CN114621587A - Reinforced halogen-free flame-retardant polyamide composite material and preparation method thereof - Google Patents
Reinforced halogen-free flame-retardant polyamide composite material and preparation method thereof Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The application provides a reinforced halogen-free flame-retardant polyamide composite material, which comprises the following components in parts by weight: 36.3 to 64.2 parts of crystalline polyamide resin; 2-10 parts of non-crystalline polyamide resin; 0.5 to 2.5 portions of organic silicon additive; 0.2 to 0.5 portion of ethylene-maleic anhydride copolymer; 10 to 15 parts of halogen-free flame retardant and 10 to 40 parts of glass fiber. According to the reinforced halogen-free flame-retardant polyamide composite material, the noncrystalline polyamide resin, the ethylene-maleic anhydride copolymer, the organic silicon additive and the halogen-free flame retardant are jointly used, the usage amount of the halogen-free flame retardant is reduced under the condition that the reinforced halogen-free flame-retardant polyamide composite material has a good flame-retardant effect, the precipitation amount of the halogen-free flame retardant is further reduced under the condition that the reinforced halogen-free flame-retardant polyamide composite material is matched with the ethylene-maleic anhydride copolymer, the corrosivity of the reinforced halogen-free flame-retardant polyamide composite material is further reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is further improved.
Description
Technical Field
The invention relates to the technical field of halogen-free flame-retardant polyamide composite materials, in particular to a reinforced halogen-free flame-retardant polyamide composite material and a preparation method thereof.
Background
The polyamide composite material is also called nylon engineering plastic, and because of excellent mechanical properties, the polyamide composite material is widely applied to industries such as automobile manufacturing, electronics and electrical, aerospace and the like, along with the continuous development and progress of science and technology, the use environment of the engineering plastic is more and more rigorous, and particularly in the field of electronic and electrical appliances, higher requirements on the aspects of strength, flame retardant efficiency, voltage resistance and the like are provided.
At present, most polyamide composite materials are halogen-containing systems or red phosphorus flame-retardant systems, the halogen-containing bromine-antimony flame-retardant systems have poor electrical performance, more harmful substances such as dense smoke, hydrogen halide and the like can be generated in the combustion process, the red phosphorus flame-retardant systems are only suitable for manufacturing dark-colored workpieces, and the defects that the contact metal parts are corroded due to precipitation exist in long-term use are overcome. Therefore, halogen-free flame retardant is a hot spot direction for the development of halogen-free flame retardant polyamide composite materials in recent years. Chinese patent CN109467925 discloses a halogen-free flame-retardant nylon composite material which can resist wet heat aging, by introducing substances capable of limiting the movement of nylon molecular chains into a hypophosphite flame-retardant nylon system, the small molecules such as water and the like are reduced to enter and exit the resin matrix, the precipitation of a flame retardant in the use process is reduced or avoided, the flame retardant is beneficial to stabilizing the flame retardant property, but the addition amount of the flame retardant is larger, and the influence of the mechanical property reduction caused by the flame retardant cannot be overcome, Chinese patent CN112409786 discloses a low-mould-fouling halogen-free flame-retardant thermoplastic polyamide composition, ethylene copolymer is added as an adsorbent, and by controlling the adding amount of the additive, the release amount of small molecular substances in the injection molding process can be effectively reduced, the mold fouling amount generated in the injection molding process is greatly reduced, however, the ethylene copolymer, as an elastomer, has a large influence on flame retardancy and strength, resulting in an increase in the amount of the flame retardant and a further decrease in strength.
Therefore, how to search for a reinforced halogen-free flame-retardant polyamide composite material which can reduce the precipitation of a flame retardant to reduce the corrosion to equipment and has excellent mechanical properties.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the reinforced halogen-free flame-retardant polyamide composite material which can reduce the precipitation of a flame retardant and has excellent mechanical property and flame retardant property.
The purpose of the invention is realized by the following technical scheme:
the reinforced halogen-free flame-retardant polyamide composite material comprises the following components in parts by weight:
in one embodiment, the halogen-free flame retardant is a phosphorus-nitrogen system halogen-free flame retardant based on aluminum diethylphosphinate.
In one embodiment, the amorphous polyamide resin is a semi-aromatic polyamide resin.
In one embodiment, the semi-aromatic polyamide resin includes at least one of PA6I and PA 6T.
In one embodiment, the ethylene-maleic anhydride copolymer has a copolymerization ratio of ethylene to maleic anhydride of 1: 1.
In one embodiment, the silicone additive is an organomodified polysiloxane.
In one embodiment, the composition further comprises the following components in parts by mass:
0.3 to 1.0 portion of lubricant;
0.2 to 0.5 portion of antioxidant.
In one embodiment, the lubricant comprises at least one of pentaerythritol tetrastearate, montan wax, and ethylene bis-stearamide.
In one embodiment, the antioxidant comprises at least one of N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
A preparation method of a reinforced halogen-free flame-retardant polyamide composite material is used for preparing the reinforced halogen-free flame-retardant polyamide composite material in any embodiment, and comprises the following steps:
stirring and mixing the crystalline polyamide resin, the non-crystalline polyamide resin, the organic silicon additive and the ethylene-maleic anhydride copolymer to obtain a premix;
and carrying out extrusion granulation operation on the premix, the halogen-free flame retardant and the glass fiber to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Compared with the prior art, the invention has at least the following advantages:
the reinforced halogen-free flame-retardant polyamide composite material uses the crystalline polyamide resin and the amorphous polyamide resin, effectively improves the flow property of the crystalline polyamide resin, is beneficial to fully dispersing the halogen-free flame retardant and the glass fiber in the crystalline polyamide resin and the amorphous polyamide resin, and is further beneficial to improving the mechanical property and toughness of the reinforced halogen-free flame-retardant polyamide composite material. In addition, the ethylene-maleic anhydride copolymer and the organic silicon additive are beneficial to promoting the formation of more uniform melt and reducing the release of smoke, so that a more complete carbon layer is formed in the combustion process, and a better synergistic flame retardant effect is achieved. Therefore, the noncrystalline polyamide resin, the ethylene-maleic anhydride copolymer, the organic silicon additive and the halogen-free flame retardant are jointly used, the dosage of the halogen-free flame retardant is reduced under the condition that the reinforced halogen-free flame retardant polyamide composite material has a better flame retardant effect, the addition amount of the halogen-free flame retardant in the reinforced halogen-free flame retardant polyamide composite material is reduced, the precipitation amount of the halogen-free flame retardant is reduced, the corrosivity of the reinforced halogen-free flame retardant polyamide composite material is reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a preparation method of the reinforced halogen-free flame-retardant polyamide composite material according to an embodiment of the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The application provides a reinforced halogen-free flame-retardant polyamide composite material, which comprises the following components in parts by weight: 36.3 to 64.2 parts of crystalline polyamide resin; 2-10 parts of non-crystalline polyamide resin; 0.5 to 2.5 portions of organic silicon additive; 0.2 to 0.5 portion of ethylene-maleic anhydride copolymer; 10-15 parts of halogen-free flame retardant.
The reinforced halogen-free flame-retardant polyamide composite material uses the crystalline polyamide resin and the amorphous polyamide resin, effectively improves the flow property of the crystalline polyamide resin, is beneficial to fully dispersing the halogen-free flame retardant and the glass fiber in the crystalline polyamide resin and the amorphous polyamide resin, and is further beneficial to improving the mechanical property and the flexibility of the reinforced halogen-free flame-retardant polyamide composite material. In addition, the ethylene-maleic anhydride copolymer and the organosilicon additive are favorable for promoting the formation of more uniform melt, reducing the release of smoke, further forming a more complete carbon layer in the combustion process and playing a better synergistic flame retardant effect, so that the noncrystalline polyamide resin, the ethylene-maleic anhydride copolymer, the organosilicon additive and the halogen-free flame retardant are jointly used, the dosage of the halogen-free flame retardant is reduced under the condition of ensuring that the reinforced halogen-free flame retardant polyamide composite material has a better flame retardant effect, the addition amount of the halogen-free flame retardant in the reinforced halogen-free flame retardant polyamide composite material is reduced, the precipitation amount of the halogen-free flame retardant is further reduced, the corrosivity of the reinforced halogen-free flame retardant polyamide composite material is reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is further improved.
For better understanding of the reinforced halogen-free flame-retardant polyamide composite material of the present invention, the reinforced halogen-free flame-retardant polyamide composite material of the present invention is further explained below, and the reinforced halogen-free flame-retardant polyamide composite material of an embodiment comprises the following components in parts by weight: 36.3 to 64.2 portions of crystalline polyamide resin; 2-10 parts of non-crystalline polyamide resin; 0.5 to 2.5 portions of organic silicon additive; 0.2 to 0.5 portion of ethylene-maleic anhydride copolymer; 10 to 15 parts of halogen-free flame retardant and 10 to 40 parts of glass fiber.
The reinforced halogen-free flame-retardant polyamide composite material uses the crystalline polyamide resin and the amorphous polyamide resin, effectively improves the flow property of the crystalline polyamide resin, is beneficial to fully dispersing the halogen-free flame retardant and the glass fiber in the crystalline polyamide resin and the amorphous polyamide resin, and is further beneficial to improving the mechanical property and toughness of the reinforced halogen-free flame-retardant polyamide composite material. In addition, the ethylene-maleic anhydride copolymer and the organic silicon additive are beneficial to promoting the formation of more uniform melt and reducing the release of smoke, so that a more complete carbon layer is formed in the combustion process, and a better synergistic flame retardant effect is achieved. Therefore, the noncrystalline polyamide resin, the ethylene-maleic anhydride copolymer, the organic silicon additive and the halogen-free flame retardant are jointly used, the dosage of the halogen-free flame retardant is reduced under the condition that the reinforced halogen-free flame retardant polyamide composite material has a better flame retardant effect, the addition amount of the halogen-free flame retardant in the reinforced halogen-free flame retardant polyamide composite material is reduced, the precipitation amount of the halogen-free flame retardant is reduced, the corrosivity of the reinforced halogen-free flame retardant polyamide composite material is reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is improved.
It should be noted that, when the reinforced halogen-free flame retardant polyamide composite material is burned, the reinforced halogen-free flame retardant polyamide composite material is easily carbonized at high temperature to form an attached carbonized layer, so that the transfer of flame heat to the interior of the reinforced halogen-free flame retardant polyamide composite material can be effectively reduced, and the ethylene-maleic anhydride copolymer and the organic silicon additive can promote the crosslinking reaction between the crystalline polyamide resin and the amorphous polyamide resin in the reinforced halogen-free flame retardant polyamide composite material, so as to promote the surface of the reinforced halogen-free flame retardant polyamide composite material to form a complete carbonized layer, thereby achieving a better flame retardant effect. In addition, the added ethylene-maleic anhydride copolymer enables the melts of the crystalline polyamide resin and the non-crystalline polyamide resin to have good fluidity so as to reduce the difficulty of processing and molding.
In one embodiment, the halogen-free flame retardant is a phosphorus-nitrogen system halogen-free flame retardant based on aluminum diethylphosphinate. The halogen-free flame retardant is a halogen-free and environment-friendly phosphorus-nitrogen system flame retardant based on diethyl phosphinate, and when the phosphorus-nitrogen system halogen-free flame retardant based on diethyl phosphinate is combusted, on one hand, the phosphorus-nitrogen system halogen-free flame retardant based on diethyl phosphinate can react with a polymer in the reinforced halogen-free flame-retardant polyamide composite material, so that a complete carbon layer is formed on the surface of the reinforced halogen-free flame-retardant polyamide composite material to achieve a good flame-retardant effect, and on the other hand, the phosphorus-nitrogen system halogen-free flame retardant based on diethyl phosphinate can release a phosphorus-containing compound into flame, and then the generated phosphorus-containing compound is converted into a phosphorus-containing radical quencher with flame-retardant capability at high temperature of the flame, so that the better flame-retardant effect is achieved.
In one embodiment, the crystalline polyamide resin comprises at least one of polyamide 66 and polyamide 6. It can be understood that the polyamide 66 and the polyamide 6 contain polar amide amino groups in the repeating units on the main chain of the nylon molecule, so that intermolecular hydrogen bonds can be formed, the polyamide 66 and the polyamide 6 have crystallinity, and a plurality of polar amide amino groups are regularly arranged, so that intermolecular interaction force is large, the crystal arrangement of the polyamide 66 and the polyamide 6 is compact, and better mechanical properties are provided for the reinforced halogen-free flame-retardant polyamide composite material. In addition, the polyamide 66 and the polyamide 6 have low permeability to gases such as oxygen, so that the reinforced halogen-free flame-retardant polyamide composite material has excellent barrier property, thereby achieving a good flame-retardant effect.
In one embodiment, the amorphous polyamide resin is a semi-aromatic polyamide resin. It can be understood that, because the semi-aromatic polyamide resin contains benzene ring group, on one hand, the performance defects caused by poor heat resistance and large water absorption of the crystalline polyamide resin can be improved, namely, the mechanical property and the processing fluidity of the reinforced halogen-free flame-retardant polyamide composite material are improved, so that the processing molding is facilitated; on the other hand, when the semi-aromatic polyamide resin is combusted, the benzene ring group can provide a precursor for forming carbon for a carbonization layer attached to the reinforced halogen-free flame retardant polyamide composite material, so that the solid-phase flame retardant effect of the phosphorus-nitrogen system halogen-free flame retardant of aluminum diethylphosphinate is ensured. In addition, the semi-aromatic polyamide resin is added to inhibit the activity of polar amide amino groups in the crystalline polyamide resin, so that the problem of precipitation of the halogen-free flame retardant caused by the small molecules such as moisture entering and exiting the crystalline polyamide resin is solved.
In one embodiment, the semi-aromatic polyamide resin includes at least one of PA6I and PA 6T. It can be understood that since PA6I is fully called m-phenylene isophthalate hexamethyl diamine and fiber, PA6T is fully called poly (hexamethylene terephthalamide), both of which contain benzene ring groups, can provide a carbon precursor for the enhanced halogen-free flame retardant polyamide composite material during combustion, so as to ensure the solid phase flame retardant effect of the phosphorus-nitrogen system halogen-free flame retardant of aluminum diethylphosphinate and achieve better flame retardant effect.
In one embodiment, the copolymerization ratio of ethylene to maleic anhydride in the ethylene-maleic anhydride copolymer is 1:1, and the copolymerization ratio of ethylene to maleic anhydride is 1:1, so that the compatibility of the halogen-free flame retardant with the crystalline polyamide resin and the amorphous polyamide resin can be well improved, a more stable system can be formed, the problem of precipitation of the halogen-free flame retardant can be well avoided, and the ethylene-maleic anhydride copolymer is particularly suitable for nylon plastic processing.
In one embodiment, the glass fiber also comprises 10 to 40 parts of glass fiber. It can be understood that by adding 10-40 parts of glass fiber, the glass fiber has high modulus, good insulation, high temperature resistance and good corrosion resistance, so that various mechanical properties of the reinforced halogen-free flame-retardant polyamide composite material can be improved.
In one embodiment, the glass fibers are alkali-free chopped glass fibers. Because the alkali-free chopped glass fiber does not contain alkali metal oxide, mainly contains aluminoborosilicate, the alkali-free chopped glass fiber has no corrosivity on production equipment, so that the production equipment is well protected, and meanwhile, the alkali-free chopped glass fiber can improve the strength of the reinforced halogen-free flame-retardant polyamide composite material. In a preferred embodiment, the glass fibers have a diameter of 7 to 14 microns. The glass fiber within the diameter range ensures that the melt of the reinforced halogen-free flame-retardant polyamide composite material has better fluidity, and ensures that the reinforced halogen-free flame-retardant polyamide composite material with good strength is obtained.
In one embodiment, the silicone additive is an organomodified polysiloxane. It can be understood that the organic modified polysiloxane can promote the cross-linking reaction of the polymer in the reinforced halogen-free flame-retardant polyamide composite material, so that a better carbonization layer is formed on the surface of the reinforced halogen-free flame-retardant polyamide composite material to achieve a better flame-retardant effect.
In one embodiment, the organomodified polysiloxane is Dow Corning 43-821. Specifically, because Dow Corning 43-821 has excellent flame-retardant synergistic performance, and because the organic silicon additive contains organic functional groups, the added organic modified polysiloxane can be well dispersed between crystalline polyamide resin and non-crystalline polyamide resin, and can well promote the formation of a carbide layer on the surface of the reinforced halogen-free flame-retardant polyamide composite material, thereby achieving better flame-retardant effect, so that when the organic modified polysiloxane is used in combination with ethylene-maleic anhydride copolymer and non-crystalline polyamide resin, the use amount of the halogen-free flame retardant can be reduced under the condition of ensuring that the reinforced halogen-free flame-retardant polyamide composite material has better flame-retardant effect, thereby greatly reducing the investment of production raw materials, saving the production cost, and avoiding the corrosivity of the addition amount of a larger halogen-free flame retardant to production equipment, thereby having good protection effect on equipment.
In one embodiment, the composition further comprises the following components in parts by mass: 0.3 to 1.0 portion of lubricant; 0.2 to 0.5 portion of antioxidant. It can be understood that the addition of 0.3 to 1.0 part of lubricant can reduce the internal friction between molecules in the reinforced halogen-free flame retardant polyamide composite material, thereby improving the internal friction heat generation of the melt material of the reinforced halogen-free flame retardant polyamide composite material and the fluidity of the melt, and on the other hand, can reduce the external friction on the surface of the reinforced halogen-free flame retardant polyamide composite material, thereby improving the friction between the reinforced halogen-free flame retardant polyamide composite material and the hot metal surface of the equipment, so that the reinforced halogen-free flame retardant polyamide composite material can be easily processed and demoulded; 0.2-0.5 part of antioxidant is added, and the antioxidant is added to effectively improve the oxidation resistance of the reinforced halogen-free flame-retardant polyamide composite material, so that the reinforced halogen-free flame-retardant polyamide composite material is ensured to have excellent mechanical properties and flame retardance.
In one embodiment, the lubricant comprises at least one of pentaerythritol tetrastearate, montan wax, and ethylene bis-stearamide. The added pentaerythritol tetrastearate is white hard high-melting-point wax which has good internal and external lubricity, can effectively improve the thermal stability of the reinforced halogen-free flame-retardant polyamide composite material, and is non-toxic and good in safety; the added montan wax has low volatility, so that the lubricating effect on the reinforced halogen-free flame-retardant polyamide composite material is ensured, and the reinforced halogen-free flame-retardant polyamide composite material is better processed and demoulded; the added ethylene bis stearamide can improve the internal friction heat generation of the melt of the reinforced halogen-free flame-retardant polyamide composite material and the fluidity of the melt, and is beneficial to better demolding of the reinforced halogen-free flame-retardant polyamide composite material.
In one embodiment, the antioxidant comprises at least one of N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate. It can be understood that the added N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can effectively prevent the reinforced halogen-free flame retardant polyamide composite material from being oxidized, so as to ensure the service life of the reinforced halogen-free flame retardant polyamide composite material.
In one embodiment, the mass part ratio of the N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine to the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate is 1: 1. it will be appreciated that by reacting N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine with bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate according to 1:1, the reinforced halogen-free flame-retardant polyamide composite material can be better prevented from being oxidized so as to ensure the service life of the reinforced halogen-free flame-retardant polyamide composite material.
The application also provides a preparation method of the reinforced halogen-free flame-retardant polyamide composite material, which is used for preparing the reinforced halogen-free flame-retardant polyamide composite material in any one of the above items, and the preparation method of the reinforced halogen-free flame-retardant polyamide composite material comprises the following steps: stirring and mixing the crystalline polyamide resin, the non-crystalline polyamide resin, the organic silicon additive and the ethylene-maleic anhydride copolymer to obtain a premix; and carrying out extrusion granulation operation on the premix, the halogen-free flame retardant and the glass fiber to obtain the reinforced halogen-free flame-retardant polyamide composite material.
According to the preparation method of the reinforced halogen-free flame-retardant polyamide composite material, the crystalline polyamide resin, the amorphous polyamide resin, the organic silicon additive and the ethylene-maleic anhydride copolymer are respectively added into a mixer to be stirred and mixed so as to enable the crystalline polyamide resin and the amorphous polyamide resin to be uniformly dispersed, so that a pre-mixture which is uniformly mixed and has good stability is obtained, then the pre-mixture, the halogen-free flame retardant and the glass fiber are added into an extruder to be subjected to melt extrusion granulation, so that the reinforced halogen-free flame-retardant polyamide composite material is obtained, the pre-mixture which is uniformly mixed and has good stability is prepared, so that the halogen-free flame retardant and the glass fiber can be better and more quickly dispersed in the pre-mixture, and the problem of precipitation of the halogen-free flame retardant caused by long-time stirring friction is avoided, and the problem that the long diameter of the glass fiber is reduced and the strength is reduced due to the long-time shearing of the glass fiber.
In order to better understand the preparation method of the reinforced halogen-free flame-retardant polyamide composite material of the present invention, the preparation method of the reinforced halogen-free flame-retardant polyamide composite material of the present invention is further explained below, referring to fig. 1, the preparation method of the reinforced halogen-free flame-retardant polyamide composite material of an embodiment includes the following steps:
s100, stirring and mixing the crystalline polyamide resin, the non-crystalline polyamide resin, the organic silicon additive and the ethylene-maleic anhydride copolymer to obtain a premix.
It is understood that the crystalline polyamide resin, the non-crystalline polyamide resin, the silicone additive and the ethylene-maleic anhydride copolymer are separately added to a mixer according to the formulation and stirred to uniformly disperse the crystalline polyamide resin and the non-crystalline polyamide resin, thereby obtaining a premix with uniform mixing and good stability. It can be further understood that the crystalline polyamide resin in the premix can provide basic substrate guarantee for the reinforced halogen-free flame-retardant polyamide composite material, so as to ensure the strength and heat resistance of the reinforced halogen-free flame-retardant polyamide composite material, the use of the crystalline polyamide resin and the amorphous polyamide resin effectively improves the flow property of the crystalline polyamide resin, is beneficial to the sufficient dispersion of the halogen-free flame retardant, the crystalline polyamide resin and the amorphous polyamide resin, and is further beneficial to the improvement of the mechanical property and flexibility of the reinforced halogen-free flame-retardant polyamide composite material, further, the ethylene-maleic anhydride copolymer is added, the ethylene-maleic anhydride copolymer effectively improves the compatibility of the crystalline polyamide resin and the amorphous polyamide resin, and further effectively reduces the precipitation problem of the halogen-free flame retardant dispersed in the crystalline polyamide resin and the amorphous polyamide resin, and further improves the mechanical property of the reinforced halogen-free flame-retardant polyamide composite material, in addition, the ethylene-maleic anhydride copolymer and the organic silicon additive are beneficial to promoting the carbon formation of the amorphous polyamide resin and the crystalline polyamide resin, and then are easy to carbonize at high temperature to form an attached carbonized layer, so as to play a good flame-retardant effect, so that the amorphous polyamide resin, the ethylene-maleic anhydride copolymer, the organic silicon additive and the halogen-free flame retardant are jointly used, the using amount of the halogen-free flame retardant is reduced under the condition of ensuring that the reinforced halogen-free flame-retardant polyamide composite material has a good flame-retardant effect, the adding amount of the halogen-free flame retardant in the reinforced halogen-free flame-retardant polyamide composite material is reduced, and further the precipitation amount of the halogen-free flame retardant is reduced under the condition of being matched with the ethylene-maleic anhydride copolymer, and the corrosivity of the reinforced halogen-free flame-retardant polyamide composite material is reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is improved.
In one embodiment, the stirring operation is performed for 3min to 5min to obtain a uniformly mixed premix.
In one embodiment, in the step of separately adding the crystalline polyamide resin, the non-crystalline polyamide resin, the silicone additive, and the ethylene-maleic anhydride copolymer to a mixer to perform a stirring operation, a lubricant and an antioxidant are further added to the mixer.
It can be understood that the lubricant and the antioxidant are added into the mixer together, and the added lubricant can help to reduce the internal friction between molecules in the reinforced halogen-free flame-retardant polyamide composite material on one hand, so as to improve the internal friction heat generation of the melt material of the reinforced halogen-free flame-retardant polyamide composite material and the fluidity of the melt, and can reduce the external friction on the surface of the reinforced halogen-free flame-retardant polyamide composite material on the other hand, so as to improve the friction condition between the reinforced halogen-free flame-retardant polyamide composite material and the hot metal surface of equipment, so as to enable the reinforced halogen-free flame-retardant polyamide composite material to be easily demoulded; the antioxidant is added to improve the oxidation resistance of the reinforced halogen-free flame-retardant polyamide composite material, so that the reinforced halogen-free flame-retardant polyamide composite material is ensured to have excellent mechanical properties and flame retardance.
In one embodiment, before the step of mixing the crystalline polyamide resin, the non-crystalline polyamide resin, the silicone additive and the ethylene-maleic anhydride copolymer, the method further comprises drying the crystalline polyamide resin and the non-crystalline polyamide resin respectively to obtain the crystalline polyamide resin and the non-crystalline polyamide resin with low moisture content.
It can be understood that the crystalline polyamide resin and the amorphous polyamide resin are weighed according to the formula, and then the crystalline polyamide resin and the amorphous polyamide resin are subjected to drying treatment under the conditions of the temperature of 90-110 ℃ and the time of 8-12 h, so that the crystalline polyamide resin and the amorphous polyamide resin with low moisture content are obtained, and the problem that the polymer in the reinforced halogen-free flame-retardant polyamide composite material is degraded due to high moisture content is effectively avoided.
S200, carrying out extrusion granulation operation on the premix, the halogen-free flame retardant and the glass fiber to obtain the reinforced halogen-free flame-retardant polyamide composite material.
It can be understood that the mixed premix is firstly added into a main feeding port in an extruder, and then the halogen-free flame retardant and the glass fiber are added into the extruder through a forced side feeding device, so that the halogen-free flame retardant can be rapidly dispersed into the premix to form a stable dispersion system, the shearing heat of the semi-molten crystalline polyamide resin and the semi-molten amorphous polyamide resin to the halogen-free flame retardant is small, the destructiveness of the halogen-free flame retardant is small, and the problem that the halogen-free flame retardant is easy to precipitate can be effectively reduced. If the halogen-free flame retardant, the crystalline polyamide resin and the amorphous polyamide resin are mixed together, the halogen-free flame retardant is sheared very little and the shearing heat is high in the mixing and stirring operation, so that the halogen-free flame retardant is easy to migrate to the surface of equipment during long-time mixing and stirring, and the precipitation rate of the halogen-free flame retardant is improved.
It can be understood that the glass fiber is added into the extruder by the forced side feeding device, on one hand, the glass fiber can keep a certain length-diameter ratio, and the crystalline polyamide resin and the amorphous polyamide resin in a semi-molten state have small shearing heat and destructiveness to the glass fiber, so that the added glass fiber can be ensured to play a good role in reinforcing the reinforced halogen-free flame retardant polyamide composite material.
In one embodiment, the processing technology of the extrusion granulation operation comprises a first-zone temperature of 250-260 ℃, a second-zone temperature of 265-280 ℃, a third-zone temperature of 265-280 ℃, a fourth-zone temperature of 265-280 ℃, a fifth-zone temperature of 260-275 ℃, a sixth-zone temperature of 250-265 ℃, a seventh-zone temperature of 240-260 ℃, an eighth-zone temperature of 240-260 ℃, a ninth-zone temperature of 240-265 ℃ and a main engine rotation speed of 240-400 r/min. It can be understood that the premix, the halogen-free flame retardant and the glass fiber are added into the extruder, then the processing temperature of the extruder is controlled, the premix, the halogen-free flame retardant and the glass fiber are heated in a first zone, a second zone, a third zone and a fourth zone, so that the premix, the halogen-free flame retardant and the glass fiber can be gradually melted to ensure that all the components can be well dispersed and combined, a better and more stable reinforced halogen-free flame retardant polyamide composite material molten mass is formed, and then the five zones, the six zones, the seven zones, the eight zones and the nine zones are gradually cooled, so that the extruder can better extrude and granulate the reinforced halogen-free flame retardant polyamide composite material.
In one embodiment, after the step of adding the pre-mixture and the halogen-free flame retardant into an extruder for extrusion granulation, the reinforced halogen-free flame retardant polyamide composite material is cooled, dried and granulated, so that the reinforced halogen-free flame retardant polyamide composite material with low water content and regular particles can be obtained.
Some specific examples are listed below, and if mentioned%, all are expressed in weight percent. It should be noted that the following examples are not intended to be exhaustive of all possible cases, and that the materials used in the following examples are commercially available without specific recitation.
Example 1
51.8kg of crystalline polyamide resin and 2kg of amorphous polyamide resin are dried, wherein the drying condition is that the temperature is 90 ℃ and the time is 12 h; respectively adding dried crystalline polyamide resin, non-crystalline polyamide resin, 0.5kg of organic silicon additive, 0.2kg of ethylene-maleic anhydride copolymer, 0.3kg of lubricant and 0.2kg of antioxidant into a mixer for stirring operation, wherein the stirring operation time is 3min, so as to obtain a premix; adding the premix into a main feed inlet in an extruder, and adding 15kg of the halogen-free flame retardant and 30kg of the glass fiber into the extruder through a forced side feeding device respectively for extrusion granulation, wherein the extrusion granulation processing technology comprises 250 ℃ in a first zone, 265 ℃ in a second zone, 265 ℃ in a third zone, 265 ℃ in a fourth zone, 260 ℃ in a fifth zone, 250 ℃ in a sixth zone, 240 ℃ in a seventh zone, 240 ℃ in an eighth zone, 240 ℃ in a ninth zone, and 240 revolutions per minute of a main engine, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Example 2
50.2kg of crystalline polyamide resin and 5kg of amorphous polyamide resin are dried, and the drying conditions are that the temperature is 100 ℃ and the time is 8 h; respectively adding dried crystalline polyamide resin, dried non-crystalline polyamide resin, 1.5kg of organic silicon additive, 0.5kg of ethylene-maleic anhydride copolymer, 0.5kg of lubricant and 0.3kg of antioxidant into a mixer for stirring for 4min to obtain a premix; adding the premix into a main feeding port in an extruder, and then adding 12kg of the halogen-free flame retardant and 30kg of the glass fiber into the extruder through a forced side feeding device for extrusion granulation, wherein the processing technology of the extrusion granulation comprises the steps of 255 ℃ in a first zone, 272 ℃ in a second zone, 270 ℃ in a third zone, 272 ℃ in a fourth zone, 268 ℃ in a fifth zone, 260 ℃ in a sixth zone, 255 ℃ in a seventh zone, 248 ℃ in an eighth zone, 250 ℃ in a ninth zone, and 300 revolutions per minute of a main engine, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Example 3
Drying 51kg of crystalline polyamide resin and 5kg of amorphous polyamide resin under the conditions of 110 ℃ for 10 hours; respectively adding dried crystalline polyamide resin, non-crystalline polyamide resin, 1kg of organic silicon additive, 0.2kg of ethylene-maleic anhydride copolymer, 0.5kg of lubricant and 0.3kg of antioxidant into a mixer for stirring operation, wherein the stirring operation lasts for 5min, and obtaining a premix; adding the premix into a main feed inlet in an extruder, and then adding 12kg of the halogen-free flame retardant and 30kg of the glass fiber into the extruder through a forced side feeding device for extrusion granulation, wherein the processing technology of the extrusion granulation comprises the steps of first zone temperature of 260 ℃, second zone temperature of 280 ℃, third zone temperature of 280 ℃, fourth zone temperature of 280 ℃, fifth zone temperature of 275 ℃, sixth zone temperature of 265 ℃, seventh zone temperature of 260 ℃, eighth zone temperature of 260 ℃, ninth zone temperature of 265 ℃ and host rotation speed of 400 r/min, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Example 4
47.1kg of crystalline polyamide resin and 10kg of amorphous polyamide resin are dried, wherein the drying conditions are that the temperature is 100 ℃ and the time is 8 h; respectively adding dried crystalline polyamide resin, non-crystalline polyamide resin, 2kg of organic silicon additive, 0.3kg of ethylene-maleic anhydride copolymer, 0.3kg of lubricant and 0.3kg of antioxidant into a mixer for stirring, wherein the stirring time is 4min, so as to obtain a premix; adding the premix into a main feeding port in an extruder, and then adding 10kg of the halogen-free flame retardant and 30kg of the glass fiber into the extruder through a forced side feeding device for extrusion granulation, wherein the processing technology of the extrusion granulation comprises the steps of 255 ℃ in a first zone, 268 ℃ in a second zone, 270 ℃ in a third zone, 272 ℃ in a fourth zone, 274 ℃ in a fifth zone, 260 ℃ in a sixth zone, 255 ℃ in a seventh zone, 248 ℃ in an eighth zone, 245 ℃ in a ninth zone, and 300 revolutions per minute of a main machine, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Example 5
64.2kg of crystalline polyamide resin and 10kg of non-crystalline polyamide resin are dried, wherein the drying condition is that the temperature is 100 ℃ and the time is 8 h; respectively adding dried crystalline polyamide resin, non-crystalline polyamide resin, 2.5kg of organic silicon additive, 0.5kg of ethylene-maleic anhydride copolymer, 0.5kg of lubricant and 0.3kg of antioxidant into a mixer for stirring operation, wherein the stirring operation time is 5min, so as to obtain a premix; adding the premix into a main feeding port in an extruder, and then adding 12kg of the halogen-free flame retardant and 10kg of the glass fiber into the extruder through a forced side feeding device for extrusion granulation, wherein the processing technology of the extrusion granulation comprises the steps of 255 ℃ in a first zone, 268 ℃ in a second zone, 270 ℃ in a third zone, 272 ℃ in a fourth zone, 274 ℃ in a fifth zone, 260 ℃ in a sixth zone, 255 ℃ in a seventh zone, 248 ℃ in an eighth zone, 245 ℃ in a ninth zone, and 300 revolutions per minute of a main machine, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Example 6
Drying 36.3kg of crystalline polyamide resin and 10kg of non-crystalline polyamide resin under the conditions of 100 ℃ and 8 hours; respectively adding dried crystalline polyamide resin, non-crystalline polyamide resin, 2kg of organic silicon additive, 0.2kg of ethylene-maleic anhydride copolymer, 1kg of lubricant and 0.5kg of antioxidant into a mixer for stirring operation, wherein the stirring operation lasts for 5min, so as to obtain a premix; adding the premix into a main feeding port in an extruder, and then adding 10kg of the halogen-free flame retardant and 40kg of the glass fiber into the extruder through a forced side feeding device for extrusion granulation, wherein the processing technology of the extrusion granulation comprises the steps of 255 ℃ in a first zone, 268 ℃ in a second zone, 270 ℃ in a third zone, 272 ℃ in a fourth zone, 274 ℃ in a fifth zone, 260 ℃ in a sixth zone, 255 ℃ in a seventh zone, 248 ℃ in an eighth zone, 245 ℃ in a ninth zone, and 300 revolutions per minute of a main machine, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
Comparative example 1
51.8kg of crystalline polyamide resin is dried at the temperature of 100 ℃ for 8 h; respectively adding the dried crystalline polyamide resin, 0.3kg of lubricant and 0.2kg of antioxidant into a mixer for stirring operation, wherein the stirring operation time is 3min, so as to obtain a premix; adding the premix into a main feed inlet in an extruder, and then adding 18kg of the halogen-free flame retardant and 30kg of the glass fiber into the extruder through a forced side feeding device for extrusion granulation, wherein the processing technology of the extrusion granulation comprises the steps of 250 ℃ in a first zone, 265 ℃ in a second zone, 265 ℃ in a third zone, 265 ℃ in a fourth zone, 260 ℃ in a fifth zone, 250 ℃ in a sixth zone, 240 ℃ in a seventh zone, 240 ℃ in an eighth zone, 240 ℃ in a ninth zone and 240 revolutions per minute of a main engine, so as to obtain the reinforced halogen-free flame-retardant polyamide composite material.
The reinforced halogen-free flame-retardant polyamide composite material prepared by the preparation method of the reinforced halogen-free flame-retardant polyamide composite material is subjected to various performance tests as follows:
and (3) testing items: tensile Strength test was conducted according to ASTM-D638, specimen type I, specimen size (mm): (165. + -.2) × (12.70. + -. 0.2) × (3.20. + -. 0.2), and a drawing speed of 50 mm/min; flexural strength was tested according to ASTM-D790, specimen size (mm): (127. + -. 2) × (12.7. + -. 0.2) × (3.20. + -. 0.2), bending speed 2 mm/min; the notched impact strength was examined in accordance with ASTM-D256, and the type of the specimen was a type A notch, and the specimen size (mm): 63.5 × (12.7 ± 0.2) × (3.2 ± 0.2); the flame retardant property is tested by injection molding into a standard combustion test strip according to the US UL standard; the melt flow rate was tested according to ASTM-D1238.
TABLE 1 reinforced halogen-free flame-retardant polyamide composite material Performance Table
As can be seen from Table 1, the reinforced halogen-free flame retardant polyamide composite materials of examples 1-4 and 6 have better mechanical properties, flame retardant properties and melt flow rate than those of comparative example 1, by compounding the non-crystalline polyamide resin, the organic silicon additive and the ethylene-maleic anhydride copolymer, the usage amount of the halogen-free flame retardant is reduced under the condition of ensuring that the reinforced halogen-free flame-retardant polyamide composite material has better flame-retardant effect, the addition amount of the halogen-free flame retardant in the reinforced halogen-free flame-retardant polyamide composite material is reduced, and the precipitation amount of the halogen-free flame retardant is further reduced under the condition of being matched with the ethylene-maleic anhydride copolymer, and the corrosivity of the reinforced halogen-free flame-retardant polyamide composite material is reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is improved. Among them, it can be seen in example 4 that the reinforced halogen-free flame retardant polyamide composite material prepared by adding a small amount of ethylene-maleic anhydride copolymer, amorphous polyamide resin and organosilicon additive has good mechanical properties, flame retardancy and melt flow rate.
Compared with the prior art, the invention has at least the following advantages:
the reinforced halogen-free flame-retardant polyamide composite material uses the crystalline polyamide resin and the amorphous polyamide resin, effectively improves the flow property of the crystalline polyamide resin, is beneficial to fully dispersing the halogen-free flame retardant and the glass fiber in the crystalline polyamide resin and the amorphous polyamide resin, and is further beneficial to improving the mechanical property and toughness of the reinforced halogen-free flame-retardant polyamide composite material. In addition, the ethylene-maleic anhydride copolymer and the organic silicon additive are beneficial to promoting the formation of more uniform melt and reducing the release of smoke, so that a more complete carbon layer is formed in the combustion process, and a better synergistic flame retardant effect is achieved. Therefore, the noncrystalline polyamide resin, the ethylene-maleic anhydride copolymer, the organic silicon additive and the halogen-free flame retardant are jointly used, the dosage of the halogen-free flame retardant is reduced under the condition of ensuring that the reinforced halogen-free flame retardant polyamide composite material has a better flame retardant effect, namely the addition amount of the halogen-free flame retardant in the reinforced halogen-free flame retardant polyamide composite material is reduced, the precipitation amount of the halogen-free flame retardant is further reduced, the corrosivity of the reinforced halogen-free flame retardant polyamide composite material is reduced, the maintenance period and the cost of equipment are favorably reduced, and the production efficiency is further improved.
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 reinforced halogen-free flame-retardant polyamide composite material is characterized by comprising the following components in parts by weight:
2. the reinforced halogen-free flame retardant polyamide composite material according to claim 1, wherein the halogen-free flame retardant is a phosphorus-nitrogen system halogen-free flame retardant based on aluminum diethylphosphinate.
3. The reinforced halogen-free flame retardant polyamide composite material according to claim 1, wherein the amorphous polyamide resin is a semi-aromatic polyamide resin.
4. The reinforced halogen-free flame retardant polyamide composite material according to claim 3, wherein the semi-aromatic polyamide resin comprises at least one of PA6I and PA 6T.
5. The reinforced halogen-free flame retardant polyamide composite material according to claim 1, wherein the copolymerization ratio of ethylene to maleic anhydride in the ethylene-maleic anhydride copolymer is 1: 1.
6. The reinforced halogen-free flame retardant polyamide composite material according to claim 1, characterized in that the silicone additive is an organo-modified polysiloxane.
7. The reinforced halogen-free flame-retardant polyamide composite material as claimed in claim 1, further comprising the following components in parts by weight:
0.3 to 1.0 portion of lubricant;
0.2 to 0.5 portion of antioxidant.
8. The reinforced halogen-free, flame-retardant polyamide composite material of claim 7 wherein the lubricant comprises at least one of pentaerythritol tetrastearate, montan wax, and ethylene bis-stearamide.
9. The reinforced halogen-free, flame-retardant polyamide composite material of claim 7, wherein the antioxidant comprises at least one of N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
10. A preparation method of the reinforced halogen-free flame-retardant polyamide composite material, which is used for preparing the reinforced halogen-free flame-retardant polyamide composite material as claimed in any one of claims 1 to 9, and comprises the following steps:
stirring and mixing the crystalline polyamide resin, the non-crystalline polyamide resin, the organic silicon additive and the ethylene-maleic anhydride copolymer to obtain a premix;
and carrying out extrusion granulation operation on the premix, the halogen-free flame retardant and the glass fiber to obtain the reinforced halogen-free flame-retardant polyamide composite material.
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