CN112646367B - Flame-retardant polyamide composite material and preparation method and application thereof - Google Patents

Flame-retardant polyamide composite material and preparation method and application thereof Download PDF

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CN112646367B
CN112646367B CN202011383517.5A CN202011383517A CN112646367B CN 112646367 B CN112646367 B CN 112646367B CN 202011383517 A CN202011383517 A CN 202011383517A CN 112646367 B CN112646367 B CN 112646367B
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composite material
flame
polyamide composite
retardant polyamide
polyamide
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CN112646367A (en
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陈清平
曾宪伸
马杰伟
周海昇
余雄春
相荣霆
郭工厂
袁和兵
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Anhui Jushi Technology Co ltd
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Polyrocks Suzhou Co ltd
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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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • 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

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Abstract

The invention discloses a flame-retardant polyamide composite material and a preparation method and application thereof. The flame-retardant polyamide composite material comprises the following components: polyamide resins, organic hypophosphites, microporous aluminum phosphites, corrosion inhibitors, silicone masterbatches and fibers; wherein the microporous aluminum phosphite accounts for 2-4% of the flame-retardant polyamide composite material by mass; the anticorrosive agent comprises esterified polyol and at least one of zinc borate and zinc stannate. The invention provides a synergistic flame-retardant reinforced polyamide composite material based on microporous aluminum phosphite, which has good stability, mechanical property and electrical property, outstanding physical abrasion resistance and chemical corrosion resistance in the processing process and very wide application prospect.

Description

Flame-retardant polyamide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a flame-retardant polyamide composite material as well as a preparation method and application thereof.
Background
Organic hypophosphite has been demonstrated to have a good flame retardant effect in polyamides, and is widely used as the mainstream halogen-free flame retardant. However, the introduction of organic phosphinate salts can exacerbate the corrosive wear on processing machines (extruders or injection molding machines). This wear phenomenon is more severe especially when fibrous hard fillers (e.g. glass fibers) are present together.
Metallic chemicals of zinc or tin, such as zinc oxide, zinc hydroxide, zinc borate, zinc hydroxide silicate, and zinc stannate, tin oxide hydrate, etc., are described in CN107223149A as having significant efficacy in improving corrosion of molds. In addition, boehmite also has some efficacy. CN109575586A also reports that hydrotalcite, calcium oxide, aluminum oxide, calcium hydroxide, etc. have an obvious effect on reducing the stability of the corrosive substances generated in the organic hypophosphite processing process on the mold and the material itself.
Although organic hypophosphites work synergistically with certain components, particularly with certain nitrogen-containing compounds, such as melamine polyphosphate (MPP) or Melamine Cyanurate (MCA). However, as mentioned in CN103154110A, CN109575586A, CN105264001A and CN108102361A, the introduction of MPP increases the corrosion effect relative to the organophosphinate system alone. To avoid the above problems, aluminum phosphite is a relatively preferred choice. Unfortunately, however, the aluminum phosphite salts mentioned in the current patents and publications are significantly inferior to MPP in flame retardant synergistic efficiency, and thus more addition is required.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention aims at providing a synergistic flame-retardant polyamide composite material based on microporous aluminum phosphite, the invention aims at providing a preparation method of the flame-retardant polyamide composite material, and the invention aims at providing an application of the flame-retardant polyamide composite material.
The invention provides the aluminum phosphite with a microporous structure and a higher synergistic effect and the organic hypophosphite flame retardant which are used together in a fiber reinforced polyamide system, so that the prepared composite material has high stability, good mechanical property and excellent electrical property, has outstanding physical abrasion resistance and chemical corrosion resistance in the processing process, and has wide application prospect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a first aspect of the invention provides a flame retardant polyamide composite material comprising the following components: polyamide resins, organic hypophosphites, microporous aluminum phosphites, corrosion inhibitors, silicone masterbatches and fibers;
the microporous aluminum phosphite accounts for 2-4% of the mass of the flame-retardant polyamide composite material;
the anticorrosive agent comprises esterified polyol and at least one of zinc borate and zinc stannate.
Preferably, in the flame-retardant polyamide composite material, the polyamide resin is one or a combination of aliphatic polyamide and semi-aromatic polyamide. The source of the synthetic monomer upstream of the polyamide resin can be traditional petroleum base or biological base.
Preferably, in the polyamide resin, the melting point of the aliphatic polyamide is more than or equal to 250 ℃, so that the requirement of high-temperature injection molding can be better met.
Preferably, in the polyamide resin, the semi-aromatic thermoplastic polyamide is at least one homopolymer, copolymer, terpolymer or high polymer derived from an aryl-containing monomer. The aryl-containing monomer may include terephthalic acid and derivatives thereof, isophthalic acid and derivatives thereof, p-xylylenediamine or m-xylylenediamine. Further preferred semi-aromatic polyamides include poly (m-xylylene adipamide) (polyamide MXD, 6), poly (dodecamethyleneterephthalamide) (polyamide 12T), poly (decamethyleneterephthalamide) (polyamide 10T), poly (nonanediamide terephthalamide) (polyamide 9T), hexamethylene terephthalamide/2-methylpentamethylenediamine terephthalamide copolyamide (polyamide 6T/DT), hexamethylene adipamide/hexamethylene terephthalamide/hexamethylene isophthalamide copolyamide (polyamide 66/6T/6I), poly (caprolactam-hexamethylene terephthalamide) (polyamide 6/6T), hexamethylene terephthalamide/hexamethylene isophthalamide (polyamide 6T/6I) copolymers.
Preferably, the polyamide resins are all injection molding grade.
Preferably, in the flame-retardant polyamide composite material, the molecular structural formula of the organic hypophosphite is shown as a formula (1) or a formula (2):
Figure BDA0002810343660000021
in the formula (1), R 1 、R 2 Each is a linear or branched C1-C6 alkyl group; r is 1 And R 2 May be the same or different; m is Mg, ca, al, sb, sn, ge, ti, zn, fe, zr, ce, bi, sr, mn, li, na, K or protonated nitrogen-containing base; m =1 to 4;
Figure BDA0002810343660000031
in the formula (2), R 3 、R 4 Each is a linear or branched C1-C6 alkyl group; r 3 And R 4 May be the same or different; r is 5 Is a linear or branched C1-C10 alkylene, C6-C10 arylene, C7-C20 alkylarylene or C7-C20 arylalkylene group; a is Mg, ca, al, sb, sn, ge, ti, zn, fe, zr, ce, bi, sr, mn, li, na, K or protonated nitrogen-containing base; a =1 to 4; n =1 to 4; x =1 to 4.
Preferably, the organic hypophosphite is ExolitTM series organic hypophosphite manufactured by the Corlaien company; further preferably, the organic hypophosphite is one or a combination of OP1230 and OP 1240.
Preferably, in the flame-retardant polyamide composite material, the particle size of the microporous aluminum phosphite is 0.2-20 microns.
Preferably, the purity of the microporous aluminum phosphite is more than or equal to 95%.
In some embodiments of the present invention, in order to avoid the influence of moisture possibly existing in the pores of the microporous aluminum phosphite, a vacuum drying process is required before use.
Preferably, in the anticorrosive agent for the flame-retardant polyamide composite material, the mass ratio of the esterified polyol to at least one of zinc borate and zinc stannate is 1: (3-5); further preferably, the mass ratio of the esterified polyol to at least one of zinc borate and zinc stannate is 1: (3-4).
Preferably, the zinc borate or the zinc stannate is anhydrous.
Preferably, in the anticorrosive, the esterified polyol is plenlize HC-103S produced by ajinomoto.
Preferably, in the flame-retardant polyamide composite material, the appearance of the silicone master batch is transparent or semitransparent particles, and the carrier does not contain organic compound components.
Preferably, the silicone masterbatch satisfies at least one of:
the effective content of organic silicon in the silicone master batch is more than or equal to 70 percent;
the molecular weight of the silicone master batch is more than or equal to 100 ten thousand;
the thermal weight loss temperature of the silicone master batch is more than or equal to 350 ℃.
More preferably, the molecular weight of the silicone master batch is 100 to 150 ten thousand; still more preferably, the molecular weight of the silicone masterbatch is 120 to 130 ten thousand.
Preferably, in the flame-retardant polyamide composite material, the fiber is at least one selected from glass fiber, carbon fiber and basalt fiber.
The fibers may be continuous long fibers or short fibers. Preferably, the external form of the fibers is chopped fibers.
Preferably, the fibers are chopped glass fibers. Therefore, the interference caused by judging the color change of the light-colored product except the color of the fiber can be eliminated. More preferably, the fibers are alkali-free chopped glass fibers, and the appearance form of the fibers can be common alkali-free chopped glass fibers or flat alkali-free chopped glass fibers.
Preferably, the fibers may be surface modified, in particular adhesion promoters or adhesion promoter systems, such as surface modification, particularly preferably silane-based. It is to be noted that the pre-treatment of the surface modification is not absolute. In addition, in addition to using silanes, polymer dispersions, film formers, branching agents, or fiber processing aids may also be used for treatment.
Preferably, the polyamide resin accounts for 35 to 58 percent of the mass of the flame-retardant polyamide composite material; 12 to 15 percent of organic hypophosphite; the anticorrosive agent accounts for 1.2 to 2.0 percent; 1.5 to 2.0 percent of silicone master batch; the fiber accounts for 25 to 40 percent.
Preferably, the flame retardant polyamide composite material further comprises an additive.
Preferably, in the flame-retardant polyamide composite material, the additive comprises at least one of an antioxidant, a polyamide stabilizer and a lubricant. The antioxidant comprises a primary antioxidant and a secondary antioxidant. Further preferably, the additive is a composition consisting of a primary antioxidant, a secondary antioxidant, a polyamide stabilizer and a lubricant. In the additive, the mass ratio of the main antioxidant to the auxiliary antioxidant to the polyamide stabilizer to the lubricant is preferably 1: (1.5-2.5): (0.5-1.5): (4-6). The primary antioxidant is preferably a triazine antioxidant, and in some embodiments of the present invention, the primary antioxidant is antioxidant 1790, such as antioxidant 1790 available from Cyanid corporation. The secondary antioxidant is preferably a bis-phosphorus antioxidant, and in some embodiments of the invention, the secondary antioxidant is the antioxidant P-EPQ. The polyamide stabilizer is preferably at least one of a copper salt in combination with an iodide and/or a phosphorus-containing compound, or a divalent manganese salt. The lubricant is preferably one of PETS (pentaerythritol stearate), TAF (modified ethylene bis fatty acid amide), or a combination thereof.
Preferably, the flame-retardant polyamide composite material consists of the following components in percentage by mass: 35 to 58 percent of polyamide resin, 12 to 15 percent of organic hypophosphite, 2 to 4 percent of microporous aluminum phosphite, 1.2 to 2.0 percent of anticorrosive agent, 1.0 to 1.2 percent of additive, 1.5 to 2.0 percent of silicone master batch and 25 to 40 percent of fiber. The sum of the mass percentages of the components is 100 percent.
Preferably, the polyamide resin accounts for 36.5 to 56.8 percent of the mass of the flame-retardant polyamide composite material.
Preferably, the additive accounts for 1.0-1.2% of the mass of the flame-retardant polyamide composite material.
The flame-retardant polyamide composite material can be continuously injected and used at a higher temperature. Preferably, the injection molding temperature of the flame-retardant polyamide composite material is 260-330 ℃; further preferably, the injection molding temperature of the flame-retardant polyamide composite material is 260-320 ℃.
The flame-retardant polyamide composite material can be natural color or dyed by adding a coloring agent.
A second aspect of the invention provides a method for preparing a flame retardant polyamide composite material according to the first aspect of the invention.
A preparation method of a flame-retardant polyamide composite material comprises the following steps:
mixing polyamide resin, an anticorrosive agent and silicone master batch, and adding into a main feeding port of a double-screw extruder;
mixing organic hypophosphite and microporous aluminum phosphite, and adding the mixture into a first-stage side feeding port of a double-screw extruder;
adding fibers into a second-stage side feeding port of the double-screw extruder;
and performing melt extrusion by using a double-screw extruder to obtain the flame-retardant polyamide composite material.
Preferably, in the preparation method of the flame-retardant polyamide composite material, the double-screw extruder at least satisfies one of the following conditions:
the double-screw extruder is a co-rotating double-screw extruder;
the length-diameter ratio of the screw is (44-52): 1;
the processing temperature is 240-300 ℃;
the rotating speed of the screw is 220 r/min-400 r/min.
Preferably, in the preparation method of the flame-retardant polyamide composite material, the dimethyl silicone oil is added in a certain proportion when the polyamide resin, the anticorrosive agent and the silicone master batch are mixed, so that the adsorption effect of the anticorrosive agent in the polyamide particles can be improved. More preferably, the amount of the dimethylsilicone oil added is 0.5 to 1.0% by mass of the polyamide resin.
Preferably, in the preparation method of the flame-retardant polyamide composite material, when the components of the flame-retardant polyamide composite material comprise the additive, the additive is mixed with the polyamide resin, the anticorrosive agent and the silicone master batch, and then the mixture is added into a main feeding port of a double-screw extruder. In this case, it is preferable to add dimethylsilicone oil, so that the adsorption effect of the additive in the polyamide particles can be improved.
Preferably, in the preparation method of the flame-retardant polyamide composite material, the materials are added into a double-screw extruder by weight-loss metering.
Preferably, the preparation method of the flame-retardant polyamide composite material further comprises the steps of cooling, drying and granulating after the melt extrusion by a double-screw extruder.
Preferably, in the preparation method of the flame-retardant polyamide composite material, the raw materials for preparing the flame-retardant polyamide composite material and the prepared flame-retardant polyamide composite material need to be dried before use. In this way, the influence of moisture can be eliminated.
A third aspect of the invention provides the use of a flame retardant polyamide composite according to the first aspect of the invention.
The flame-retardant polyamide composite material is applied to the fields of electronic appliances, automobiles or aerospace.
The beneficial effects of the invention are:
the invention provides a synergistic flame-retardant reinforced polyamide composite material based on microporous aluminum phosphite, which has good stability, mechanical property and electrical property, and has outstanding physical abrasion resistance and chemical corrosion resistance in the processing process, thereby having very wide application prospect.
Specifically, compared with the prior art, the invention has the following advantages:
1) The fiber flame-retardant polyamide composite material with high flame-retardant efficiency, excellent electrical property and excellent corrosion resistance is prepared by adopting aluminum phosphite with lower corrosivity relative to MPP;
2) By adopting microporous aluminum phosphite, the flame retardant synergistic efficiency of the aluminum phosphite with the traditional crystal structure is improved relative to the low MPP, and simultaneously, the corrosion of the MPP to injection molding parts or apparatuses (such as a mold) under the conditions of high-temperature processing and injection molding, or the possible phenomenon of spray frost or mold fouling under the damp and hot conditions is overcome;
3) The esterified polyol, the zinc borate (or the zinc stannate) and the silicone master batch show good synergistic effect, not only solves the physical abrasion effect brought by hard filler, but also well eliminates the chemical corrosivity caused by an organic hypophosphite flame-retardant system.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or may be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The raw materials used in the following examples are illustrated below:
polyamide resin: PA66 brand of
Figure BDA0002810343660000061
A27, supplied by basf, germany; PPA number of
Figure BDA0002810343660000062
HT plusM1000, provided by the Germany winning initiative;
the organic hypophosphite salt is supplied by German Kelain, and the commercial grade of the organic hypophosphite salt is OP1230;
with MPP of basf
Figure BDA0002810343660000063
200；
Zinc borate is provided by Borax, inc. of America
Figure BDA0002810343660000064
500；
Zinc stannate is available from Wilmbay, inc. of England under the trade designation
Figure BDA0002810343660000065
S；
The esterified polyol is produced by Japanese monosodium glutamate, and the commercialized trade mark of the esterified polyol is PLENLIZER HC-103S;
the silicone master batch is provided for Hangzhou Qianji plastic, wherein the molecular weight of the silicone master batch is 120 ten thousand;
antioxidant 1790 is provided by Cyanite, and auxiliary antioxidant is provided by P-EPQ for Craine;
polyamide stabilizer H3336 was supplied by brugman, lubricant PETS from craine;
the non-microporous aluminum phosphite and the microporous aluminum phosphite are provided by southern university, the purity of the non-microporous aluminum phosphite and the microporous aluminum phosphite is more than or equal to 95%, and the particle size range of the non-microporous aluminum phosphite and the microporous aluminum phosphite is 0.2-20 μm.
The aliphatic polyamide composite component compositions of examples 1 to 8 are shown in table 1, the semi-aromatic polyamide composite component compositions of examples 9 to 16 are shown in table 2, and the polyamide composite component compositions of comparative examples 1 to 11 are shown in table 3. The amounts of the components in tables 1 to 3 are given in mass%. The additive used is composed of an antioxidant 1790, an antioxidant P-EPQ, a polyamide stabilizer H3336 and a lubricant PETS according to the mass ratio of 1.
TABLE 1 compositions of Polyamide composite components of examples 1 to 8
Composition (A) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8
PA66 55.3 50.8 39.5 50 51 48.2 47.2 36.5
OP1230 13 13 13 13 12 14 15 15
Microporous aluminum phosphite 3 2.5 3 3 3 3.5 3.5 4
Zinc borate 0.9 0.9 1.5 1.2 1.2 1.5 1.5 1.5
Esterified polyols 0.3 0.3 0.5 0.3 0.3 0.3 0.3 0.5
Silicone masterbatch 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Additive agent 1 1 1 1 1 1 1 1
Chopped glass fiber 25 30 40 30 30 30 30 40
TABLE 2 compositions of Polyamide composite components of examples 9 to 16
Figure BDA0002810343660000071
TABLE 3 Polyamide composite composition of comparative examples 1 to 11
Figure BDA0002810343660000081
The polyamide composite materials of examples 1 to 16 were prepared as follows: respectively according to the compositions of tables 1-2, uniformly stirring polyamide resin, an anticorrosive agent (zinc borate or zinc stannate, esterified polyol), an additive and a silicone master batch, and then feeding the mixture into a main feed of a co-rotating twin-screw extruder with a screw length-diameter ratio of 48; uniformly mixing organic hypophosphite and microporous aluminum phosphite in proportion, and introducing the mixture through a weight-loss metering scale at a first-stage side feeding port; chopped glass fibers are added through the second side inlet. The processing temperature of the double-screw extruder is 240-310 ℃, and the screw rotating speed is 300r/min. And (3) extracting the melted and homogenized polymer, cooling and shaping by water, air-drying, and granulating to finally obtain the flame-retardant polyamide composite material. The homogenized polymer strand is drawn off, cooled in a water bath and then granulated. After the resulting composite material has been sufficiently dried, the molding composition is processed on an injection molding machine at a batch temperature of from 260 ℃ to 320 ℃ to form test specimens.
The polyamide composite materials of comparative examples 1 to 11 were produced according to the same production methods as in the examples, except that the compositions of comparative examples 1 to 11 were the compositions described in Table 3.
The sample detection evaluation methods of examples 1 to 16 and comparative examples 1 to 11 were as follows:
the testing of tensile splines is performed with reference to ISO 527.
Flame retardant testing the flame retardant tests were tested and rated with reference to UL 94.
Tracking is carried out with reference to the method GB/T4207-2012.
The high temperature and high humidity evaluation conditions were 80 ℃ and 95% humidity for 168 hours, and the surface was observed for the presence of precipitates.
The continuous processability is that whether the surface of a mould is mould fouling or corrosion phenomenon is observed after the composite material is continuously processed for 14 days under the condition of injection molding temperature of 260-320 ℃.
Corrosion resistance the corrosion was investigated by means of the foil method. The flake process developed at DKI (German institute for plastics) was used to model comparative evaluations of metallic materials or the corrosion and abrasion strength of plasticized molding compositions. In this test, two samples are arranged in pairs in a die such that they form a rectangular gap for the passage of the plastic melt, which is 12mm long and 10mm wide and has a height of adjustable height of 0.1mm to a maximum of 1 mm. Through this gap, the plastic melt is extruded (or injected) from the plasticizing component, wherein large local shear stresses and shear rates occur in the gap. The abrasion parameter is the weight loss of the sample, which is determined by differential weighing of the sample using an analytical electronic balance with an error of 0.1 mg. The mass of the samples was determined before and after the corrosion test at a polymer throughput of 25kg on 1.2379 steel. After a predetermined throughput, the sample wafers were unloaded and subjected to a physical/chemical wash to remove adhered plastic. Physical cleaning is accomplished by removing the hot plastic material by wiping it off with cotton. Chemical washing was accomplished by heating the sample in m-cresol for 20 minutes at 60 ℃. The plastic mass still adhering after the boiling operation is removed by wiping with a soft cotton ball.
Δ E means a color difference value of molded articles of the 5 th mold and the 1000 th mold in the case of continuous injection molding, and the result thereof was measured with a color difference meter. When the delta E is less than or equal to 1.0, the color change can not be observed by naked eyes, the color change is obvious when the delta E is more than or equal to 2, and the delta E is more than or equal to 5 when the color is gray.
All tests in the respective series, unless otherwise stated, were carried out under identical conditions (temperature program, screw geometry, injection molding parameters, etc.) for reasons of comparability.
The results of the performance tests on the polyamide composites of examples 1 to 8 are shown in Table 4, the results of the performance tests on the polyamide composites of examples 9 to 16 are shown in Table 5, and the results of the performance tests on the polyamide composites of comparative examples 1 to 11 are shown in Table 6.
TABLE 4 results of Properties test of Polyamide composites of examples 1 to 8
Figure BDA0002810343660000101
TABLE 5 results of Properties test of Polyamide composites of examples 9 to 16
Figure BDA0002810343660000102
TABLE 6 results of the Properties test of the polyamide composite materials of comparative examples 1 to 11
Figure BDA0002810343660000111
From the results of the performance tests in tables 4 to 6, it can be seen that: when non-microporous aluminum phosphite is used, the required dosage of the non-microporous aluminum phosphite is obviously higher than that of microporous aluminum phosphite, so that the flame retardance of the composite material reaches 0.8mm V0. With respect to MPP, when an anticorrosive agent and a silicone master batch are present, no surface separation or mold fouling occurs regardless of the structure of the aluminum phosphite used. It can be seen from examples 15 and 10 and comparative examples 9 and 11 that aluminum phosphite does solve the problem of MPP aggravating the corrosion behavior of the organic hypophosphite system on the mold. It can be seen from a combination of the examples and comparative examples 5-7 that the silicone master batch mainly acts to resist physical abrasion, while the corrosion inhibitor consisting of zinc borate or stannate in combination with esterified polyol acts to reduce the corrosivity of the acidic properties. When the zinc borate (or zinc stannate), the esterified polyol and the silicone master batch are not simultaneously generated in the system, the system has obvious color change or corrosion (or abrasion) phenomena with different degrees, which indicates that the three have very remarkable cooperativity.
The invention effectively solves the defects of low synergistic efficiency and large addition amount of aluminum phosphite with a traditional crystal structure by using the aluminum phosphite with a micropore structure. Meanwhile, by means of the synergistic effect of the esterified polyol, the zinc borate (or the zinc stannate) and the silicone master batch, the phenomenon that the physical and chemical double corrosion is easy to occur when an organic hypophosphite system is used for enhancing the flame-retardant polyamide is successfully solved.
The synergistic flame-retardant reinforced polyamide composite material based on the microporous aluminum phosphite provided by the invention can be widely applied to the fields of electronic appliances, automobiles or aerospace.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A flame retardant polyamide composite characterized by: comprises the following components: polyamide resins, organic hypophosphites, microporous aluminum phosphites, corrosion inhibitors, silicone masterbatches and fibers;
based on the mass of the flame-retardant polyamide composite material, the polyamide resin accounts for 35-58 percent; the organic hypophosphite accounts for 12 to 15 percent; the anticorrosive agent accounts for 1.2-2.0%; 1.5 to 2.0 percent of silicone master batch; the fiber accounts for 25 to 40 percent; the microporous aluminum phosphite accounts for 2-4% of the mass of the flame-retardant polyamide composite material; the sum of the mass percentages of the components of the flame-retardant polyamide composite material is 100%;
the anticorrosive agent comprises esterified polyol and at least one of zinc borate and zinc stannate;
in the anticorrosive agent, the mass ratio of esterified polyol to at least one of zinc borate and zinc stannate is 1: (3-5); the esterified polyol is PLENLIZERHC-103S.
2. A flame retardant polyamide composite material according to claim 1, characterized in that: the polyamide resin is one or a combination of aliphatic polyamide and semi-aromatic polyamide.
3. A flame retardant polyamide composite material according to claim 1, characterized in that: the particle size of the microporous aluminum phosphite is 0.2-20 microns.
4. A flame retardant polyamide composite material according to claim 1, characterized in that: the fiber is at least one selected from glass fiber, carbon fiber and basalt fiber.
5. A flame retardant polyamide composite material according to any one of claims 1 to 4, characterized in that: the flame retardant polyamide composite further comprises an additive; the additive comprises at least one of an antioxidant, a polyamide stabilizer and a lubricant.
6. A method for preparing the flame retardant polyamide composite material as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
mixing polyamide resin, an anticorrosive agent and silicone master batch, and adding into a main feeding port of a double-screw extruder;
mixing organic hypophosphite and microporous aluminum phosphite, and adding the mixture into a first-stage feeding port of a double-screw extruder;
adding fibers into a second-stage side feeding port of the double-screw extruder;
and carrying out melt extrusion by a double-screw extruder to obtain the flame-retardant polyamide composite material.
7. The method of manufacturing according to claim 6, characterized in that: the double-screw extruder at least satisfies one of the following conditions: the double-screw extruder is a co-rotating double-screw extruder;
the length-diameter ratio of the screw is (44-52): 1;
the processing temperature is 240-300 ℃;
the rotating speed of the screw is 220 r/min-400 r/min.
8. Use of the flame retardant polyamide composite material according to any one of claims 1 to 5 in the fields of electronics, automotive or aerospace.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1454230A (en) * 2000-10-04 2003-11-05 旭化成株式会社 Flame-retardant reinforced polyamide resin composition
JP2006071914A (en) * 2004-09-01 2006-03-16 Showa Electric Wire & Cable Co Ltd Flame-retardant acoustic material
CN104448672A (en) * 2013-09-12 2015-03-25 黑龙江鑫达企业集团有限公司 Antioxidant, high flow, halogen-free and flame retardant ABS and preparation process thereof
CN106082266A (en) * 2016-05-31 2016-11-09 南开大学 The method that two kinds of microporous crystals coordinate conversion to prepare SAPO 34 molecular sieve
CN107223149A (en) * 2015-04-13 2017-09-29 科莱恩塑料和涂料有限公司 The method for preparing fire-retardant, noncorrosive and stable polyamide moulding composition
CN108976471A (en) * 2018-06-27 2018-12-11 杭州本松新材料技术股份有限公司 Fire retardant compound system and halogen-free flame-retardant resin based composites comprising it
CN110540750A (en) * 2019-04-22 2019-12-06 江苏集萃先进高分子材料研究所有限公司 flame-retardant nylon 66 composite material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1454230A (en) * 2000-10-04 2003-11-05 旭化成株式会社 Flame-retardant reinforced polyamide resin composition
JP2006071914A (en) * 2004-09-01 2006-03-16 Showa Electric Wire & Cable Co Ltd Flame-retardant acoustic material
CN104448672A (en) * 2013-09-12 2015-03-25 黑龙江鑫达企业集团有限公司 Antioxidant, high flow, halogen-free and flame retardant ABS and preparation process thereof
CN107223149A (en) * 2015-04-13 2017-09-29 科莱恩塑料和涂料有限公司 The method for preparing fire-retardant, noncorrosive and stable polyamide moulding composition
CN106082266A (en) * 2016-05-31 2016-11-09 南开大学 The method that two kinds of microporous crystals coordinate conversion to prepare SAPO 34 molecular sieve
CN108976471A (en) * 2018-06-27 2018-12-11 杭州本松新材料技术股份有限公司 Fire retardant compound system and halogen-free flame-retardant resin based composites comprising it
CN110540750A (en) * 2019-04-22 2019-12-06 江苏集萃先进高分子材料研究所有限公司 flame-retardant nylon 66 composite material and preparation method thereof

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