CN111978719A - Polyamide 66 composite material and preparation method thereof - Google Patents
Polyamide 66 composite material and preparation method thereof Download PDFInfo
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- CN111978719A CN111978719A CN202010886648.9A CN202010886648A CN111978719A CN 111978719 A CN111978719 A CN 111978719A CN 202010886648 A CN202010886648 A CN 202010886648A CN 111978719 A CN111978719 A CN 111978719A
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Abstract
The invention relates to a polyamide 66 composite material and a preparation method thereof, wherein the polyamide 66 composite material is prepared from the following raw materials: polyamide 66, mica powder, flat glass fiber, calcium sulfate whisker, titanate coupling agent, ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, long-chain linear saturated sodium carboxylate salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate. The polyamide 66 composite material has excellent mechanical property and processability, low linear expansion coefficient and low warpage, and can be applied to the fields of automobiles, aviation, electronics and electrics, household appliances and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a polyamide 66 composite material and a preparation method thereof.
Background
The current automotive industry requires that the assembly gap between different material parts be as small as possible and that dimensional stability be high, which requires that the polymer material have a low warpage and linear expansion Coefficient (CLTE). Polyamide 66(PA66) has excellent mechanical properties and solvent resistance, but has a shrinkage of 1-1.5%, poor dimensional stability and a large linear expansion coefficient, and is difficult to meet large-scale parts in the automobile field with high requirements on parts assembly.
The coefficient of linear expansion (CLTE) is the ratio of the change in length (Δ L) of a material over a unit change in temperature (Δ T) to the initial length (L), CLTE ═ Δ L/(L × Δ T). The CLTE of a material has a large dimensional relationship with the material, which affects the assembly of the material parts and the dimensional stability after assembly. There are generally two ways to reduce the linear expansion coefficient of a polymer: (1) the crystallinity of a polymer crystallization area is improved, and the linear expansion coefficient of the polymer is reduced because the mobility of a polymer molecular chain is obviously weakened after crystallization; (2) the activity of molecules in an amorphous region is inhibited by adding inorganic fillers such as talcum powder, mica powder, glass fiber, wollastonite and the like, and meanwhile, the expansion of the inorganic fillers generated by heating is very low, so that the linear expansion coefficient of the polymer can be reduced.
Currently, some studies on polymer composition systems with low linear expansion coefficients are made in the prior art, such as: chinese patent CN103131166A discloses a thermoplastic resin composition with low thermal expansion coefficient, a preparation method and an application thereof, wherein the composition is prepared from the following components in parts by weight: 340-900 parts of thermoplastic resin, 100-500 parts of carbon fiber, 0-5 parts of antioxidant, 0-5 parts of lubricant and 0-150 parts of toughening agent; chinese patent CN103788634A discloses a low-shrinkage glass fiber reinforced PP/PA composite material composition and a preparation method thereof; the composition comprises: 10-80 parts of polypropylene, 10-80 parts of polyamide, 5-25 parts of a compatilizer, 10-80 parts of glass fiber, 0.1-5 parts of an antioxidant and 0.1-5 parts of a lubricating dispersant; chinese patent CN106832992A discloses a rigid composite material using biomass as a raw material, which has the advantages of low linear thermal expansion coefficient and creep resistance, the rigid biomass composite material is prepared by using a biomass material with a large length-diameter ratio as a main body and using a PE/ABS/PA alloy with excellent comprehensive performance as a plastic adhesive, and the prepared rigid biomass composite material has a low linear thermal expansion coefficient and excellent creep resistance.
Disclosure of Invention
Based on this, the object of the present invention is to provide a polyamide 66 composite material having excellent mechanical properties and processability, as well as a low linear expansion coefficient and low warpage, which can be applied to the fields of automobiles, aviation, electronics and electrical, home appliances, and the like.
In order to achieve the purpose, the invention adopts the following scheme:
the polyamide 66 composite material is prepared from the following raw materials in parts by weight:
65-85 parts of polyamide 66(PA66),
15-35 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
in some embodiments, the polyamide 66 composite material is prepared from the following raw materials in parts by weight:
65-77 parts of polyamide 66(PA66),
23-35 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
in some embodiments, the polyamide 66 composite material is prepared from the following raw materials in parts by weight:
68-77 parts of polyamide 66(PA66),
23-32 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
in some embodiments, the polyamide 66 composite material is further preferably prepared from the following raw materials in parts by weight:
74-76 parts of polyamide 66(PA66),
24-26 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
in some of these embodiments, the polyamide 66 has an intrinsic viscosity of 1.42 to 1.88 dL/g.
In some of these embodiments, the mica powder has a thickness to diameter ratio of no less than 80: 1.
In some embodiments, the ratio of thickness to diameter of the mica powder is 80-100: 1.
In some of these embodiments, the flat glass fibers have a cross-sectional aspect ratio of 3.5 to 4.5: 1.
In some embodiments, the aspect ratio of the calcium sulfate whiskers is 20-100: 1.
In some embodiments, the aspect ratio of the calcium sulfate whiskers is 40-60: 1.
In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
In some of these embodiments, the sodium salt of a long chain linear saturated carboxylic acid has a carbon number of 28 to 32.
Another object of the present invention is to provide a method for preparing the above polyamide 66 composite material.
The preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 and mixing with the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, long chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) mixing the mica powder, the calcium sulfate whisker and the titanate coupling agent;
(3) and (2) feeding the mixed mixture obtained in the step (1) into a parallel twin-screw extruder through a feeder, feeding the mixed mixture obtained in the step (2) into the parallel twin-screw extruder in the lateral direction (for example, the fourth zone) of the parallel twin-screw extruder (total eight zones), and feeding the flat glass fibers into the parallel twin-screw extruder in the other lateral direction (for example, the third zone) of the parallel twin-screw extruder for melt extrusion and granulation.
In some embodiments, the drying temperature in step (1) is 80-110 ℃, and the drying time is 4-8 hours.
In some embodiments, the drying temperature in step (1) is 90-100 ℃, and the drying time is 4-6 hours.
In some of the embodiments, the process parameters of the parallel twin-screw extruder described in step (3) include: the temperature of the first zone is 280-300 ℃, the temperature of the second zone is 285-305 ℃, the temperature of the third zone is 285-305 ℃, the temperature of the fourth zone is 290-310 ℃, the temperature of the fifth zone is 290-310 ℃, the temperature of the sixth zone is 285-305 ℃, the temperature of the seventh zone is 285-305 ℃, the temperature of the eighth zone is 285-305 ℃, the temperature of the die head is 285-305 ℃, and the rotating speed of the screw is 200-600 rpm.
In some of the embodiments, the process parameters of the parallel twin-screw extruder described in step (3) include: the temperature of the first zone is 285-295 ℃, the temperature of the second zone is 290-300 ℃, the temperature of the third zone is 290-300 ℃, the temperature of the fourth zone is 295-305 ℃, the temperature of the fifth zone is 295-305 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the eighth zone is 290-300 ℃, the temperature of the die head is 290-300 ℃ and the rotating speed of the screw is 300-500 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is a single flight.
In some of these embodiments, the ratio L/D of the screw length L to the diameter D of the parallel twin-screw extruder is 35 to 50.
In some of these embodiments, the parallel twin-screw extruder has a ratio L/D of screw length L to diameter D of 35 to 45.
In some of these embodiments, the screws of the parallel twin-screw extruder are provided with more than 1 (including 1) intermeshing zone and more than 1 (including 1) counter-flight zone.
In some of these embodiments, the screws of the parallel twin screw extruder are provided with 2 intermeshing block zones and 1 counter-flight zone.
In some embodiments, in step (1) and/or step (2), the mixing step is performed by using a stirrer, wherein the rotation speed of the stirrer is 500-.
The principle of the polyamide 66 composite material of the invention is as follows:
in order to solve the defects of larger linear expansion coefficient, poor dimensional stability and the like of the polyamide 66 composite material, the invention reduces the linear expansion coefficient and warpage of the polyamide 66 composite material by compounding and using mica powder, calcium sulfate whiskers, flat glass fibers and long-chain linear saturated sodium carboxylate, and improves the compatibility between PA66 and a filler, and the processing performance and impact performance of the PA66 composite material by compounding and using a titanate coupling agent, an ethylene-maleic anhydride-glycidyl methacrylate copolymer and 2,2' - (1, 3-phenylene) -bisoxazoline. According to the invention, the addition of the auxiliary agent improves the interface bonding force and compatibility between the PA66 and the filler, simultaneously improves the mechanical property and the processing property of the PA66 composite material, and reduces the linear expansion coefficient and the warping degree of the PA66 composite material, so that the polyamide 66 composite material with excellent comprehensive properties is prepared.
The mica powder adopted by the invention belongs to monoclinic crystal, the crystal is scaly, the preferable thickness-diameter ratio is not less than 80:1, the linear expansion coefficient is low, and when the mica powder is filled between polyamide 66 molecular chains, the molecular mobility of the polyamide 66 molecular chains can be effectively inhibited, and the linear expansion coefficient is reduced; the calcium sulfate whisker adopted by the invention integrates the advantages of the reinforcing fiber and the superfine inorganic filler, has the advantages of high strength, high modulus, high dielectric strength, wear resistance, high temperature resistance and the like, can reinforce polyamide 66, and can be used as a nucleating agent to promote PA66 crystallization and reduce the linear expansion coefficient; the flat glass fibers employed in the present invention provide better flow (increase spiral flow), reduce friction and viscosity by reducing resin shear, and optimize the thermoplastic processing process by reducing fiber entanglement and breakage, reducing warpage, since flat glass fibers tend to flow in a planar state like mica, rather than rolling and tumbling as conventional round glass fibers; the nucleating mechanism of the long-chain linear saturated sodium carboxylate in the polymer is complex, which is mainly related to the chemical structure of the long-chain linear saturated sodium carboxylate, and the nucleating agent plays roles of heterogeneous nucleation and chemical nucleation in the PA66 composite material, so that the nucleating capability of PA66 can be improved, the crystallization rate of PA66 can be increased, and the linear expansion coefficient and warping degree of the PA66 composite material can be reduced.
The effect of the titanate coupling agent used according to the invention is attributed to its effect on the interface, i.e. it forms chemical bridges between the inorganic filler and the organic polymer, which couple directly by chemical action of its alkoxy groups with the trace of hydroxyl groups adsorbed on the filler surface, while its organic phase is very compatible with PA 66.
According to the invention, a titanate coupling agent, an ethylene-maleic anhydride-glycidyl methacrylate copolymer and 2,2' - (1, 3-phenylene) -bisoxazoline are compounded to improve the compatibility between PA66 and a filler, and the processability and impact property of PA 66. Wherein, the terminal group of PA66 and the terminal hydroxyl group of the filler can react with the maleic anhydride group and the epoxy group of the ethylene-maleic anhydride-glycidyl methacrylate copolymer and react with the oxazoline group of 2,2' - (1, 3-phenylene) -bisoxazoline to improve the compatibility and the interfacial bonding force among the two, and meanwhile, the ethylene structural unit in the ethylene-maleic anhydride-glycidyl methacrylate copolymer can improve the toughness of the PA66 composite material.
The melting point of the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide adopted by the invention is 272 ℃, the boiling point is more than 360 ℃, the thermal stability is better in the blending process of the PA66 composite material, and the hindered piperidyl can provide an antioxidation effect and improve the dyeing property of the composition.
The bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate adopted by the invention has the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for a PA66 composite material in a blending process, can prevent thermal degradation of the PA66 composite material in a high-temperature process, and inhibits thermo-oxidative discoloration caused by long-time extrusion processing, and also provides a Nitrogen Oxide (NO) in the flame retardantx) Color stability in gas environment, and prevention of discoloration of fumigant.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the defects of larger linear expansion coefficient, poor dimensional stability and the like in the existing polyamide 66 composite material, the linear expansion coefficient and warpage of the polyamide 66 composite material are reduced by compounding and using mica powder, calcium sulfate whiskers, flat glass fibers and long-chain linear saturated sodium carboxylate, the compatibility between PA66 and a filler is improved by compounding and using a titanate coupling agent, an ethylene-maleic anhydride-glycidyl methacrylate copolymer and 2,2'- (1, 3-phenylene) -bisoxazoline, meanwhile, the toughness of the PA66 composite material can be improved by using an ethylene structural unit in the ethylene-maleic anhydride-glycidyl methacrylate copolymer, and N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1 is compounded and used, the yellowing phenomenon and the thermal stability of the polyamide 66 composite material in the blending processing process are improved by 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, and the raw material components are matched with each other, so that the obtained polyamide 66 composite material has excellent mechanical property and processing property, low linear expansion coefficient and low warpage, and can be applied to the fields of automobiles, aviation, electronics and electrical and household appliances and the like.
The preparation method of the polyamide 66 composite material provided by the invention has the advantages of simple process, easiness in control and low requirements on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the industrial production is facilitated.
Drawings
Fig. 1 is a flow chart of a process for preparing a polyamide 66 composite material according to an embodiment of the present invention.
Detailed Description
In order to further understand the features and technical means of the present invention and achieve the specific objects and functions, the advantages and spirit of the present invention are further illustrated by the following embodiments.
The reaction mechanism of the polyamide 66 composite material of one embodiment of the invention is as follows (see FIG. 1 for a flow chart of the preparation process)
Wherein R is one of mica powder, calcium sulfate whisker and flat glass fiber.
Mechanism of reaction
According to the reaction formula, the terminal group of the polyamide 66, the mica powder coated with the titanate coupling agent, the calcium sulfate whisker and the terminal hydroxyl group of the flat glass fiber can react with the maleic anhydride group and the epoxy group of the ethylene-maleic anhydride-glycidyl methacrylate copolymer and react with the oxazoline group of 2,2' - (1, 3-phenylene) -bisoxazoline, so that the compatibility and the interface cohesiveness between the polyamide 66 and the filler mica powder, between the calcium sulfate whisker and the flat glass fiber are improved, the mechanical property and the processing property of the polyamide 66 composite material are improved, and the linear expansion coefficient and the warping degree are improved.
The examples of the invention and the comparative examples used the following raw materials:
polyamide 66 with an intrinsic viscosity of 1.65dL/g, selected from the chemical industry llc of nylon, santoma cruzi;
mica powder with the thickness-diameter ratio of 90:1 is selected from Shijiazhuangxing industry Co Ltd;
flat glass fibers having a cross-sectional aspect ratio of 4:1 selected from Chongqing International composite materials, Inc.;
the length-diameter ratio of the calcium sulfate crystal whisker is 50:1, and the calcium sulfate crystal whisker is selected from New materials science and technology Limited of Changzhou Guangwei;
the titanate coupling agent is a mono-alkoxy fatty acid titanate coupling agent (the type is the titanate coupling agent TC-130), and is selected from a chemical auxiliary oil plant in Tianchan city;
ethylene-maleic anhydride-glycidyl methacrylate copolymer selected from Shenyankotong plastics Co., Ltd;
2,2' - (1, 3-phenylene) -bisoxazoline selected from the group consisting of Hubei constant Techno chemical Co., Ltd;
the long-chain linear saturated carboxylic acid sodium salt (model is NAV101), the carbon number of the long-chain linear saturated carboxylic acid sodium salt is 28-32, and the long-chain linear saturated carboxylic acid sodium salt is selected from Claien chemical industry (China) Co., Ltd;
n, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, selected from Toxongitai chemical Co., Ltd;
bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate selected from Shanghai Yaozao Fine chemical Co., Ltd.
Example 1:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
6685 parts of polyamide, including by weight,
15 parts of mica powder, namely 15 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 300 deg.C, the temperature in the second zone was 305 deg.C, the temperature in the third zone was 305 deg.C, the temperature in the fourth zone was 310 deg.C, the temperature in the fifth zone was 310 deg.C, the temperature in the sixth zone was 305 deg.C, the temperature in the seventh zone was 305 deg.C, the temperature in the eighth zone was 305 deg.C, the temperature in the die was 305 deg.C, and the.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 50, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 2:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
polyamide 6665 parts by weight of polyamide 6665 parts by weight,
35 parts of mica powder, namely 35 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 280 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 290 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the seventh zone is 285 ℃, the temperature of the eighth zone is 285 ℃, the temperature of the die head is 285 ℃ and the rotating speed of the screw is 200 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 35, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 3:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
6682 parts of polyamide (A), by weight,
18 parts of mica powder, namely 18 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 295 deg.C, the temperature in the second zone was 300 deg.C, the temperature in the third zone was 300 deg.C, the temperature in the fourth zone was 305 deg.C, the temperature in the fifth zone was 305 deg.C, the temperature in the sixth zone was 300 deg.C, the temperature in the seventh zone was 300 deg.C, the temperature in the eighth zone was 300 deg.C, the temperature in the die head was 300 deg.C, and.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 45, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 4:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
6668 parts of polyamide (A), 6668 parts of polyamide (B),
32 parts of mica powder, namely 32 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 285 deg.C, the temperature in the second zone was 290 deg.C, the temperature in the third zone was 290 deg.C, the temperature in the fourth zone was 295 deg.C, the temperature in the fifth zone was 295 deg.C, the temperature in the sixth zone was 290 deg.C, the temperature in the seventh zone was 290 deg.C, the temperature in the eighth zone was 290 deg.C, the temperature in the die head was 290 deg.C, and.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 35, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 5:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
polyamide 6680 parts by weight of polyamide (I),
20 parts of mica powder, namely 20 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 6:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
6670 parts of polyamide, a synthetic polyamide resin,
30 parts of mica powder, namely 30 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 7:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 8:
the embodiment provides a polyamide 66 composite material, which is prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back-thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 1:
the comparative example provides a polyamide 66 composite material prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 2:
the comparative example provides a polyamide 66 composite material prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 3:
the comparative example provides a polyamide 66 composite material prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, a long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder and the calcium sulfate whiskers into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 4:
the comparative example provides a polyamide 66 composite material prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 5:
the comparative example provides a polyamide 66 composite material prepared from the following raw materials in parts by weight:
6675 parts of polyamide, namely, polyamide 6675,
25 parts of mica powder, namely 25 parts of mica powder,
the sum of the parts by weight of the polyamide 66 and the mica powder is 100 parts,
the preparation method of the polyamide 66 composite material comprises the following steps:
(1) drying the polyamide 66 at the temperature of 95 ℃ for 5 hours, cooling, and adding the cooled polyamide 66, the ethylene-maleic anhydride-glycidyl methacrylate copolymer, the long-chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the mica powder, the calcium sulfate whisker and the titanate coupling agent into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding flat glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 290 ℃, the temperature in the second zone was 295 ℃, the temperature in the third zone was 295 ℃, the temperature in the fourth zone was 300 ℃, the temperature in the fifth zone was 300 ℃, the temperature in the sixth zone was 295 ℃, the temperature in the seventh zone was 295 ℃, the temperature in the eighth zone was 295 ℃, the temperature in the die head was 295 ℃ and the screw speed was 400 rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 40, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
The following is a list of raw material compositions of examples and comparative examples (table 1).
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
Remarking: a, changing a screw structure;
wherein, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate of the above examples and comparative examples were added in amounts of 0.2 parts each.
The polyamide 66 composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: the thickness of the sample strip is 4mm according to the test of GB/T1843-2008 standard;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 275 ℃, and the load is 2.16 kg;
coefficient of linear expansion: the lower the value, the better according to the GB/T36800.2-2018 standard test;
warping degree: the test panels were measured according to GB/T25257-2010 with dimensions 100mm 3mm, the lower the values the better.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the Polyamide 66 composites of the examples and comparative examples
In the embodiments 1 to 7, the addition amounts of mica powder, flat glass fiber, calcium sulfate whisker, titanate coupling agent, EMG, PBO and long-chain linear saturated sodium carboxylate salt are adjusted, and it can be seen from the table that as the addition amounts of mica powder and flat glass fiber are increased, the tensile strength and notch impact strength of the polyamide 66 composite material are improved, and the linear expansion coefficient and warping degree thereof are reduced, mainly because the mica powder and flat glass fiber can play a role of reinforcing the material, and at the same time, the mica powder can effectively inhibit the molecular mobility of the molecular chain of polyamide 66, reduce the linear expansion coefficient thereof, and the flat glass fiber can flow in a planar state like mica, and does not roll and roll like the conventional round glass fiber, so that the warping degree of the polyamide 66 composite material is reduced; EMG contains ethylene building blocks which can act as toughening for polyamide 66 composites, but mica powder has a negative impact on impact performance. Under the combined action of various factors, the polyamide 66 composite material obtained in example 7 has the best comprehensive performance and the best mixture ratio of the raw materials.
Example 7 compared with example 8, the screw shape of the parallel twin-screw extruder of example 8 was double-screw thread, and the screw shape of the parallel twin-screw extruder of example 7 was single-screw thread, and it can be found by comparison that the polyamide 66 composite material prepared by using the screw parameters of the parallel twin-screw extruder described in example 7 has better tensile strength, notch impact strength and melt index, and lower coefficient of linear expansion and warpage.
Example 7 compared with comparative example 1, comparative example 1 does not add flat glass fibers and calcium sulfate whiskers, so the polyamide 66 composite material prepared in comparative example 1 has a higher linear expansion coefficient and warpage and lower tensile strength and notched impact strength, mainly because the flat glass fibers and the calcium sulfate whiskers can play a role in reinforcing the composite material and absorbing external impact energy while reducing the linear expansion coefficient and warpage of the polyamide 66 composite material by matching mica powder and long-chain linear saturated sodium carboxylate; compared with the comparative example 2, the comparative example 2 does not use calcium sulfate whiskers, and can play a role in reinforcing resin and reducing the linear expansion coefficient and the warpage, so that the tensile strength and the notch impact strength of the polyamide 66 composite material obtained in the comparative example 2 are lower than those of the example 7, and the linear expansion coefficient and the warpage are higher than those of the example 7, therefore, the mica powder, the calcium sulfate whiskers, the flat glass fibers and the long-chain linear saturated sodium carboxylate salt have a synergistic effect, and the four components are compounded to be used for more effectively reducing the linear expansion coefficient and the warpage of the polyamide 66 composite material and more effectively improving the tensile strength and the notch impact strength of the polyamide 66 composite material; example 7 compared to comparative example 3, comparative example 3 has no titanate coupling agent added, and the interfacial bonding force and compatibility between polyamide 66 and the filler are weakened, resulting in a polyamide 66 composite material having a tensile strength and a notched impact strength lower than those of example 7 and a linear expansion coefficient and warpage higher than those of example 7; example 7 compared to comparative example 4, comparative example 4 without EMG and PBO addition produced polyamide 66 composite material with tensile strength and notched impact strength lower than example 7 and linear expansion coefficient and warpage higher than example 7, mainly because terminal hydroxyl groups of polyamide 66, mica powder coated with titanate coupling agent, calcium sulfate whisker and flat glass fiber can react with maleic anhydride group and epoxy group of ethylene-maleic anhydride-glycidyl methacrylate copolymer and with oxazoline group of 2,2' - (1, 3-phenylene) -bisoxazoline, thus improving compatibility and interface cohesiveness between polyamide 66 and filler mica powder, calcium sulfate whisker and flat glass fiber, and improving mechanical properties and processability of polyamide 66 composite material, improving linear expansion coefficient and warping degree; compared with the comparative example 5, the comparative example 5 is not added with the PBO, the tensile strength and the notch impact strength of the prepared polyamide 66 composite material are lower than those of the example 7, and the linear expansion coefficient and the warping degree are higher than those of the example 7, because the lack of the PBO can cause the deterioration of the compatibility and the interface cohesiveness among the polyamide 66, the filler mica powder, the calcium sulfate whisker and the flat glass fiber, so the mechanical property, the linear expansion coefficient and the warping degree are influenced, and the PBO, the EMG and the titanate coupling agent are compounded to have the synergistic effect, so the tensile strength and the notch impact strength of the polyamide 66 composite material can be more effectively improved and the linear expansion coefficient and the warping degree of the polyamide 66 composite material can be more effectively reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polyamide 66 composite material is characterized by being prepared from the following raw materials in parts by weight:
2. the polyamide 66 composite material of claim 1, which is prepared from the following raw materials in parts by weight:
3. the polyamide 66 composite material of claim 2, which is prepared from the following raw materials in parts by weight:
4. the polyamide 66 composite of any one of claims 1-3, wherein the polyamide 66 has an intrinsic viscosity of 1.42 to 1.88 dL/g; and/or the thickness-diameter ratio of the mica powder is not less than 80: 1; and/or the aspect ratio of the cross section of the flat glass fiber is 3.5-4.5: 1; and/or the length-diameter ratio of the calcium sulfate whisker is 20-100: 1; and/or the titanate coupling agent is a mono-alkoxy fatty acid titanate coupling agent; and/or the carbon number of the long-chain linear saturated carboxylic acid sodium salt is 28-32.
5. A method for preparing a polyamide 66 composite material according to any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) drying the polyamide 66 and mixing with the ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, long chain linear saturated carboxylic acid sodium salt, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) mixing the mica powder, the calcium sulfate whisker and the titanate coupling agent;
(3) and (3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder in the lateral direction, adding the flat glass fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating.
6. The method according to claim 5, wherein the drying temperature in step (1) is 80 to 110 ℃, and the drying time is 4 to 8 hours; and/or the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 280-300 ℃, the temperature of the second zone is 285-305 ℃, the temperature of the third zone is 285-305 ℃, the temperature of the fourth zone is 290-310 ℃, the temperature of the fifth zone is 290-310 ℃, the temperature of the sixth zone is 285-305 ℃, the temperature of the seventh zone is 285-305 ℃, the temperature of the eighth zone is 285-305 ℃, the temperature of the die head is 285-305 ℃, and the rotating speed of the screw is 200-600 rpm.
7. The method according to claim 6, wherein the drying temperature in step (1) is 90 to 100 ℃ and the drying time is 4 to 6 hours; and/or the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 285-295 ℃, the temperature of the second zone is 290-300 ℃, the temperature of the third zone is 290-300 ℃, the temperature of the fourth zone is 295-305 ℃, the temperature of the fifth zone is 295-305 ℃, the temperature of the sixth zone is 290-300 ℃, the temperature of the seventh zone is 290-300 ℃, the temperature of the eighth zone is 290-300 ℃, the temperature of the die head is 290-300 ℃ and the rotating speed of the screw is 300-500 rpm.
8. The production method according to any one of claims 5 to 7, wherein the screw shape of the parallel twin-screw extruder is a single-screw thread; and/or the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 35-50; and/or more than 1 meshing block area and more than 1 reverse thread area are arranged on the screw of the parallel double-screw extruder.
9. The production method according to claim 8, wherein the ratio L/D of the screw length L to the diameter D of the parallel twin-screw extruder is 35 to 45; and/or the screw of the parallel double-screw extruder is provided with 2 meshing block areas and 1 reverse thread area.
10. The method according to any one of claims 5 to 7, wherein the mixing step is performed with a stirrer having a rotation speed of 500 to 1500 rpm in the step (1) and/or the step (2).
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