An additive composition and its application

Abstract

This invention belongs to the field of polymer additive technology, and provides an additive composition and its application. The additive composition comprises, by weight, the following components: 65-84 parts of aluminum diethylphosphinate, 7-16 parts of melamine polyphosphate, 7.5-16 parts of flame retardant synergist, and 0.1-1 parts of aluminum alkylphosphinate; the water content in the additive composition is 0.4%-0.6% by weight. Through the design and synergistic effect of the components, and by controlling the water content, this invention enables the additive composition to possess excellent flame retardant properties, stability, and anti-exudation properties. The additive composition is used for flame retardancy in polymer systems, particularly enabling polyamide compositions containing it to exhibit excellent flame retardant properties, flame retardant stability, and high-temperature and high-humidity resistance. It maintains excellent flame retardancy even after high-temperature and high-humidity aging, and inhibits or avoids additive exudation problems, greatly improving the overall performance of flame-retardant polyamides.

Description

Technical Field

[0001] This invention belongs to the field of polymer additive technology, and specifically relates to an additive composition and its application. Background Technology

[0002] Aluminum diethylphosphonate is a halogen-free, environmentally friendly flame retardant. It is a white powder that is insoluble in water and most organic solvents, but readily soluble in strong acid and alkali solutions. It features high flame retardancy, high thermal stability, low smoke, small particle size, low specific gravity, good dispersibility and compatibility, and is widely used in flame retardant applications for thermoplastic plastics (such as PPA, PA66, PBT), fibers, and textiles.

[0003] Aluminum diethylphosphonate alone does not provide ideal flame retardancy and usually needs to be used in combination with other flame retardants. For example, US6365071B1 discloses a synergistic flame retardant for polymers, comprising aluminum diethylphosphonate and a nitrogen-containing compound, including benzomelamine, tris(hydroxyethyl)isocyanurate, melamine cyanurate, melamine polyphosphate, melamine pyrophosphate, etc.; this synergistic flame retardant has a better flame retardant synergistic effect than aluminum diethylphosphonate alone. CN112812366A discloses a flame-retardant composition comprising the following components: 55-65 wt% aluminum diethylphosphinate, 15-26 wt% melamine polyphosphate, 10-15 wt% melamine cyanurate, 4-8 wt% organically modified montmorillonite, and 0-5 wt% aluminum phosphite. The flame-retardant material containing this composition decomposes during combustion to form a char layer, which serves as a heat-insulating and oxygen-barrier protective layer. The nitrogen-containing compounds in the flame-retardant composition also have foaming and char-reinforcing effects, and the aluminum phosphite provides a synergistic flame-retardant effect, resulting in a flame-retardant material with good flame retardancy and maintaining good mechanical properties.

[0004] Currently, compound flame-retardant systems of aluminum diethyl phosphonate are widely used in the field of halogen-free flame-retardant glass fiber reinforced engineering plastics. Common systems include: aluminum diethyl phosphonate compounded with melamine polyphosphate (MPP), aluminum diethyl phosphonate compounded with melamine cyanuric acid (MCA), and aluminum diethyl phosphonate with aluminum phosphite. These systems have advantages such as high flame-retardant efficiency, high temperature resistance, and low performance loss to the resin matrix. However, in the research on flame retardant thermoplastic nylon, it was found that whether aluminum diethyl phosphonate is used alone or combined with melamine polyphosphate to form a compound flame retardant, the flame-retardant performance of the flame-retardant nylon material will decrease under high temperature and high humidity conditions.

[0005] Furthermore, research has revealed a significant issue with the release of existing flame retardant additives. This release not only causes a white, hazy substance to appear on the surface of flame-retardant materials, affecting their appearance, but also reduces their flame-retardant properties, leading to environmental pollution. This poses a serious quality problem for products requiring high fire resistance standards. Therefore, addressing the issue of flame retardant release is crucial for improving product quality.

[0006] Therefore, there is a desire in the art to develop a flame retardant additive for use in the flame retardancy of polymers such as polyamide (nylon), so that the polymers maintain excellent flame retardant properties under high temperature and high humidity conditions, and the additive is not easily exuded. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the present invention aims to provide an additive composition and its application. Through the design and mutual compounding of the components, the additive composition has excellent flame retardant properties and stability, and the polyamide composition containing it has excellent flame retardancy. It maintains excellent flame retardant stability in high temperature and high humidity environments, while inhibiting or avoiding the problem of additive precipitation.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides an additive composition comprising, by weight, the following components:

[0010] 65-84 parts of aluminum diethylphosphinate

[0011] 7-16 parts of melamine polyphosphate

[0012] Flame retardant synergist 7.5-16 parts,

[0013] 0.1-1 part of aluminum alkylphosphonite;

[0014] The additive composition contains 0.4%-0.6% water by mass; the flame retardant synergist includes any one or more of zinc borate, zirconium phosphate, zinc selenate, sodium antimonate, and antimony oxide.

[0015] The additive composition provided by this invention comprises a combination of aluminum diethylphosphonate, melamine polyphosphate, a flame retardant synergist, and aluminum alkylphosphonate. Through the design and synergistic interaction of these four components, the additive composition exhibits excellent flame retardant properties, stability, and anti-exudation properties. Simultaneously, the additive composition contains a specific proportion of water, which further enhances its stability and anti-exudation properties. When used for flame retardancy in polymer systems, the additive composition imparts excellent flame retardant properties, flame retardant stability, and high-temperature and high-humidity resistance to polyamide compositions containing it. It maintains excellent flame retardancy even after high-temperature and high-humidity aging and inhibits or avoids additive exudation problems, significantly improving the overall performance of flame-retardant polyamides.

[0016] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0017] In this invention, the aluminum diethylphosphonate has a mass fraction of 65-84 parts, for example, 66 parts, 68 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, or 83 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0018] In this invention, aluminum diethylphosphonate is the main component of the additive composition, preferably with a mass percentage of ≥60%, for example, 62%, 65%, 66%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, or 84%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0019] The melamine polyphosphate is in the range of 7-16 parts by weight, for example, 8, 9, 10, 11, 12, 13, 14 or 15 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0020] Preferably, the melamine polyphosphate content in the additive composition is ≥5% by mass, for example, it can be 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or 16%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0021] The flame retardant synergist is present in a mass fraction of 7.5-16 parts, for example, 8, 9, 10, 11, 12, 13, 14 or 15 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0022] Preferably, the flame retardant synergist in the additive composition has a mass percentage content of ≥5%, for example, it can be 6%, 7%, 7.5%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or 16%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0023] The aluminum alkylphosphonate is in the range of 0.1-1 parts by weight, for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts or 0.9 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0024] Preferably, the mass percentage of aluminum alkylphosphonate in the additive composition is ≥0.05%, for example, it can be 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0025] The water in the additive composition may be water of crystallization and / or free water. As water of crystallization, it may be incorporated into any one or at least two of aluminum diethylphosphinate, melamine polyphosphate, flame retardant synergist, aluminum alkylphosphinate, optionally aluminum ethylbutylphosphinate, optionally aluminum monoethylphosphinate, and optionally aluminum phosphite.

[0026] The water content in the additive composition is 0.4%-0.6% by mass, for example, it can be 0.42%, 0.45%, 0.48%, 0.5%, 0.52%, 0.55% or 0.58%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0027] In this invention, the source of water (water of crystallization and / or free water) in the additive composition is not specifically limited. It can be derived from any one or at least two of aluminum diethylphosphinate, melamine polyphosphate, flame retardant synergist, aluminum alkylphosphinate, optionally aluminum ethylbutylphosphinate, optionally aluminum monoethylphosphinate, and optionally aluminum phosphite. If none of the aforementioned components contain water or the water content is extremely low, water can be introduced into the composition by external addition. If the water content in the aforementioned components is high, a portion of the water can be removed by drying to make the water content in the additive composition 0.4%-0.6% by mass.

[0028] Polymers containing polar groups in their molecular chains (such as polyamides) exhibit strong water absorption, with the amount of water absorbed depending on relative humidity, water temperature, and time. The water absorption characteristic of polyamides is due to the breaking of hydrogen bonds in their molecular chains and the formation of hydrogen bonds between water molecules. After absorbing water, the adsorbed water alters the microstructure of the polyamide molecules, leading to changes in various properties of the polyamide material. Conditioning polyamides utilizes this water-absorbing characteristic, controlling humidity and temperature to achieve the optimal moisture content. The purpose of conditioning is to bring the polyamide material to a balanced moisture content in a specific operating environment, thereby ensuring its performance stability. During the flame-retardant modification of polyamides, the presence of moisture can lead to the hydrolysis of the polyamide macromolecular chains and a decrease in relative molecular weight, resulting in a decline in the overall mechanical properties of the polyamide. Therefore, during polyamide modification, it is generally necessary to ensure that the polyamide does not absorb water or to perform pre-drying treatment.

[0029] During the research process, this invention discovered that by controlling the water content in the additive composition to 0.4%-0.6% by mass, it is possible to achieve excellent flame-retardant properties, flame-retardant stability, and anti-exudation effects in the flame-retardant modified polyamide composite material without compromising the mechanical properties of the polyamide. If the water content is <0.4% by mass, it will affect the stability of the additive composition, causing a decrease in the flame-retardant performance of the polyamide composition containing it after high-temperature and high-humidity aging; if the water content is >0.6%, it will lead to the degradation of the polyamide resin macromolecular chains, thereby reducing the performance of the polyamide composition.

[0030] For example, the water content in the additive composition can be obtained by infrared heating evaporation method; for example, the water content is automatically determined after placing the sample in an infrared moisture analyzer (model MA 35, Sartorius, Germany) at 120°C for 30 min.

[0031] In this invention, the flame retardant synergist includes any one or more of zinc borate, zirconium phosphate, zinc selenate, sodium antimonate, and antimony oxide; "multiple" indicates a combination of at least two.

[0032] Preferably, the flame retardant synergist includes zinc borate.

[0033] Preferably, the alkylphosphonite aluminum comprises ethylphosphonite aluminum and / or butylphosphonite aluminum, and more preferably ethylphosphonite aluminum.

[0034] Preferably, the additive composition further comprises 0.1-3 parts by weight of aluminum ethylbutylphosphinic acid, wherein the parts by weight of aluminum ethylbutylphosphinic acid can be 0.2, 0.3, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, or 2.8 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0035] And / or, preferably, the additive composition further comprises 0.01-0.8 parts by weight of aluminum monoethylphosphinic acid, wherein the parts by weight of aluminum monoethylphosphinic acid may be 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts or 0.7 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0036] Preferably, the additive composition further includes aluminum phosphite.

[0037] Preferably, the mass fraction of aluminum phosphite in the additive composition is ≤1 part, for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0038] In a preferred embodiment, the additive composition comprises the following components in parts by weight:

[0039] 65-84 parts of aluminum diethylphosphinate

[0040] 7-16 parts of melamine polyphosphate

[0041] Flame retardant synergist 7.5-16 parts,

[0042] 0.1-1 part of aluminum alkylphosphonite

[0043] Aluminum ethyl butylphosphinate 0.1-3 parts,

[0044] Aluminum monoethylphosphonate 0.01-0.8 parts,

[0045] 0-1 part aluminum phosphite;

[0046] The water content in the additive composition is 0.4%-0.6% by mass.

[0047] In this invention, the aluminum diethylphosphite, melamine polyphosphate, flame retardant synergist, aluminum alkylphosphite, aluminum ethylbutylphosphite, aluminum monoethylphosphite, and aluminum phosphite can be purchased from the market or prepared by synthetic methods known in the art.

[0048] For example, the method for preparing the additive composition includes: mixing aluminum diethylphosphinate, melamine polyphosphate, flame retardant synergist, aluminum alkylphosphinate, optionally aluminum ethylbutylphosphinate, optionally aluminum monoethylphosphinate, and optionally aluminum phosphite evenly to obtain the additive composition.

[0049] In a preferred embodiment, after the mixture is homogeneously mixed, the mass content of water in the mixture is tested. If the mass content of water is 0.4%-0.6%, the additive composition is obtained.

[0050] In another preferred embodiment, after the mixture is homogeneously mixed, the mass content of water in the mixture is tested. If the mass content of water is <0.4%, water is added to the mixture to control the mass content of water to 0.4%-0.6%, thereby obtaining the additive composition.

[0051] Preferably, the method of adding water includes: placing the mixture in a humid environment to absorb water.

[0052] Optionally, the humidity of the humid environment is 80-98%, for example, it can be 82%, 85%, 88%, 90%, 92%, 95% or 96%, etc.

[0053] Optionally, the temperature of the humid environment is 15-38°C, for example, it can be 16°C, 18°C, 20°C, 22°C, 25°C, 26°C, 28°C, 30°C, 32°C or 35°C, and more preferably room temperature / normal temperature.

[0054] In another preferred embodiment, after the mixture is homogeneously mixed, the mass content of water in the mixture is tested. If the mass content of water is >0.6%, the mixture is dried to control the mass content of water to 0.4%-0.6%, thereby obtaining the additive composition.

[0055] In a second aspect, the present invention provides the use of the additive composition as described in the first aspect in polymer materials.

[0056] Preferably, the additive composition is applied as a flame retardant to the polymer material.

[0057] Preferably, the polymer material includes any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyolefin, polyphenylene ether, and polyacrylate.

[0058] Thirdly, the present invention provides a polyamide composition comprising a polyamide and an additive composition as described in the first aspect.

[0059] Preferably, the polyamide composition comprises, by weight, the following components:

[0060] 40-70 parts of polyamide

[0061] The additive composition is 5-35 parts.

[0062] Preferably, the polyamide is in the range of 40-70 parts by weight, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts or 70 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0063] In the polyamide composition, polyamide is used as the matrix material, preferably with a mass percentage of ≥40%, for example, 42%, 45%, 50%, 55%, 60%, 65%, or 70%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0064] Preferably, the additive composition is in the range of 5-35 parts by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts or 34 parts, and specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0065] The additive composition can exert a highly efficient flame retardant effect. Preferably, the mass percentage of the additive composition in the polyamide composition is ≥4%, for example, it can be 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, or 35%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 6%-30% is further preferred.

[0066] Preferably, the polyamide includes any one or a combination of at least two of polyamide resin and polyamide elastomer.

[0067] As a polyamide, it includes any one or a combination of at least two of the following: condensation products of dicarboxylic acids and diamines, condensation products of ω-amino acids, and ring-opening polymerization products of lactams. The dicarboxylic acids exemplarily include, but are not limited to, any one or a combination of at least two of adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid. The diamines exemplarily include, but are not limited to, any one or a combination of at least two of pentanediamine, hexamethylenediamine, decanediamine, dodecanediamine, butanediamine, p-phenylenediamine, and m-phenylenediamine. The lactams exemplarily include, but are not limited to, any one or a combination of at least two of caprolactam, octanolactam, undecanolactam, and dodecalactam. The ω-amino acids exemplarily include, but are not limited to, any one or a combination of at least two of the ω-amino acids formed by ring-opening of the aforementioned lactams and aminobenzoic acid.

[0068] Preferably, the polyamide includes any one or a combination of at least two of the following: polyamide 6 (polycaprolactam), polyamide 11 (polyundecanolactam), polyamide 12 (polydodecanolactam), polyamide 56 (polypentyl adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene decanediamide), polyamide 612 (polyhexamethylene dodecyl diamine), polyamide 1010 (polydecyl decanediamide), polyamide 1012 (polydodecyl decanediamide), polyamide 1212 (polydodecyl dodecyl diamine), polyamide 6T (polyhexamethylene terephthalamide), polyamide 10T (polydecanediamide), and PPA (poly(p-phenylene terephthalamide)).

[0069] It should be noted that the polyamide composition of the present invention may also include any other fillers, other additives, etc. that are motivated to be added in the art.

[0070] Preferably, the polyamide composition further comprises 5-45 parts by weight of reinforcing material, wherein the reinforcing material may be 6 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 42 parts, or 44 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0071] Preferably, the reinforcing material includes any one or two of glass fiber and carbon fiber, with glass fiber being more preferred.

[0072] Preferably, the glass fiber includes any one or a combination of at least two of the following: alkali-free glass fiber (E glass fiber), medium-alkali glass fiber (C glass fiber), high-alkali glass fiber (A glass fiber), special glass fiber (S glass fiber), D glass fiber, and quartz glass fiber.

[0073] Preferably, the polyamide composition further includes any one or a combination of at least two of the following: a lubricant, an antioxidant, and a colorant.

[0074] Preferably, the polyamide composition further comprises 0.01-1 parts by weight of a lubricant, wherein the lubricant may be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, or 0.9 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0075] Preferably, the lubricant includes any one or a combination of at least two of the following: ester lubricants, alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, and metal soap lubricants.

[0076] Preferably, the polyamide composition further comprises 0.01-1 parts by weight of an antioxidant, wherein the antioxidant may be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, or 0.9 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0077] Preferably, the antioxidant includes any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

[0078] Preferably, the polyamide composition further comprises 0.01-3 parts by weight of a colorant, wherein the colorant may be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, or 2.8 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0079] In this invention, the colorant is not specifically limited, and any colorant that can be used in polymer systems is applicable to this invention. The colorant can be any one or a combination of at least two of color powder, color paste, and color masterbatch, and the color of the colorant can be adjusted according to the appearance requirements of the product.

[0080] Preferably, the polyamide composition further includes fillers and / or ultraviolet absorbers.

[0081] In a preferred embodiment, the polyamide composition comprises the following components in parts by weight:

[0082] 40-70 parts of polyamide

[0083] 5-45 parts of reinforcing material

[0084] The additive composition is 5-35 parts.

[0085] Antioxidant 0-1 part,

[0086] 0-1 part lubricant

[0087] Colorant 0-3 parts.

[0088] For example, the method for preparing the polyamide composition includes: melting and blending the components of the polyamide composition and then extruding them to obtain the polyamide composition.

[0089] Preferably, the melt blending is carried out in a screw extruder.

[0090] Preferably, the screw extruder is a twin-screw extruder.

[0091] Preferably, the temperature of the screw extruder is 180-330℃, for example, it can be 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃ or 320℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0092] Preferably, the extrusion process further includes granulation and drying steps.

[0093] Compared with the prior art, the present invention has the following beneficial effects:

[0094] The additive composition provided by this invention, through the design and synergistic interaction of aluminum diethylphosphonate, melamine polyphosphate, flame retardant synergist, and aluminum alkylphosphonate, endows the additive composition with excellent flame retardant properties and stability. Simultaneously, the additive composition contains a specific proportion of water, which further enhances its stability and anti-exudation properties. This additive composition is used for flame retardancy in polymer systems, particularly giving polyamide compositions containing it excellent flame retardant properties, flame retardant stability, and high-temperature and high-humidity resistance. It maintains excellent flame retardancy even after high-temperature and high-humidity aging and effectively inhibits or avoids additive exudation problems, greatly improving the overall performance of flame-retardant polyamides. Detailed Implementation

[0095] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0096] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not limited to those elements and may also include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0097] In the following specific embodiments, the water content in each mixture and additive composition is obtained by infrared heating evaporation method. The specific method is as follows: 5±0.1 g of the sample to be tested is placed in an infrared moisture analyzer (MA 35 type, Sartorius, Germany), and its moisture content is automatically tested after being placed at a temperature of 120℃ for 30 min.

[0098] The following are exemplary examples of several additive compositions according to the present invention. The material information used in the following examples is shown in the table below:

[0099]

[0100] Examples 1-8, Comparative Examples 1-6

[0101] An additive composition, the types and amounts of each component are shown in Table 1. Except for water, the amount of each component is in "parts by mass"; the water content is the mass content, in "%".

[0102] Table 1

[0103]

[0104] The preparation methods of the additive compositions provided in Examples 1-8 and Comparative Examples 3-6 are as follows:

[0105] (1) Weigh ADP, MPP, zinc borate, aluminum ethyl phosphite, aluminum ethyl butyl phosphite, aluminum monoethyl phosphite and optional aluminum phosphite. Mix each component in a ribbon mixer for 30 min in a dry and sealed environment at room temperature to obtain a mixture. The additive composition with the contents of each component shown in Table 1 is then placed in an aluminum foil bag, vacuumed, and sealed for later use.

[0106] (2) Test the water content in the mixture. If it is within the range of 0.4%-0.6%, the additive composition is obtained. If the water content is <0.4%, place the sample in an environment with 95% humidity and 25°C to absorb water, and control the water content in the product to 0.4%-0.6% to obtain the additive composition. If the water content is >0.6%, place the mixture in an oven at 60°C to dry, and control the water content in the product to 0.4%-0.6% to obtain the additive composition.

[0107] The additive composition provided in Comparative Example 1 was prepared as follows: The additive composition provided in Example 3 was placed in an oven and dried at 60°C to obtain an additive composition with a water content of 0.18%.

[0108] The preparation method of the additive composition provided in Comparative Example 2 is as follows: The additive composition provided in Example 3 is placed in an environment of 25°C and 95% humidity to absorb water, so that the water content of the product is 0.7% by mass, and the additive composition is obtained.

[0109] The polyamide compositions of the present invention will be described in detail below using application examples, but the polyamide compositions are not limited to these application examples.

[0110] In the following application examples, the specific information of the materials used is as follows:

[0111]

[0112] Application Example 1-9, compared with Application Example 1-8

[0113] A polyamide composition, the types and amounts of each component are shown in Tables 2 and 3, and the unit of amount of each component is "parts by mass"; "--" indicates that the component was not added.

[0114] The preparation method of the polyamide composition includes: mixing polyamide, lubricant, antioxidant and black seed according to the formula amount, and feeding them into the main feed port of the screw through a loss-in-weight weigher at a set weight ratio; feeding glass fiber and additive composition into the first and second side feed ports of the screw through a loss-in-weight weigher at a set ratio; the screw speed of the twin-screw extruder is 350 rpm; the temperatures of zones 1-12 are 80℃, 120℃, 260℃, 250℃, 220℃, 220℃, 220℃, 220℃, 220℃, 250℃, and 260℃ respectively; and obtaining polyamide composition particles by melt mixing, extrusion granulation.

[0115] The following performance tests were performed on the polyamide composition:

[0116] (1) Flame retardancy: The test sample is injection molded into a 125 mm × 13 mm × 1.6 mm strip and tested according to ANSI / UL-94-1985 standard. "t1+t2" represents the afterflame time, in seconds.

[0117] (2) Flame retardant performance after high temperature and high humidity aging: The sample to be tested was injection molded into a 125 mm × 13 mm × 1.6 mm strip, and placed in a humid heat aging chamber. It was aged at 85℃ and 85% humidity for 168 h. After taking it out, the flame retardant performance was tested according to the method in (1).

[0118] (3) Precipitation: The sample to be tested was injection molded into a strip of 125 mm × 13 mm × 1.6 mm. The strip was placed in a humid heat aging chamber and aged at 85°C and 85% humidity for 168 h. The precipitation on the surface of the strip was observed visually. If a lot of white spots (>5) were visible to the naked eye on each strip, it was obvious precipitation; if a few white spots (1-5) were visible, it was a small amount of precipitation; if it was not visible to the naked eye, it was observed by magnifying it to 200-1000 times with an electron microscope. If the precipitation was observed, it was a trace amount of precipitation. If no precipitation was observed, there was no precipitation.

[0119] (4) Bending strength: The bending strength before and after aging was tested according to the method in standard GB / T9341-2008; the aging conditions were: aging in a damp heat aging chamber at 85°C and 85% humidity for 168 h.

[0120] The test data are shown in Tables 2 and 3.

[0121] Table 2

[0122]

[0123] Table 3

[0124]

[0125] As can be seen from the performance data in Table 2, the additive composition provided by this invention, through the design and synergistic compounding of each component and the control of a specific water content, exhibits excellent flame retardant properties, stability, and anti-exudation properties. The additive composition is used for the flame retardant modification of polyamides, enabling the polyamide composition to achieve a V-0 flame retardant rating. After 168 h of damp heat aging under double 85 conditions, it still maintains a V-0 flame retardant rating, and the additive shows no or only trace amounts of exudation.

[0126] Comparing the data in Tables 2 and 3, it can be seen that the water content in additive composition D1 in Comparative Application Examples 1 and 7 is too low, resulting in a significant decrease in the flame retardancy of the polyamide composition using it after damp heat aging and the precipitation of additives. Conversely, the water content in the additive compositions in Comparative Application Examples 2 and 8 is too high, leading not only to significant deterioration in the flame retardancy and the precipitation of additives in the polyamide composition after damp heat aging, but also to a decrease in mechanical properties. The additive compositions D3-D6 in Comparative Application Examples 3-6 do not contain the compounding system defined by the present invention and in the specific amounts, resulting in a significant decrease in one or more of their flame retardancy, stability, and anti-precipitation properties. When used for flame retardant modification of polyamide materials, their flame retardant performance after damp heat aging is significantly reduced, and the amount of precipitation increases.

[0127] The applicant declares that the above embodiments illustrate the additive composition and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound additive composition, characterized in that, The additive composition comprises the following components in parts by weight: 65-84 parts of aluminum diethylphosphinate 7-16 parts of melamine polyphosphate Flame retardant synergist 7.5-16 parts, 0.1-1 part of aluminum alkylphosphonite; The additive composition contains 0.4%-0.6% water by mass. The flame retardant synergist includes any one or more of zinc borate, zirconium phosphate, zinc selenate, sodium antimonate, and antimony oxide.

2. The compound additive composition according to claim 1, characterized in that, The alkyl phosphonates include aluminum ethyl phosphonates and / or aluminum butyl phosphonates.

3. The compound additive composition according to claim 1, characterized in that, The additive composition further includes 0.1-3 parts by weight of aluminum ethylbutylphosphonate; And / or, the additive composition further comprises 0.01-0.8 parts by weight of aluminum monoethylphosphonate.

4. The compound additive composition according to claim 1, characterized in that, The additive composition also includes aluminum phosphite; The mass fraction of aluminum phosphite in the additive composition is ≤1 part.

5. The use of a compound additive composition as described in any one of claims 1-4 in polymer materials.

6. A polyamide composition, characterized in that, The polyamide composition includes polyamide and a compound additive composition as described in any one of claims 1-4.

7. The polyamide composition according to claim 6, characterized in that, The polyamide composition comprises the following components in parts by weight: 40-70 parts of polyamide The compound additive composition is 5-35 parts.

8. The polyamide composition according to claim 7, characterized in that, The polyamide composition further includes 5-45 parts by weight of reinforcing material; The reinforcing material includes any one or two of glass fiber and carbon fiber.

9. The polyamide composition according to claim 7, characterized in that, The polyamide composition further includes 0.01-1 parts by weight of lubricant; And / or, the polyamide composition further comprises 0.01-1 parts by weight of antioxidant; And / or, the polyamide composition further includes 0.01-3 parts by weight of colorant.

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