CN111363351A - Polyamide 66 composition and preparation method thereof - Google Patents
Polyamide 66 composition and preparation method thereof Download PDFInfo
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- CN111363351A CN111363351A CN202010345339.0A CN202010345339A CN111363351A CN 111363351 A CN111363351 A CN 111363351A CN 202010345339 A CN202010345339 A CN 202010345339A CN 111363351 A CN111363351 A CN 111363351A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a polyamide 66 composition and a preparation method thereof, wherein the polyamide 66 composition is prepared from the following raw materials: the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, hollow glass microspheres, the polyhedral oligomeric silsesquioxane polymer, a titanate coupling agent, polytetrafluoroethylene resin, a hyperbranched polyester polymer, erucamide, 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 composition has excellent mechanical property, processability and low dielectric constant, and can be applied to shells, coating materials, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
Description
Technical Field
The invention relates to the field of materials, in particular to a polyamide 66 composition and a preparation method thereof.
Background
Dielectric materials, also known as dielectrics, are electrically insulating materials. There are high dielectric materials and low dielectric materials, depending on the properties. With the rapid advance of electronic information technology, electronic products are being developed toward light weight, high performance and multiple functions, and development of low dielectric constant (D) having good performance is increasingly required for low dielectric materialsk<3) A material. Meanwhile, with the coming of the 5G era, the requirements on the transmission speed and the loss of electronic signals are higher than those of 4G products, generally, the dielectric constant of the 4G products for the resin material is only required to be less than 3.7(1GHz), and the dielectric constant of the 5G products for the resin material is required to be less than 3.2(1 GHz).
Generally, there are three methods for reducing the dielectric constant of a polymer, which are ① introducing fluorine atoms into a polymer molecular chain to reduce the stacking density of the molecular chain and increase the free movement space of the molecular chain, ② introducing a bulky structure (such as polyhedral oligomeric silsesquioxane polymer) or a microporous structure or introducing large molecular chain side groups (such as benzene rings) by a physical or chemical method, ③ reducing the dielectric constant of a blend by blending other materials with lower dielectric constant, such as blending with Polytetrafluoroethylene (PTFE) with a relative dielectric constant of 2.0(1GHz), or blending with materials such as polyhedral oligomeric silsesquioxane Polymer (POSS) which can increase the free volume, and the like.
Polyamide (PA) has excellent mechanical property, wear resistance and corrosion resistance, and is widely used for replacing metals such as copper and the like in the industries of machinery, chemical engineering, instruments, automobiles and the like to manufacture bearings, gears, pump blades and other parts and the like. However, polyamide has low notched impact strength, strong hygroscopicity, poor dimensional stability and high dielectric constant, so that it is necessary to toughen and reinforce PA and blend other materials with lower dielectric constant to reduce the dielectric constant of the composition, so as to meet the requirements in the fields of electronics and electricians, integrated circuit packaging, electromagnetic wave shielding and the like.
Currently, some research is done in the prior art on PA dielectric systems, such as: chinese patent CN 108410167a discloses a glass fiber reinforced low dielectric nylon material and a preparation method thereof, the nylon material mainly comprises: nylon resin, quartz glass fiber, nucleating agent, lubricant, thermal oxygen stabilizer and the like as raw materials; chinese patent CN 108148396a discloses a polyamide molding compound, which has a relative dielectric constant at 2.45GHz of not more than 3.5 and comprises: (A)25 to 80 weight percent of a mixture formed from: aa) from 50.1 to 90% by weight of at least one partially crystalline aliphatic polyamide, and Ab) from 10 to 49.9% by weight of at least one amorphous or microcrystalline polyamide, the proportions of components Aa) and Ab) in mixture (A) adding up to 100% by weight, and the mixture of components Aa) and Ab) having on average at least 5.7C atoms not involved in the polyamide per amide group, (B) from 20 to 65% by weight of at least one glass filler consisting of a glass having a content of alkali metal oxide and alkaline earth metal oxide of from 0 to 12% by weight, relative to the glass composition, the glass filler being selected from the group consisting of fibers, milled fibers, particles, flakes, spheres and mixtures thereof, and (C) from 0 to 10% by weight of additives, the sum of components (A), (B) and (C) adding up to 100% by weight; chinese patent CN 110461930a discloses an aliphatic polyamide composition comprising an aliphatic polyamide, glass fibers and optionally one or more additives, which composition has similar dielectric properties and significantly improved mechanical properties; chinese patent CN 107573683A discloses a glass fiber reinforced polyamide material with low dielectric constant and a preparation method thereof, wherein the material comprises the following components in parts by weight: PA6610-70 parts, PA6I/6T copolymer 5-20 parts, glass fiber 20-60 parts, zeolite 5-10 parts, antioxidant 0.8-1.2 parts, and lubricant 0.5-1 part; chinese patent CN 104448804A discloses a polyamide composition and a preparation method thereof, wherein the polyamide composition comprises the following components in parts by weight: 45-85 parts of polyamide resin, 10-40 parts of hollow glass fiber and 1-15 parts of other auxiliary agents.
Disclosure of Invention
Based on the above, the present invention aims to provide a polyamide 66 composition with excellent mechanical properties and processability and a low dielectric constant, which can be applied to 5G base stations, micro base station systems, data communication terminals, housings and coatings of antennas and radio frequency modules, protective materials, and the like.
In order to achieve the purpose, the invention adopts the following scheme:
the polyamide 66 composition is prepared from the following raw materials in parts by weight:
60-93 parts of low-viscosity polyamide 66 resin (PA66),
5 to 20 parts of high-viscosity polyamide 66 resin (PA66),
2-20 parts of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH),
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the intrinsic viscosity of the low-viscosity polyamide 66 resin is 1.32-1.47 dL/g; the intrinsic viscosity of the high-viscosity polyamide 66 resin is 1.75-1.92 dL/g; the compressive strength of the hollow glass beads is not lower than 53 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand.
In some embodiments, the polyamide 66 composition is prepared from the following raw materials in parts by weight:
68-85 parts of low-viscosity polyamide 66 resin (PA66),
9 to 16 parts of high-viscosity polyamide 66 resin (PA66),
6-16 parts of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH),
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
in some embodiments, the polyamide 66 composition is further preferably prepared from the following raw materials in parts by weight:
72-78 parts of low-viscosity polyamide 66 resin (PA66),
12 to 14 parts of high-viscosity polyamide 66 resin (PA66),
10-14 parts of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH),
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
in some embodiments, the polyamide 66 composition is further preferably prepared from the following raw materials in parts by weight:
74-76 parts of low-viscosity polyamide 66 resin (PA66),
12 to 14 parts of high-viscosity polyamide 66 resin (PA66),
11-13 parts of ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH),
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
in some of the embodiments, the compressive strength of the hollow glass microspheres is 55-65 MPa.
In some of these embodiments, the polytetrafluoroethylene resin has a number average molecular weight of 3 to 7 ten thousand.
In some embodiments, the maleic anhydride grafting rate of the ethylene-octene copolymer grafted with maleic anhydride is 1.0-1.4%.
In some of these embodiments, the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group.
In some of these embodiments, the polyhedral oligomeric silsesquioxane polymer is epoxycyclohexylethyl-POSS and/or glycidyl-POSS.
In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
It is another object of the present invention to provide a process for the preparation of polyamide 66 compositions.
The preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin, and mixing the dried low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin with the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic diamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide;
(3) and (2) 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 (totally eight zones) (for example, a fourth zone), performing melt extrusion, and granulating.
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 255-275 ℃, the temperature of the second zone is 260-280 ℃, the temperature of the third zone is 260-280 ℃, the temperature of the fourth zone is 265-285 ℃, the temperature of the fifth zone is 265-285 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the seventh zone is 260-280 ℃, the temperature of the eighth zone is 260-280 ℃, the temperature of the die head is 260-280 ℃, 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 260-270 ℃, the temperature of the second zone is 265-275 ℃, the temperature of the third zone is 265-275 ℃, the temperature of the fourth zone is 270-280 ℃, the temperature of the fifth zone is 270-280 ℃, the temperature of the sixth zone is 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 265-275 ℃, the temperature of the die head is 265-275 ℃ and the rotation speed of the screw is 300-500 rpm.
In some embodiments, the drying temperature in step (1) is 90-120 ℃, and the drying time is 4-8 hours.
In some embodiments, the drying temperature in step (1) is 100-110 ℃, and the drying time is 4-6 hours.
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, and the rotation speed of the stirrer is 500-1500 rpm.
The principle of the polyamide 66 composition of the invention is as follows:
in order to solve the defect of poor compatibility of PA, low dielectric filler hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane (POSS) in a polyamide 66 composition, the compatibility between the PA and the low dielectric filler is improved by adding a compatilizer POE-g-MAH, the compatibility between the PA and the low dielectric filler is improved by adding a titanate coupling agent, and the effect of the titanate coupling agent on coating the low dielectric filler and the processing performance of the PA composition are improved by adding a lubricating dispersant hyperbranched polyester polymer and erucamide. According to the invention, the addition of the auxiliary agent improves the interface bonding force and compatibility between the PA and the low dielectric filler, and simultaneously improves the mechanical property and the processing property of the PA composition, so that the polyamide 66 composition with excellent comprehensive properties is prepared.
The low-viscosity polyamide 66 resin adopted by the invention has the intrinsic viscosity of 1.32-1.47 dL/g, good processing performance and general mechanical performance, while the high-viscosity polyamide 66 resin has the intrinsic viscosity of 1.75-1.92 dL/g, good mechanical performance and general processing performance, so that the polyamide 66 composition with excellent mechanical performance and processing performance is obtained by compounding the two PA resins.
The maleic anhydride group in the compatilizer POE-g-MAH adopted by the invention can react with the terminal amino group of the PA, the terminal hydroxyl group of the hollow glass microsphere and the coupling agent coated with the low dielectric filler, so that the compatibility between the PA and the low dielectric filler is improved, and the impact property of the polyamide 66 composition can be improved by the POE-g-MAH.
The hollow glass micro-beads (HGS) adopted by the invention are hollow spherical powdery inorganic nonmetallic materials, the main components of the hollow spherical powdery inorganic nonmetallic materials are soda lime borosilicate glass, and inert gases such as thin nitrogen, carbon dioxide and the like are filled in the cavity of the hollow spherical inorganic nonmetallic materials, so that the dielectric constant of the hollow glass micro-beads is only 1.2-1.5 (1 GHz).
The polyhedral oligomeric silsesquioxane Polymer (POSS) adopted by the invention has a highly symmetrical cubic cage type framework, has internal nanopores so that the POSS has a very low dielectric constant of 2.1-2.5 (1GHz), can effectively reduce the dielectric constant of a blend, does not obviously influence the mechanical property of the blend, has good compatibility with a base material resin, can effectively reduce particle agglomeration, contains an inorganic core consisting of silicon and oxygen in POSS molecules, has good thermal stability and larger molecular size, and has the effect of blocking the chain segment movement of polymer molecules, so that the addition of the POSS is beneficial to improving the thermal stability of the composition. In addition, the polyhedral oligomeric silsesquioxane polymer is preferably a polyhedral oligomeric silsesquioxane polymer with an epoxy group as a terminal group, and the epoxy group of POSS can react with the terminal hydroxyl group of HGS or a coupling agent, so that the compatibility between PA and the low dielectric filler can be further improved.
The effect of the titanate coupling agent used in the present invention is attributed to its effect on the interface, i.e. it can form a chemical bridge between the inorganic filler and the organic polymer, which is coupled by the direct chemical action of its alkoxy groups with the trace amount of hydroxyl groups adsorbed on the surface of the low dielectric filler, while its organic phase has good compatibility with PA.
The polytetrafluoroethylene resin adopted by the invention is mainly used as a modifier and a release agent of the polyamide 66 composition by utilizing the special lubricating property and non-stick property, and the dielectric constant of the polytetrafluoroethylene resin is lower and is only 2.0(1 GHz).
The hyperbranched polyester polymer adopted by the invention is a high temperature resistant dendritic structure additive with a polyester structural unit, which can obviously improve the processing fluidity of the polyamide 66 composition and the coating effect of the coupling agent, improve the dispersion degree of the filler in the polyamide 66 composition system, effectively solve the surface defect and simultaneously improve the surface glossiness of the product.
The erucamide adopted by the invention has higher melting point and good thermal stability, can obviously improve the processing fluidity of the polyamide 66 composition and the coating effect of the coupling agent, improves the dispersion degree of the filler in the polyamide 66 composition system, and has little influence on the mechanical property of the polyamide 66 composition.
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 in the PA blending process is better, 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 PA in a blending process, can prevent thermal degradation of PA in a high-temperature process, and inhibits thermo-oxidative discoloration of PA caused by long-time extrusion processing, and also provides a method for preparing Nitrogen Oxide (NO)x) 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 defect of poor compatibility of PA, low dielectric filler hollow glass microspheres (HGS) and polyhedral oligomeric silsesquioxane Polymers (POSS) in the existing polyamide 66 composition, the compatibility between PA and the low dielectric filler is improved by adding compatilizer POE-g-MAH, titanate coupling agent, lubricating dispersant hyperbranched polyester polymer and erucamide, the processability of the composition is improved by adopting low molecular weight PTFE, the dielectric constant of the composition is reduced by using HGS, POSS and PTFE in a compounding way, the yellowing phenomenon and the thermal stability of the polyamide 66 composition in the blending processing process are improved by using N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate in a compounding way, the raw material components are matched with each other, so that the obtained polyamide 66 composition has excellent mechanical property, processability and low dielectric constant, and can be applied to shells, coating materials, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
The preparation method of the polyamide 66 composition 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 composition according to one 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 composition according to an embodiment of the present invention is as follows (see fig. 1 for a flow chart of the preparation process):
R1＝POE，R2＝POSS，R3HGS or coupling agents
Mechanism of reaction
As can be seen from the above reaction formula, the acid anhydride group of POE-g-MAH reacts with the terminal amino group of PA, and the epoxy group of POSS reacts with the terminal hydroxyl group of HGS or coupling agent, thereby improving the compatibility between PA and low dielectric filler.
The examples of the invention and the comparative examples used the following raw materials:
low viscosity polyamide 66 resin with intrinsic viscosity of 1.32dL/g, selected from engineering plastics of Hippocampus Temminck;
high viscosity polyamide 66 resin with intrinsic viscosity of 1.92dL/g, selected from engineering plastics of Hill-Sharpse Ames Limited liability company;
the ethylene-octene copolymer is grafted with maleic anhydride, the grafting ratio of the maleic anhydride is 1.2%, and the maleic anhydride is selected from new molecular material science and technology company of Nantong Ri;
the hollow glass microspheres have the compressive strength of 60MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
the hollow glass microspheres have the compressive strength of 30MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
epoxycyclohexylethyl-POSS selected from the American company Hybrid Plastics;
glycidyl-POSS selected from Hybrid Plastics, USA;
mono-alkoxy fatty acid titanate coupling agent (type is titanate coupling agent TC-130), selected from chemical auxiliary oil material factory of Tianchang city;
polytetrafluoroethylene resin, molecular weight 5 ten thousand, selected from great gold fluorine chemical (China) limited;
polytetrafluoroethylene resin having a molecular weight of 200 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
the hyperbranched polyester polymer (the type is CYD-C600), the thermal decomposition temperature is more than or equal to 350 ℃, and the hyperbranched polyester polymer is selected from Wehaichen molecular new materials GmbH;
erucamide, selected from the group consisting of Haimengteng New materials science and technology, Inc.;
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.
The present invention will be described in detail with reference to specific examples.
Example 1:
the embodiment provides a polyamide 66 composition, which is prepared from the following raw materials in parts by weight:
60 parts of low-viscosity polyamide 66 resin,
20 parts of polyamide 66 resin with high viscosity,
20 parts of maleic anhydride grafted by the ethylene-octene copolymer,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 90 ℃ for 8 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, epoxy cyclohexyl ethyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 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 2:
the embodiment provides a polyamide 66 composition, which is prepared from the following raw materials in parts by weight:
93 parts of low-viscosity polyamide 66 resin,
5 parts of polyamide 66 resin with high viscosity,
2 parts of maleic anhydride grafted by the ethylene-octene copolymer,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 120 ℃ for 4 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 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 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 3:
the embodiment provides a polyamide 66 composition, which is prepared from the following raw materials in parts by weight:
68 parts of low-viscosity polyamide 66 resin,
16 parts of polyamide 66 resin with high viscosity,
16 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 100 ℃ for 6 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 265 ℃, the temperature in the seventh zone was 265 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 300 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 4:
the embodiment provides a polyamide 66 composition, which is prepared from the following raw materials in parts by weight:
85 parts of low-viscosity polyamide 66 resin,
9 parts of polyamide 66 resin with high viscosity,
6 parts of maleic anhydride grafted by the ethylene-octene copolymer,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 deg.C, the temperature in the second zone was 275 deg.C, the temperature in the third zone was 275 deg.C, the temperature in the fourth zone was 280 deg.C, the temperature in the fifth zone was 280 deg.C, the temperature in the sixth zone was 275 deg.C, the temperature in the seventh zone was 275 deg.C, the temperature in the eighth zone was 275 deg.C, the temperature in the die head was 275 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 5:
the embodiment provides a polyamide 66 composition, which is prepared from the following raw materials in parts by weight:
72 parts of low-viscosity polyamide 66 resin,
14 parts of polyamide 66 resin with high viscosity,
14 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition, which is prepared from the following raw materials in parts by weight:
78 parts of low-viscosity polyamide 66 resin,
12 parts of polyamide 66 resin with high viscosity,
10 parts of maleic anhydride grafted by the ethylene-octene copolymer,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition, which is prepared from the following raw materials in parts by weight:
75 parts of low-viscosity polyamide 66 resin,
13 parts of high-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition, which is prepared from the following raw materials in parts by weight:
75 parts of low-viscosity polyamide 66 resin,
13 parts of high-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 deg.C, and.
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 composition prepared from the following raw materials in parts by weight:
88 parts of low-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin at 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic diamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition prepared from the following raw materials in parts by weight:
75 parts of low-viscosity polyamide 66 resin,
13 parts of high-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition prepared from the following raw materials in parts by weight:
75 parts of low-viscosity polyamide 66 resin,
13 parts of high-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition prepared from the following raw materials in parts by weight:
75 parts of low-viscosity polyamide 66 resin,
13 parts of high-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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 composition prepared from the following raw materials in parts by weight:
75 parts of low-viscosity polyamide 66 resin,
13 parts of high-viscosity polyamide 66 resin,
12 parts of ethylene-octene copolymer grafted maleic anhydride,
the sum of the parts by weight of the low-viscosity polyamide 66 resin, the high-viscosity polyamide 66 resin and the ethylene-octene copolymer grafted maleic anhydride is 100 parts,
the preparation method of the polyamide 66 composition comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 66 resin, the cooled high-viscosity polyamide 66 resin, the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, 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 hollow glass beads, glycidyl-POSS and monoalkoxyl fatty acid titanate coupling agent into another stirrer for mixing;
(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 (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 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 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; b, the compressive strength of the hollow glass beads is 30 MPa; c, the molecular weight of the polytetrafluoroethylene resin is 200 ten thousand;
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 compositions prepared in the above examples and comparative examples were subjected to the following property tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 275 ℃, and the load is 2.16 kg;
dielectric constant: the test frequency is 1GHz according to the test of GB/T5597-1999 standard. For the present composition, the lower the dielectric constant, the better.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the Polyamide 66 compositions of the examples and comparative examples
Examples 1 to 7 are to adjust the addition amounts of low-viscosity PA66, high-viscosity PA66, POE-g-MAH, HGS, POSS, titanate coupling agent, PTFE, hyperbranched polyester polymer, and erucamide, and as can be seen from the table, as the addition amount of PA increases (or the addition amount of POE-g-MAH decreases), the tensile strength of the obtained polyamide 66 composition tends to increase, while the impact strength and melt index tend to decrease, mainly because the tensile strength of the PA base material is higher, while the tensile strength of POE-g-MAH itself is lower, but the processing flowability of POE-g-MAH is better, and the function of toughening can be achieved at the same time; as the addition amount of HGS and POSS is reduced, the dielectric constant of the material shows a trend of increasing. The polyamide 66 composition obtained in example 7 has the best overall properties and the best proportions of the raw materials, all under the combined action of various factors.
Example 7 in comparison with example 8, the screw shape of the parallel twin-screw extruder of example 8 was a twin screw and the screw shape of the parallel twin-screw extruder of example 7 was a single screw, and it was found by comparison that the polyamide 66 composition prepared using the screw parameters of the parallel twin-screw extruder described in example 7 was better in tensile strength, notched impact strength and melt index and lower in dielectric constant.
Example 7 in comparison to comparative example 1, comparative example 1 did not use a higher intrinsic viscosity polyamide 66 resin, and thus the tensile strength and notched impact strength of the polyamide 66 composition of comparative example 1 were lower than those of example 7; example 7 compared with comparative example 2, the compressive strength of the hollow glass bead used in comparative example 2 was 30MPa, while the compressive strength of the hollow glass bead used in example 7 was 60MPa, and since the compressive strength of the hollow glass bead used in comparative example 2 was low, the hollow glass bead was easily broken during the parallel twin-screw extruder processing, and lost the characteristics of reinforcement and low dielectric constant, resulting in a great decrease in mechanical properties of the polyamide 66 composition and an increase in dielectric constant; example 7 compared to comparative example 3, the polyamide 66 composition had a higher dielectric constant than example 7 because comparative example 3 did not incorporate the low dielectric constant HGS and POSS; example 7 compared to comparative example 4, comparative example 4 used a polytetrafluoroethylene resin having a molecular weight of 200 ten thousand, which was inferior in processing fluidity during parallel twin-screw extruder processing, and was liable to suffer extrusion swell to cause strand breakage of the polyamide 66 composition, resulting in poorer tensile strength, notched impact strength and melt index, and higher dielectric constant of the polyamide 66 composition prepared in comparative example 4; example 7 compared to comparative example 5, since comparative example 5 has no added hyperbranched polyester polymer and erucamide, and the two lubricating dispersants can function to promote the dispersion of the titanate coupling agent in the polyamide 66 composition, the monoalkoxy fatty acid titanate coupling agent is less effective in coating the hollow glass microspheres and glycidyl-POSS, the interfacial bonding force and compatibility of the PA composition with the low dielectric filler are reduced, and the processability of the polyamide 66 composition is poor, so that the polyamide 66 composition prepared in comparative example 5 has poorer tensile strength, notched impact strength and melt index, and higher dielectric constant.
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 composition is characterized by being prepared from the following raw materials in parts by weight:
the intrinsic viscosity of the low-viscosity polyamide 66 resin is 1.32-1.47 dL/g; the intrinsic viscosity of the high-viscosity polyamide 66 resin is 1.75-1.92 dL/g; the compressive strength of the hollow glass beads is not lower than 53 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand.
2. The polyamide 66 composition of claim 1, prepared from the following raw materials in parts by weight:
3. the polyamide 66 composition of claim 2, which is prepared from the following raw materials in parts by weight:
4. the polyamide 66 composition of claim 1, wherein the ethylene-octene copolymer grafted maleic anhydride has a maleic anhydride grafting ratio of 1.0-1.4%; and/or the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group; and/or the titanate coupling agent is a mono-alkoxy fatty acid titanate coupling agent.
5. The polyamide 66 composition of any one of claims 1-4, wherein the hollow glass microspheres have a compressive strength of 55 to 65 MPa; and/or the number average molecular weight of the polytetrafluoroethylene resin is 3-7 ten thousand; and/or the polyhedral oligomeric silsesquioxane polymer is epoxycyclohexylethyl-POSS and/or glycidyl-POSS.
6. A process for the preparation of a polyamide 66 composition according to any one of claims 1 to 5, characterized in that it comprises the following steps:
(1) drying the low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin, and mixing the dried low-viscosity polyamide 66 resin and the high-viscosity polyamide 66 resin with the ethylene-octene copolymer grafted maleic anhydride, polytetrafluoroethylene resin, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic diamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide;
(3) and (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 parallel double-screw extruder in the lateral direction, performing melt extrusion, and granulating.
7. The method as claimed in claim 6, wherein the process parameters of the parallel twin-screw extruder in step (3) include: the temperature of the first zone is 255-275 ℃, the temperature of the second zone is 260-280 ℃, the temperature of the third zone is 260-280 ℃, the temperature of the fourth zone is 265-285 ℃, the temperature of the fifth zone is 265-285 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the seventh zone is 260-280 ℃, the temperature of the eighth zone is 260-280 ℃, the temperature of the die head is 260-280 ℃, and the rotation speed of the screw is 200-600 rpm; preferably, the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 260-270 ℃, the temperature of the second zone is 265-275 ℃, the temperature of the third zone is 265-275 ℃, the temperature of the fourth zone is 270-280 ℃, the temperature of the fifth zone is 270-280 ℃, the temperature of the sixth zone is 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 265-275 ℃, the temperature of the die head is 265-275 ℃ and the rotation speed of the screw is 300-500 rpm;
and/or the drying temperature in the step (1) is 90-120 ℃, and the drying time is 4-8 hours; preferably, the drying temperature in the step (1) is 100-110 ℃, and the drying time is 4-6 hours.
8. The production method according to claim 6 or 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 claim 6 or 7, wherein the mixing step is performed by using a stirrer having a rotation speed of 500 to 1500 rpm in the step (1) and/or the step (2).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111675900A (en) * | 2020-07-24 | 2020-09-18 | 广东工业大学 | Low-dielectric-constant glass fiber reinforced nylon composite material and preparation method thereof |
| CN115819965A (en) * | 2022-12-01 | 2023-03-21 | 上海升广科技有限公司 | Glass bead reinforced wear-resistant polyamide composite foamed plastic and preparation method thereof |
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| CN101885910A (en) * | 2009-05-12 | 2010-11-17 | 上海日之升新技术发展有限公司 | High wear-resistant PA66 composite material and preparation method thereof |
| CN102382452A (en) * | 2010-12-27 | 2012-03-21 | 重庆文理学院 | Nano-modified nylon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101885910A (en) * | 2009-05-12 | 2010-11-17 | 上海日之升新技术发展有限公司 | High wear-resistant PA66 composite material and preparation method thereof |
| CN102382452A (en) * | 2010-12-27 | 2012-03-21 | 重庆文理学院 | Nano-modified nylon composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111675900A (en) * | 2020-07-24 | 2020-09-18 | 广东工业大学 | Low-dielectric-constant glass fiber reinforced nylon composite material and preparation method thereof |
| CN115819965A (en) * | 2022-12-01 | 2023-03-21 | 上海升广科技有限公司 | Glass bead reinforced wear-resistant polyamide composite foamed plastic and preparation method thereof |
| CN115819965B (en) * | 2022-12-01 | 2024-04-02 | 上海升广科技有限公司 | Glass bead reinforced wear-resistant polyamide composite foamed plastic and preparation method thereof |
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