barium nitrate solution were added to the second modified liquid. The performance of the product showed a trend of deterioration to varying degrees. The modified compounding liquid prepared by combining the specific first modified liquid and the second modified liquid of the present invention had the most significant performance effect. In the preparation of the balanced multi-effect agent for the filler modifier, no blended balancing agent was added, no pretreated zinc oxide whisker and glass fiber were added, and no cerium oxide and dopamine hydrochloride solution were added in the preparation of the blended balancing agent, and water was used instead. The performance of the products all showed a trend of deterioration to varying degrees. The blended balancing agent obtained by the method of the present invention had the best performance effect. The balanced multi-effect agent for the filler modifier prepared by the blended balancing agent obtained by the specific method of the present invention and the modified compound liquid had the most significant performance effect. At the same time, the inventors of the present invention also found that the performance of the product showed a relatively obvious trend of deterioration when no stable replenisher was added to the product.

[0066] Based on the above tests, the stable supplement of the present invention has a greater impact on product performance. Based on this, the present invention further explores and processes it: Experimental example 1. The difference from Example 3 is that no cordierite liquid is added in the preparation of the stable supplementary agent.

[0067] Experimental example 2. The difference from Example 3 is that zirconium oxide is not added in the preparation of the stable replenisher.

[0068] Experimental Example 3. The difference from Example 3 is that no modified silica sol is added in the preparation of the stable replenisher.

[0069] Experimental Example 4. The difference from Example 3 is that no nano silica sol and sodium carboxymethyl cellulose are added to the modified silica sol.

[0070] Experimental Example 5. The difference from Example 3 is that no yttrium nitrate solution is added to the modified silica sol and the Tris-HCl buffer solution is replaced by water.

[0071]

[0072] It can be seen from Experimental Examples 1-5 that cordierite liquid is not added in the preparation of the naiwen replenishing agent, and the performance of the product deteriorates significantly. At the same time, zirconium oxide and modified silica sol are not added in the preparation of the naiwen replenishing agent, and the performance effect of the product is poor. Therefore, zirconium oxide and modified silica sol are used in combination with the cordierite liquid of the present invention. The raw materials of the product are proprietary, and the effect is not obvious when other raw materials are used in combination. At the same time, nano silica sol, sodium carboxymethyl cellulose, yttrium nitrate solution and Tris-HCl buffer solution are not added to the modified silica sol, and water is used instead of the modified silica sol. The performance of the product has a tendency to deteriorate. The modified silica sol obtained by the method of the present invention has the most significant performance effect of the product. Only when the raw materials of the present invention are used in combination, the performance effect of the product is the most significant.

[0073] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0074] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes 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; The preparation method of the balanced multi-effect agent mixed with the filler modifier is as follows: The first modifying liquid and the second modifying liquid are mixed to obtain a modified compounding liquid, and then the pretreated zinc oxide whisker, glass fiber, cerium oxide and dopamine hydrochloride solution are mixed and stirred to obtain a mixed balancing agent, and finally the modified compounding liquid and the mixed balancing agent are mixed and ball-milled to obtain a balanced multi-effect agent of a mixed filler modifier.

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 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 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) 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.

5. A highly heat-resistant bio-based polyamide material according to claim 4, 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%.

6. The highly heat-resistant bio-based polyamide material according to claim 4, 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.

7. The highly heat-resistant bio-based polyamide material according to claim 1, characterized in that: The bio-based polyamide material is further added with 5 to 8 parts of a stable replenisher, wherein the preparation method of the stable replenisher 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.

8. The highly heat-resistant bio-based polyamide material according to claim 7, 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%.

9. The method for preparing a highly heat-resistant bio-based polyamide material according to any one of claims 1 to 8, 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.

10. The method for preparing a highly heat-resistant bio-based polyamide material according to claim 9, characterized in that: The melt plasticizing temperature in the extruder is 300-330° C., and the extrusion screw speed is 500 rpm / min.

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