CN108239393B - Light polyamide composition and preparation method thereof - Google Patents
Light polyamide composition and preparation method thereof Download PDFInfo
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- CN108239393B CN108239393B CN201611221091.7A CN201611221091A CN108239393B CN 108239393 B CN108239393 B CN 108239393B CN 201611221091 A CN201611221091 A CN 201611221091A CN 108239393 B CN108239393 B CN 108239393B
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
Abstract
The invention discloses a polyamide composition and a preparation method thereof, wherein the polyamide composition comprises the following components in parts by weight: polyamide resin: 55-95 parts by weight of modified hollow inorganic powder: 5-37 parts by weight, and, a compatibilizer: 1-10 parts by weight; wherein the polyamide resin comprises a polyamide 5X resin. The modified hollow inorganic powder is adopted to prepare the light polyamide, the modified hollow inorganic powder and the compatibilizer have synergistic effect, the mechanical property, the heat resistance and the like of the composite material are improved on the premise of reducing the density of the polyamide composite material, and the modified hollow inorganic powder and the compatibilizer have inseparable effect on the density improvement and the mechanical property improvement of the light polyamide.
Description
Technical Field
The invention relates to a light polyamide composition and a preparation method thereof.
Background
Polyamides are polymers having amide-based repeating units in the polymer chain, which have a good balance of properties, such as: the high-strength and high-toughness high-heat-resistance wear-resistance high-chemical-resistance high-strength self-extinguishing high-strength self-lubricating high-wear-resistance high-chemical-resistance high-wear-. Since the 50 s in the 20 th century, a series of polyamide engineering plastics with better performance are developed by a polymer modification method, and the application field is continuously expanded.
Polyamide modification is the focus of research today. The new material with special properties obtained by modification is a relatively low-cost, simple and direct method compared with the research and development of new polymers. The polymer modification is to add inorganic or organic substances into polymers by physical and mechanical methods, or to blend different types of polymers, or to chemically realize copolymerization, grafting, blocking and crosslinking of polymers, or to combine the above methods, so as to achieve the effects of reducing the manufacturing cost of materials, improving the molding processing performance or the final use performance, or endowing the polymer materials with unique functions only on the surface and in the aspects of electricity, magnetism, light, heat, sound, combustion, and the like.
The key point of polymer modification is 'improvement', namely, the improvement can make up for the weakness, develop and retain the existing excellent performance of the polymer, inhibit and overcome the defects of the polymer, and endow the polymer with new performance according to the actual needs. The modification of the polymer is to find an optimal balance point among the service performance, the processing performance and the production cost of the polymer.
In the process of modifying polyamide, inorganic materials such as talc powder, mica, calcium carbonate, wollastonite, glass fiber, flame retardant and the like are usually selected to be blended and modified to obtain a polyamide-based composite material, so that the rigidity, heat resistance, dimensional stability, chemical resistance, surface gloss, combustibility and the like of the polyamide are further improved. However, the inorganic material is generally denser than the polyamide resin, resulting in an excessively dense composite material.
In some application fields, it is desirable that the polyamide composite material not only has excellent use performance, but also has lower density, such as light weight of an automobile, and it is desirable to reduce the service quality (weight) of the automobile as much as possible on the premise of ensuring the strength and safety performance of the automobile, thereby improving the dynamic property of the automobile, reducing the fuel consumption and reducing the exhaust pollution. Experiments have shown that the mass of the vehicle is reduced by half and the fuel consumption is also reduced by nearly half. The light weight of automobiles has become a trend of the development of automobiles in the world due to the need for environmental protection and energy conservation. As another example, a buoy; the intrinsic density of polyamides, 1.04-1.16, also becomes critical limiting their use.
Currently, the preparation of light polyamide materials is generally achieved by foaming techniques, such as expanded polystyrene (XPS), expanded polypropylene (XPP), and the like. However, in the foaming process, the shape, size and the like of the micro-bubbles are difficult to control, so that defects are usually generated inside the polyamide material product, partial excellent performances are lost, and the mechanical properties of the polymer material are often greatly reduced due to the large pores and more defects of the foaming material.
Polyamide 5X is a novel high molecular polymer, and is still in the early stage of research and development, so that it is a major challenge in the existing high molecular polymerization field to prepare light polymeric materials based on it.
Disclosure of Invention
The invention provides a novel light polyamide composition and a preparation method of a composite material thereof, aiming at overcoming the problems that the light polymer material in the prior art is difficult to meet the existing requirements on light weight, poor performance and more defects. The light polyamide composition can reduce the overall density, improve the mechanical property, the heat resistance and the like of the light polyamide composition, and improve the processing fluidity of polyamide.
One of the objects of the present invention: a polyamide composition comprises the following components in parts by weight:
polyamide resin: 55 to 95 parts by weight of a stabilizer,
modified hollow inorganic powder: 5-37 parts by weight;
and, a compatibilizer: 1-10 parts by weight;
wherein the polyamide resin comprises a polyamide 5X resin.
The following describes a preferred embodiment of the above-described embodiment:
in a preferred embodiment of the present invention, the polyamide 5X is a polyamide obtained by polymerizing 1, 5-pentanediamine and dicarboxylic acid as monomers. Wherein the dicarboxylic acid can be short-chain dicarboxylic acid (the number of carbon atoms on the carbon chain is less than 10) or long-chain dicarboxylic acid; wherein, the short-chain dibasic acid preferably comprises succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, preferably adipic acid and sebacic acid; the long carbon chain dibasic acid preferably includes undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, maleic acid, Δ 9-1, 18-octadecenedioic acid.
In a preferred embodiment of the present invention, the polyamide composition may further comprise other polyamides other than polyamide 5X, the other polyamides comprising: one or more of polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, polyamide 12, and polyamide 1414.
In a preferred embodiment of the present invention, the polyamide 5X comprises a polyamide obtained by polymerizing a bio-based polyamide monomer.
In a preferred embodiment of the present invention, the polyamide 5X monomer is preferably obtained by a biological fermentation process or by chemical processing of sustainable natural compounds. Preferably, the 1, 5-pentanediamine is obtained by a biological fermentation method.
In a preferred embodiment of the invention, the polyamide 5X comprises 35 to 100% of biomass origin.
In a preferred embodiment of the present invention, the polyamide 5X has a relative viscosity of 96% (by mass) sulfuric acid of 2.4 to 3.2.
In a preferred embodiment of the present invention, the polyamide 5X is preferably polyamide 56. The polyamide 56 is obtained by polymerizing 1, 5-pentanediamine and adipic acid serving as raw materials. The polyamide 56 preferably has a relative viscosity of 2.4 to 3.2 in terms of 96 mass% sulfuric acid.
According to a preferable technical scheme, the modified hollow inorganic powder comprises modified hollow inorganic powder obtained by modifying hollow inorganic powder with a coupling agent. The weight portion of the modified hollow inorganic powder is preferably 8-20.
Wherein the coupling agent comprises: a silane coupling agent and/or a titanate coupling agent;
the silane-based coupling agent preferably includes: gamma-aminopropyltriethoxysilane (NH)2CH2CH2CH2Si(OC2H5)3Trade name: KH550), g-aminopropyl trimethoxy silane (NH)2(CH2)3Si(OCH3)3Trade name: KH551), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (CH)2-CH(O)CH2-O(CH2)3Si(OCH3)3Trade name: KH560), gamma- (methacryloyloxy) propyltrimethoxysilane (CH)3CCH2COO(CH2)3Si(OCH3)3Trade name: KH570), N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (NH)2CH2CH2NH2CH2CH2CH2SiCH3(OCH3)2Trade name: KH602), N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (NH)2CH2CHNHCH2CH2CH2Si(OCH3)3Trade name: KH792) and vinyltriethoxysilane (CH)2＝CHSi(OCH2CH3)3Trade name: KH151) is added;
the titanate-based coupling agent preferably includes: isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate (C)55H111O9Ti, trade name: NDZ101), isopropyltrioleoxy (trioctylphosphonoxy) titanate (C)54H106O7Ti, trade name: NDZ105), isopropyl tris (dioctyl pyrophosphato acyloxy) titanate (C)51H112O22P6Ti, trade name: NDZ201) and bis (dioctyloxypyrophosphate) ethylenetitanate (C)34H74O16P4Ti, trade name: NDZ 311).
According to a preferable technical scheme of the invention, the hollow inorganic powder comprises one or more of hollow glass beads, hollow ceramic powder and hollow titanium dioxide. The particle size of the hollow inorganic powder is preferably 35-70 μm; the true density of the hollow inorganic powder is preferably 0.10-0.64g/m3。
According to a preferred technical scheme, the preparation method of the modified hollow inorganic powder comprises the following steps:
(1) under the condition of stirring, spraying a vaporous ethanol-water solution of a coupling agent into the hollow inorganic powder, and mixing to obtain a neutral product;
(2) and drying the product to obtain the product.
Wherein the concentration of the ethanol-water solution of the coupling agent is 20-40%, and the percentage is the mass percentage of the coupling agent in the ethanol-water solution.
Wherein the weight ratio of the hollow inorganic powder to the coupling agent is (5-35): (0.01-2).
Wherein the rotation speed during the mixing is preferably 600-800 rpm.
Wherein the temperature at the time of mixing is preferably 60 to 80 ℃.
Wherein the mixing time is preferably 3-5 min.
Wherein the drying temperature is preferably 70 to 90 ℃, more preferably 75 to 85 ℃.
Wherein the drying time is preferably 8 to 16h, more preferably 10 to 14h, most preferably 11 to 13 h.
In a preferred embodiment of the present invention, the compatibilizer comprises: methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-ethyl acrylate, random ethylene-butyl acrylate copolymer, random ethylene-methyl acrylate-maleic anhydride copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted ethylene-vinyl acetate, maleic anhydride grafted hydrogenated butadiene-styrene block copolymer, maleic anhydride grafted ethylene-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene terpolymer.
In a preferred embodiment of the present invention, the polyamide composition further comprises other additives, wherein the other additives comprise: one or more of a lubricant, a nucleating agent and an antioxidant.
According to a preferable technical scheme of the invention, the content of the other auxiliary agents is 1-5 parts by weight.
Wherein the lubricant preferably comprises: one or more of N, N' -ethylene bis stearamide, oxidized polyethylene wax, polyethylene-vinyl acetate wax, partially saponified polyethylene wax, oleamide, erucamide, pentaerythritol stearate, montanate, calcium stearate, zinc stearate, sodium stearate, barium stearate and high molecular silicone.
Wherein the nucleating agent preferably comprises: one or more of P22, calcium montanate, sodium montanate, polyacrylic acid ionomer, organic montmorillonite, superfine talcum powder, superfine mica, alumina and magnesia.
Among them, the antioxidant preferably includes: n, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite, pentaerythritol bis (2, 4-di-tert-butylphenyl) propionate ] diphosphite, 2-methylene-bis (4-ethyl-6-tert-butylphenol), 4-meta-butylene-bis- (6-tert-butyl-m-cresol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
Another object of the present invention is to provide a method for preparing a polyamide resin, comprising the steps of:
uniformly mixing the polyamide resin, the modified hollow inorganic powder and the compatibilizer according to the proportion, and extruding and molding;
or, the polyamide resin, the modified hollow inorganic powder, the compatibilizer and the other auxiliary agents are uniformly mixed according to the proportion, and then are extruded and molded.
Preferably, the polyamide resin and the compatibilizer are uniformly mixed and then uniformly mixed with the modified hollow inorganic powder.
Among them, it is preferable that the polyamide resin and the compatibilizer are uniformly mixed and then mixed in a mixer.
Wherein, when the polyamide resin and the compatibilizer are uniformly mixed, the rotation speed during mixing is preferably 600-800 rpm.
Wherein, when the polyamide resin and the compatibilizer are uniformly mixed, the mixing temperature is preferably 60-80 ℃.
Wherein, the time for uniformly mixing the polyamide resin and the compatibilizer is preferably 3-5 min.
Among them, the operation of uniformly mixing with the modified hollow inorganic powder is preferably performed in a twin-screw extruder, and more preferably in an in-phase twin-screw extruder.
Wherein, the temperature of the double-screw extruder is 250-285 ℃ preferably.
Wherein, preferably, when the modified hollow inorganic powder is uniformly mixed, the rotating speed of the double-screw extruder is 150-250rpm, preferably 180-220 rpm.
When the polyamide resin also comprises other auxiliary agents, the other auxiliary agents are uniformly mixed with the polyamide resin and the compatibilizer, and then the subsequent operation is carried out.
Among them, preferably, a method for preparing a polyamide composition, the method comprising the steps of:
(1) uniformly mixing polyamide resin and the compatibilizer in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 600-800rpm, and the mixing time is 3-5 min;
(2) and (2) adding the uniformly mixed material in the step (1) into a double-screw extruder through a main feeding port of the double-screw extruder, and adding the modified hollow inorganic powder into the double-screw extruder through a side feeding port of the double-screw extruder for uniform mixing, wherein the temperature of the double-screw extruder is 250-285 ℃, and the rotating speed of the double screws is 150-250 pm.
Wherein the side feeding port is positioned at the position which is 1/3-3/5 of the length of the screw away from the discharge die orifice of the double-screw extruder.
When other auxiliary agents are also included in the polyamide resin, the auxiliary agents are uniformly mixed with the polyamide resin and the compatibilizer in the step (1).
The light polyamide composition is endowed with new performance by the light polyamide composition, and can be used in the fields of automobile instrument panels, building decoration, electronics and electricity and the like.
On the other hand, the polyamide in the present invention is preferably synthesized from a bio-based polyamide monomer. Currently, more than 99% of polyamide feedstocks come from petrochemical fuels and bio-based polyamides are becoming unusually active. The bio-based polyamide produced in large scale mainly comprises full bio-based polyamide and partial bio-based polyamide, wherein the full bio-based polyamide takes castor oil and glucose as raw materials, and one of diamine or diacid raw materials of partial bio-based polyamide comes from non-petrochemical fuel or primary raw material comes from petrochemical fuel. Compared with the traditional polyamide, the industrial chain of the bio-based polyamide not only reduces the consumption of non-renewable resources, but also reduces the emission of greenhouse gases by about 50%.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
The performance detection method of the polyamide resin in the invention refers to the following test standards:
density: ISO 1183-1:2004 Plastic non-foam Density determination method part one: dipping, hydrometer and titration;
tensile property: ISO 527-2:1993 determination of tensile Properties of plastics, second part: molding and extruding plastic test conditions;
bending property: ISO 178:2001 plastic bending property test;
notched izod impact strength: ISO 180:2001 plastic Izod impact performance.
Example 1
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 4195g
Hollow glass beads (particle size 56 μm, true density 0.32 g/cm)313.78MPa resistant): 500g
Compatibilizer POE-g-MAH: 250g
Coupling agent KH-550: 5g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder and antioxidant 1098): 50g
The preparation method of the light polyamide 56 resin comprises the following steps:
(1) dispersing 5g of KH-550 in 150g of ethanol-water (mass ratio of 1: 1), and then uniformly spraying the mixed solution on the surfaces of the hollow glass microspheres under high-speed stirring to uniformly coat the hollow glass microspheres with the coupling agent; the rotating speed of the high-speed mixer is 600-800rpm, the mixing temperature is 60-80 ℃, and the mixing time is 3-5 min;
(2) drying the uniformly mixed materials at the temperature of 80 ℃ for 12 hours to obtain modified hollow glass microspheres;
(3) polyamide 56(PA56), POE-g-MAH and other auxiliary agents are combined and uniformly mixed in a high-speed mixer, the rotating speed of the high-speed mixer is 500-600rpm, the mixture is mixed at room temperature, and the mixing time is 3-5 min;
(4) placing the modified hollow glass beads obtained in the step (2) into a side feeding port of an extruder; placing the uniformly mixed material in the step (3) into a main feeding container of an extruder;
(5) the twin-screw extruder extrudes, and the temperature settings of all zones (from the main feeding section to the die head) are as follows: 180 ℃, 220 ℃, 240 ℃, 260 ℃, 270 ℃ and 265 ℃ and the rotation speed of the twin screw is 200 rpm.
Wherein, according to the routine in the art, the steps (1) and (2) and the step (3) can be carried out simultaneously, or the steps (1) and (2) can be carried out first and then the step (2) can be carried out, or the step (3) can be carried out first and then the steps (1) and (2) can be carried out.
Drying the prepared slices at 80 ℃ for 6h, then injection molding into standard test sample strips according to ISO standards, wherein the temperature of each zone of the injection molding machine is set as follows (from a feeding port to a nozzle): 240 ℃, 250 ℃, 260 ℃, 265 ℃ and 265 ℃. The test specimens were then stored sealed at 23 ℃ for 48h and tested according to ISO standards.
The test results are shown in Table 1.
Example 2
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 3690g
Hollow glass beads (particle size 56 μm, true density 0.32 g/cm)313.78MPa resistant): 1000g
Compatibilizer Lotryl 29MA 03: 250g
Coupling agent KH-550: 10g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder and antioxidant 1098): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 3
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 3185g
Hollow glass beads (particle size 56 μm, true density 0.32 g/cm)313.78MPa resistant): 1500g
Compatibilizer Lotader AX 8900: 250g
Coupling agent KH-550: 15g of
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 4
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 3690g
Hollow glass beads (particle size 45 μm, true density 0.40 g/cm)327.56MPa resistance to compression): 1000g
Compatibilizer POE-g-MAH: 250g
Coupling agent KH-550: 10g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 5
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 3185g
Hollow glass beads (particle size 45 μm, true density 0.40 g/cm)327.56MPa resistance to compression): 1500g
Compatibilizer Lotryl 29MA 03: 250g
Coupling agent KH-550: 15g of
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 6
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 4195g
Hollow glass beads (particle size 45 μm, true density 0.40 g/cm)327.56MPa resistance to compression): 500g
Compatibilizer Lotader AX 8900: 250g
Coupling agent KH-550: 5g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 7
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 3185g
Hollow glass beads (particle size 45 μm, true density 0.46 g/cm)3Pressure resistance 41.34 MPa): 1500g
Compatibilizer POE-g-MA: 250g
Coupling agent KH-550: 15g of
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 8
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 4195g
Hollow glass beads (particle size 45 μm, true density 0.46 g/cm)3Pressure resistance 41.34 MPa): 500g
Compatibilizer Lotryl 29MA 0: 250g
Coupling agent KH-550: 5g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 9
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 3690g
Hollow glass beads (particle size 45 μm, true density 0.46 g/cm)3Pressure resistance 41.34 MPa): 1000g
Compatibilizer Lotader AX 8900: 250g
Coupling agent KH-550: 10g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Example 10
Polyamide 56(PA56, 96% sulfuric acid relative viscosity 2.72): 1845g
Polyamide 1010(PA1010, 96% sulfuric acid relative viscosity 2.66): 1845g
Hollow glass beads (particle size 45 μm, true density 0.46 g/cm)3Pressure resistance 41.34 MPa): 1000g
Compatibilizer Lotader AX 8900: 250g
Coupling agent KH-550: 10g
Other auxiliary agent combinations (including EBS, calcium stearate, calcium montanate, talcum powder, antioxidant 1098 and the like): 50g
Sample preparation and testing procedures are described in example 1. See table 1 for relevant test results.
Table 1: comparison of the Properties of light Polyamide 5X (PA56) compositions
The comparative examples correspond to the respective performance parameters of the PA56 resin.
From the above table, it can be seen that: the modified hollow inorganic powder and the compatibilizer can reduce the density of the composite material and improve the tensile strength, the bending modulus and the notch impact strength of the composite material at the same time under the condition of a specific proportion.
The foregoing description of the embodiments is provided to further illustrate and practice the invention, and therefore the invention is not limited to the disclosure of the embodiments, and those skilled in the art, in light of the present disclosure, will recognize that changes may be made in the embodiments without departing from the scope of the invention.
Claims (15)
1. A polyamide composition characterized by: the polyamide composition comprises the following components in parts by weight:
polyamide resin: 55 to 95 parts by weight of a stabilizer,
modified hollow inorganic powder: 5 to 37 parts by weight of a stabilizer,
and, a compatibilizer: 1-10 parts by weight;
wherein the content of the first and second substances,
the polyamide resin is polyamide 56 resin;
the compatibilizer is a random ethylene-methyl acrylate copolymer or a random ethylene-acrylate-glycidyl methacrylate copolymer;
the preparation method of the modified hollow inorganic powder comprises the following steps:
(1) under the condition of stirring, spraying a vaporous ethanol-water solution of a coupling agent into the hollow inorganic powder, and mixing to obtain a neutral product; the particle size of the hollow inorganic powder is 35-70 mu m; the true density of the hollow inorganic powder is 0.10-0.64g/cm3；
(2) And drying the product to obtain the product.
2. The polyamide composition of claim 1, wherein:
the polyamide 56 comprises polyamide obtained by polymerizing polyamide monomers from a bio-base;
the polyamide 56 has a relative viscosity of 2.4 to 3.2 with 96% sulfuric acid;
and/or the polyamide composition further comprises other polyamides other than polyamide 56, the other polyamides comprising: one or more of polyamide 6, polyamide 66, polyamide 69, polyamide 610, polyamide 612, polyamide 1010, polyamide 11, polyamide 12, and polyamide 1414.
3. The polyamide composition of claim 1, wherein: the weight portion of the modified hollow inorganic powder is 8-20.
4. The polyamide composition of claim 1, wherein: the coupling agent comprises: a silane coupling agent and/or a titanate coupling agent;
the hollow inorganic powder comprises one or more of hollow glass beads, hollow ceramic powder and hollow titanium dioxide.
5. The polyamide composition of claim 4, wherein: the silane coupling agent includes: one or more of gamma-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, and vinyltriethoxysilane;
the titanate-based coupling agent includes: one or more of isopropyldioleate acyloxy (dioctylphosphate) titanate, isopropyltrioleate acyloxy titanate, isopropyltris (dioctylphosphate) titanate and bis (dioctyloxypyrophosphate) ethylene titanate.
6. The polyamide composition of claim 1, wherein: the concentration of the ethanol-water solution of the coupling agent is 20-40%, and the percentage is the mass percentage of the coupling agent in the ethanol-water solution;
and/or the weight ratio of the hollow inorganic powder to the coupling agent is (5-35) to (0.01-2);
and/or the rotating speed during mixing is 600-800 rpm;
and/or the temperature during the mixing is 60-80 ℃;
and/or, the mixing time is 3-5 min;
and/or the drying temperature is 70-90 ℃;
and/or the drying time is 8-16 h.
7. The polyamide composition of claim 6, wherein: the drying temperature is 75-85 ℃.
8. The polyamide composition of claim 6, wherein: the drying time is 10-14 h.
9. The polyamide composition of any one of claims 1-8, wherein: the polyamide composition further comprises other auxiliary agents, wherein the other auxiliary agents comprise: one or more of a lubricant, a nucleating agent and an antioxidant; the content of the other auxiliary agents is 1 to 5 weight portions.
10. The polyamide composition of claim 1, wherein: the polyamide 56 comprises 35-100% biomass origin.
11. A process for producing a polyamide resin composite material from the polyamide composition as claimed in any one of claims 1 to 10, characterized in that: the preparation method comprises the following steps: uniformly mixing the polyamide resin, the modified hollow inorganic powder and the compatibilizer, and extruding and molding;
or, the polyamide resin, the modified hollow inorganic powder, the compatibilizer and the other auxiliary agents are uniformly mixed according to the parts by weight of any one of claims 1 to 10 and then are extruded to form the composite material.
12. The method of claim 11, wherein:
firstly, uniformly mixing the polyamide resin and the compatibilizer, and then uniformly mixing the polyamide resin and the compatibilizer with the modified hollow inorganic powder;
and/or when the polyamide resin and the compatibilizer are uniformly mixed, the rotating speed during mixing is 600-800 rpm;
and/or when the polyamide resin and the compatibilizer are uniformly mixed, the mixing temperature is 60-80 ℃;
and/or the polyamide resin and the compatibilizer are uniformly mixed for 3-5 min;
and/or the operation of uniformly mixing the modified hollow inorganic powder with the modified hollow inorganic powder is carried out in a double-screw extruder;
when the polyamide resin also comprises other auxiliary agents, the other auxiliary agents are uniformly mixed with the polyamide resin and the compatibilizer, and then the subsequent operation is carried out.
13. The method of claim 12, wherein: the rotating speed of the double-screw extruder is 150-250 rpm.
14. The method of claim 12, wherein: the rotation speed of the twin-screw extruder is 180-220 rpm.
15. The method of claim 12, wherein: the temperature of the double-screw extruder is 250-285 ℃.
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| CN111269564B (en) * | 2018-12-04 | 2023-01-24 | 上海凯赛生物技术股份有限公司 | Polyamide 5X abrasive wire and preparation method and application thereof |
| CN109735099A (en) * | 2018-12-27 | 2019-05-10 | 会通新材料(上海)有限公司 | It is a kind of improve light aging resisting characteristic 56 composition of polyamide and its application |
| CN111592755B (en) * | 2019-02-21 | 2022-07-19 | 上海凯赛生物技术股份有限公司 | Enhanced bio-based polyamide 56 composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796459A (en) * | 2004-12-28 | 2006-07-05 | 上海杰事杰新材料股份有限公司 | Method for preparing nylon in lightweight |
| CN102276978A (en) * | 2011-06-28 | 2011-12-14 | 江苏金发科技新材料有限公司 | Lightweight noise-reducing modified nylon material and preparation method thereof |
| CN102504528A (en) * | 2011-10-21 | 2012-06-20 | 奇瑞汽车股份有限公司 | Hollow glass microsphere-filled fiber-reinforced nylon composite material and preparation method thereof |
| CN103145979A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon and preparation method thereof |
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| JP2012233087A (en) * | 2011-05-02 | 2012-11-29 | Three M Innovative Properties Co | Thermoplastic resin composite containing hollow glass microsphere |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796459A (en) * | 2004-12-28 | 2006-07-05 | 上海杰事杰新材料股份有限公司 | Method for preparing nylon in lightweight |
| CN102276978A (en) * | 2011-06-28 | 2011-12-14 | 江苏金发科技新材料有限公司 | Lightweight noise-reducing modified nylon material and preparation method thereof |
| CN102504528A (en) * | 2011-10-21 | 2012-06-20 | 奇瑞汽车股份有限公司 | Hollow glass microsphere-filled fiber-reinforced nylon composite material and preparation method thereof |
| CN103145979A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon and preparation method thereof |
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