Additive composition and application thereof

Abstract

The invention belongs to the technical field of polymer additives, and provides an additive composition and application thereof, the additive composition comprises the following components by mass: 65-84 parts of aluminum diethylphosphinate, 7-16 parts of melamine polyphosphate, 7.5-16 parts of a flame retardant synergist, and 0.1-1 part of aluminum alkyl phosphite; the mass percentage content of water in the additive composition is 0.4%-0.6%. Through design and mutual cooperation of the components and control of the water content, the additive composition has excellent flame retardance, stability and precipitation resistance. The additive composition is used for flame retardance of a polymer system, especially enables the polyamide composition containing the additive composition to have excellent flame retardance, flame retardance stability and high-temperature and high-humidity resistance, still keeps excellent flame retardance after high-temperature and high-humidity aging, inhibits or avoids the problem of additive precipitation, and is suitable for industrial production. The comprehensive performance of the flame-retardant polyamide is greatly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer additives, and in particular relates to an additive composition and application thereof. Background Art

[0002] Aluminum diethylphosphinate is a halogen-free, green and environmentally friendly flame retardant. It appears as a white powder. It is insoluble in water and most organic solvents, but easily soluble in strong acid and strong alkali solutions. It has the characteristics of high efficiency flame retardancy, high thermal stability, low smoke, small particle size, low specific gravity, good dispersibility and compatibility. It is widely used in flame retardant products such as thermoplastics (such as PPA, PA66, PBT), fibers and textiles.

[0003] The flame retardant efficiency of aluminum diethylphosphinate is not ideal when used alone, and it usually needs to be used in combination with other flame retardants. For example, US6365071B1 discloses a synergistic flame retardant for polymers, including aluminum diethylphosphinate and a nitrogen-containing compound, wherein the nitrogen-containing compound includes benzoguanamine, tris(hydroxyethyl)isocyanurate, melamine cyanurate, polyphosphate melamine, pyrophosphate melamine, etc.; the synergistic flame retardant has a better flame retardant synergistic effect than aluminum diethylphosphinate 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% organic modified montmorillonite and 0-5 wt% aluminum phosphite; the flame retardant material containing the flame retardant composition can decompose to form a coke layer during combustion, and the coke layer has the function of a heat-insulating and oxygen-barrier protective layer; the nitrogen-containing compound in the flame retardant composition also has the functions of foaming and coke enhancement; the aluminum phosphite can play a synergistic flame retardant effect, so that the flame retardant material prepared has good flame retardancy and can maintain good mechanical properties.

[0004] At present, the compound flame retardant system of aluminum diethylphosphinate is widely used in the field of halogen-free flame retardant glass fiber reinforced engineering plastics. Common systems include: aluminum diethylphosphinate compounded with melamine polyphosphate (MPP) system, aluminum diethylphosphinate compounded with melamine cyanuric acid (MCA) system, and aluminum diethylphosphinate and aluminum phosphite system. These systems have the advantages of high flame retardant efficiency, high temperature resistance, and small loss of resin matrix performance. However, in the process of studying the flame retardancy of thermoplastic nylon, it was found that whether aluminum diethylphosphinate is used alone or combined with melamine polyphosphate to form a compound flame retardant, the flame retardant performance of flame-retardant nylon materials will decrease under high temperature and high humidity conditions.

[0005] In addition, research has also found that existing flame retardant additives have obvious precipitation problems. Flame retardant precipitation not only causes white mist to appear on the surface of flame retardant material products, affecting the appearance of the product; it also causes the flame retardant performance of the material to decrease, causing environmental pollution, which is a serious quality problem for products that require high fire protection standards. Therefore, solving the flame retardant precipitation problem is of great significance to improving product quality.

[0006] Therefore, the art expects to develop a flame retardant additive, which can be used for the flame retardancy of polymers such as polyamide (nylon), so that the polymer can still maintain excellent flame retardant properties under high temperature and high humidity conditions, and the additive is not easy to precipitate. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide an additive composition and its application. Through the design and compounding of components, the additive composition has excellent flame retardant properties and stability, and the polyamide composition containing the additive has excellent flame retardancy, maintains excellent flame retardant stability under high temperature and high humidity environment, and at the same time suppresses or avoids the problem of additive precipitation.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides an additive composition, wherein the additive composition comprises the following components in parts by mass:

[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 alkyl aluminum phosphite;

[0014] The mass percentage of water in the additive composition is 0.4%-0.6%; 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 the present invention includes a combination of aluminum diethylphosphinate, melamine polyphosphate, a flame retardant synergist and alkyl aluminum phosphinate. Through the design and mutual synergy of the four components, the additive composition has excellent flame retardant properties, stability and anti-precipitation properties; at the same time, the additive composition contains a specific proportion of water, which can further improve the stability and anti-precipitation properties of the additive composition. The additive composition is used for flame retardancy of polymer systems, so that the polyamide composition containing it has excellent flame retardant properties, flame retardant stability and high temperature and high humidity resistance, and still maintains excellent flame retardancy after high temperature and high humidity aging, and suppresses or avoids the problem of additive precipitation, greatly improving the comprehensive performance of flame retardant polyamide.

[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. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0017] In the present invention, the mass parts of the diethyl phosphinate aluminum are 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0018] In the present invention, aluminum diethylphosphinate is the main component in the additive composition, and its mass percentage is preferably ≥60%, for example, it can be 62%, 65%, 66%, 68%, 70%, 72%, 75%, 78%, 80%, 82% or 84%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0019] The mass parts of the melamine polyphosphate are 7-16 parts, for example, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0020] Preferably, the mass percentage of melamine polyphosphate in the additive composition is ≥5%, for example, it can be 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or 16%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0021] The mass fraction of the flame retardant synergist is 7.5-16 parts, for example, it can be 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0022] Preferably, the mass percentage of the flame retardant synergist in the additive composition is ≥5%, for example, it can be 6%, 7%, 7.5%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or 16%, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0023] The mass fraction of the alkyl aluminum phosphite is 0.1-1 part, for example, it can be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part or 0.9 part, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0024] Preferably, the mass percentage of alkyl aluminum phosphite 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%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0025] The water in the additive composition may be crystal water and / or free water. As crystal water, it may be bound to any one or at least two of diethyl aluminum phosphinate, melamine polyphosphate, flame retardant synergist, alkyl aluminum phosphites, optionally ethylbutyl aluminum phosphites, optionally monoethyl aluminum phosphites, optionally aluminum phosphites.

[0026] The mass percentage of water in the additive composition is 0.4%-0.6%, for example, it can be 0.42%, 0.45%, 0.48%, 0.5%, 0.52%, 0.55% or 0.58%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0027] In the present invention, the source of water (crystallization water and / or free water) in the additive composition is not particularly limited, and it can be derived as crystallization water and / or free water from any one or at least two of diethyl aluminum phosphite, melamine polyphosphate, flame retardant synergist, alkyl aluminum phosphite, optionally ethylbutyl aluminum phosphite, optionally monoethyl aluminum phosphite, and optionally aluminum phosphite; if the aforementioned components do not contain water or the water content is extremely low, water can also be introduced into the composition by external addition; if the water content in the aforementioned components is high, a portion of the water can also be removed by drying so that the mass content of water in the additive composition is 0.4%-0.6%.

[0028] For polymers containing polar groups in the molecular chain (such as polyamide), their water absorption is also strong, and the amount of water absorbed is related to relative humidity, water temperature, time, etc. The water absorption characteristics of polyamide are due to the combination of the breaking of hydrogen bonds in its molecular chain and the formation of hydrogen bonds by water molecules. After absorbing water, the water adsorbed into the polyamide changes the microstructure of the molecule, resulting in changes in the performance of the polyamide material in all aspects. Polyamide humidity control is a process that utilizes the water absorption characteristics of polyamide to control humidity and temperature to make the polyamide material reach the optimal water content. The purpose of humidity control treatment is to make the polyamide material reach a balanced water content in a specific use environment, thereby ensuring its stable performance. The presence of water in the polyamide flame retardant modification process will cause the hydrolysis of the polyamide macromolecular chain and the decrease of the relative molecular weight, thereby causing the comprehensive mechanical properties of the polyamide to decrease. Therefore, in the polyamide modification process, it is generally necessary to ensure that the polyamide does not absorb water or needs to be pre-dried.

[0029] The present invention has been found in the research process that by controlling the mass content of water in the additive composition to 0.4%-0.6%, it is possible to achieve excellent flame retardancy, flame retardancy stability and anti-precipitation effects of the flame retardant modified polyamide composite material without destroying the mechanical properties of the polyamide. If the mass content of water is less than 0.4%, it will affect the stability of the additive composition, causing the flame retardancy of the polyamide composition containing it to decrease after high temperature and high humidity aging; if the water content is greater than 0.6%, it will cause the degradation of the macromolecular chain of the polyamide resin, thereby causing the performance of the polyamide composition to be reduced.

[0030] For example, the mass content of water in the additive composition can be obtained by infrared heating volatilization method; for example, the sample to be tested is placed in an infrared moisture analyzer (model MA 35, Sartorius, Germany), and its moisture mass content is automatically tested after being placed at a temperature of 120° C. for 30 minutes.

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

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

[0033] Preferably, the alkyl aluminum phosphite includes ethyl aluminum phosphite and / or butyl aluminum phosphite, and ethyl aluminum phosphite is further preferred.

[0034] Preferably, the additive composition further includes 0.1-3 parts of ethylbutyl phosphinate aluminum in parts by mass, and the mass parts of ethylbutyl phosphinate aluminum 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0035] And / or, preferably, the additive composition further includes 0.01-0.8 parts by mass of aluminum monoethylphosphinate, and the mass of aluminum monoethylphosphinate can 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0036] Preferably, the additive composition further comprises 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0038] In a preferred technical solution, the additive composition comprises the following components in parts by mass:

[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 alkyl phosphite aluminum,

[0043] 0.1-3 parts of ethylbutyl phosphinate aluminum,

[0044] 0.01-0.8 parts of aluminum monoethylphosphinate,

[0045] Aluminum phosphite 0-1 part;

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

[0047] In the present invention, the aluminum diethylphosphinate, melamine polyphosphate, flame retardant synergist, alkyl aluminum phosphites, ethylbutyl aluminum phosphites, monoethyl aluminum phosphites, and aluminum phosphites can be purchased from the market or prepared by a synthetic method known in the art.

[0048] Exemplarily, the preparation method of the additive composition comprises: uniformly mixing aluminum diethylphosphinate, melamine polyphosphate, a flame retardant synergist, an alkyl aluminum phosphite, optionally aluminum ethylbutylphosphinate, optionally aluminum monoethylphosphinate, and optionally aluminum phosphite to obtain the additive composition.

[0049] In a preferred technical solution, after the mixing is uniform, the water content in the mixture is tested. If the water content is 0.4%-0.6%, the additive composition is obtained.

[0050] In another preferred technical solution, after the mixing is uniform, the water content in the mixture is tested. If the water content is less than 0.4%, water is added to the mixture to control the water content to 0.4%-0.6% to obtain the additive composition.

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

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

[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, etc., and room temperature / normal temperature is further preferred.

[0054] In another preferred technical solution, the water content in the mixture is tested after uniform mixing. If the water content is greater than 0.6%, the mixture is dried to control the water content to 0.4%-0.6% to obtain the additive composition.

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

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

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

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

[0059] Preferably, the polyamide composition comprises the following components in parts by mass:

[0060] Polyamide 40-70 parts,

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

[0062] Preferably, the mass parts of the polyamide are 40-70 parts, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts or 70 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0063] In the polyamide composition, polyamide is used as the matrix material, and its mass percentage is preferably ≥40%, for example, it can be 42%, 45%, 50%, 55%, 60%, 65% or 70%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0064] Preferably, the mass parts of the additive composition are 5-35 parts, 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0065] The additive composition can exert a high-efficiency 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%, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 6%-30% is further preferred.

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

[0067] As a polyamide, it includes any one or a combination of at least two of the condensation products of dicarboxylic acids and diamines, condensation products of ω-amino acids, and ring-opening polymerization products of cyclic 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, dodecanedioic 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 pentamethylenediamine, hexamethylenediamine, decanediamine, dodecanediamine, butanediamine, p-phenylenediamine, and m-phenylenediamine. The cyclic lactams exemplarily include but are not limited to: any one or a combination of at least two of caprolactam, capryllactam, undecane lactam, and lauryl lactam. 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 and aminobenzoic acids formed by the ring opening of the aforementioned cyclic lactams.

[0068] Preferably, the polyamide includes any one of polyamide 6 (polycaprolactam), polyamide 11 (polyundecalactam), polyamide 12 (polydodecalactam), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecane diamide), polyamide 1010 (polydecanediamide), polyamide 1012 (polydecanediamide), polyamide 1212 (polydodecane diamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 10T (polydecanediamide), and PPA (polyparaphenylene terephthalamide), or a combination of at least two thereof.

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

[0070] Preferably, the polyamide composition further includes 5-45 parts of reinforcing material by mass, and the reinforcing material can 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

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

[0072] Preferably, the glass fiber includes any one of 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, or a combination of at least two thereof.

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

[0074] Preferably, the polyamide composition further includes 0.01-1 parts of lubricant by mass, and 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 points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

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

[0076] Preferably, the polyamide composition further includes 0.01-1 parts of antioxidant by mass, and 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 points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

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

[0078] Preferably, the polyamide composition further includes 0.01-3 parts of colorant by mass, and the colorant may be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

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

[0080] Preferably, the polyamide composition further comprises a filler and / or an ultraviolet absorber.

[0081] In a preferred technical solution, the polyamide composition comprises the following components in parts by mass:

[0082] Polyamide 40-70 parts,

[0083] 5-45 parts of reinforcement material,

[0084] 5-35 parts of the additive composition,

[0085] Antioxidant 0-1 part,

[0086] Lubricant 0-1 part,

[0087] Colorant 0-3 parts.

[0088] Illustratively, the method for preparing the polyamide composition comprises: melt-blending the components of the polyamide composition and then extruding the mixture 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°C, for example, it can be 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C or 320°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

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

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

[0094] In the additive composition provided by the present invention, the additive composition has excellent flame retardant properties and stability through the design and mutual cooperation of aluminum diethylphosphinate, melamine polyphosphate, flame retardant synergist and alkyl aluminum phosphinate; at the same time, the additive composition contains a specific proportion of water, which can further improve the stability and anti-precipitation performance of the additive composition. The additive composition is used for flame retardant of polymer systems, especially the polyamide composition containing it has excellent flame retardant properties, flame retardant stability and high temperature and high humidity resistance, and still maintains excellent flame retardancy after high temperature and high humidity aging, and effectively suppresses or avoids the problem of additive precipitation, greatly improving the comprehensive performance of flame retardant polyamide. DETAILED DESCRIPTION

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

[0096] As used herein, the terms "comprises," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0097] In the following specific embodiments, the water content in each mixture and additive composition is obtained by infrared heating volatilization method, and 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 model, Sartorius, Germany), and its moisture mass content is automatically tested after being placed at a temperature of 120°C for 30 minutes.

[0098] Several examples of the additive composition of the present invention are listed below. In the following examples, the material information used is shown in the following table:

[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, the amount units of each component except water are "parts by mass"; the water content is the mass content, the unit is "%".

[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) ADP, MPP, zinc borate, aluminum ethylphosphite, aluminum ethylbutylphosphinate, aluminum monoethylphosphinate and optionally aluminum phosphite were weighed, and the components were mixed by a ribbon mixer for 30 min in a dry and closed environment at room temperature to uniformly mix the components to obtain a mixture, and an additive composition having the content of each component shown in Table 1 was obtained, and the mixture was placed in an aluminum foil bag, evacuated 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 less than 0.4%, place the sample in an environment of 95% humidity and 25°C to absorb water, and control the water content in the product to be 0.4%-0.6%, and obtain the additive composition. If the water content is greater than 0.6%, place the mixture in an oven at 60°C for drying, and control the water content in the product to be 0.4%-0.6%, and obtain the additive composition.

[0107] The preparation method of the additive composition provided in Comparative Example 1 is as follows: the additive composition provided in Example 3 is placed in an oven and dried at 60° C. to make the mass content of water in the product be 0.18%, thereby obtaining an additive composition.

[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 mass content of water in the product is 0.7%, thereby obtaining an additive composition.

[0109] The polyamide composition of the present invention will be described in detail below by taking application examples as examples, but the polyamide composition is 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, Comparative Application Example 1-8

[0113] A polyamide composition, the types and amounts of the components are shown in Table 2 and Table 3, the amount units of the components are all "parts by mass"; "--" means that the component is not added.

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

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

[0116] (1) Flame retardancy: The sample to be tested was made into a 125 mm × 13 mm × 1.6 mm strip by injection molding and tested according to the ANSI / UL-94-1985 standard. “t1+t2” represents the afterflame time in seconds.

[0117] (2) Flame retardant properties after high temperature and high humidity aging: The sample to be tested was made into a 125 mm × 13 mm × 1.6 mm specimen by injection molding, placed in a damp heat aging chamber, aged for 168 h at 85°C and 85% humidity, and then taken out and tested for flame retardant properties according to the method in (1);

[0118] (3) Precipitation: The sample to be tested is made into a 125 mm × 13 mm × 1.6 mm specimen by injection molding, and placed in a wet heat aging chamber. After aging for 168 h at 85°C and 85% humidity, the precipitation on the surface of the specimen is visually observed. If there are many (>5) white spots of precipitation visible to the naked eye on each specimen, it is obvious precipitation; if there are few (1-5) white spots of precipitation, it is a small amount of precipitation; if it is not visible to the naked eye, the precipitation observed by electron microscope at a magnification of 200-1000 times is trace precipitation, and no precipitation is observed.

[0119] (4) Flexural strength: The flexural 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 box at 85°C and 85% humidity for 168 h;

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

[0121] Table 2

[0122]

[0123] Table 3

[0124]

[0125] It can be seen from the performance data in Table 2 that the additive composition provided by the present invention has excellent flame retardant properties, stability and anti-precipitation properties through the design and synergistic compounding of each component and the control of a specific water content. The additive composition is used for flame retardant modification of polyamide, so that the polyamide composition achieves V-0 flame retardancy, and still maintains V-0 flame retardancy after 168 h of wet heat aging under double 85 conditions, and the additive has no precipitation or only a trace precipitation.

[0126] Comparing the data in Table 2 and Table 3, it can be seen that the water content in the 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 wet heat aging, and precipitation of the additive; the water content in the additive composition in comparative application examples 2 and 8 is too high, which not only leads to obvious deterioration of the flame retardancy and precipitation of the additive in the polyamide composition after wet heat aging, but also deterioration of the mechanical properties. The additive compositions D3-D6 in comparative application examples 3-6 do not contain the composite system of the components and specific amounts defined in the present invention, resulting in a significant decrease in one or more of its flame retardancy, stability, and precipitation resistance. It is used for flame retardant modification of polyamide materials, resulting in a significant decrease in the flame retardancy of the polyamide composition after wet heat aging, and an increase in the precipitation amount.

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

Claims

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

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

3. The additive composition according to claim 1, characterized in that The additive composition further comprises 0.1-3 parts by mass of ethylbutyl aluminum phosphinate; And / or, the additive composition further comprises 0.01-0.8 parts by mass of aluminum monoethylphosphinate.

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

5. Use of the additive composition according to any one of claims 1 to 4 in polymer materials.

6. A polyamide composition, characterized in that The polyamide composition comprises polyamide and the additive composition according to any one of claims 1 to 4.

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

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

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

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