A polymer additive, its preparation method and use

Abstract

The present application provides a kind of polymer additive and its preparation method and application, the polymer additive includes diethyl aluminum phosphinate, the particle size of the polymer additive meets the following relationship: 1.1≤100×(D 75 ‑D 25 ) / (D 50 ) 2 ≤1.8;0.5≤(D 97 ×D 50 ) / (D 10 ×100)≤2.0;The D 50 Particle size of the polymer additive is 25-50 μm.The present application is by designing its particle size distribution meets the relationship of formula I and formula II, it has specific particle size distribution parameters, realizes the uniform dispersion of polymer additive in polymer system, makes the apparent defect such as no color spot, white spot of the polymer composition containing it, greatly improves the quality of flame-retardant polymer product.

Description

Technical Field

[0001] This invention belongs to the field of polymer additive technology, specifically relating to a polymer additive, its preparation method, and its application. Background Technology

[0002] Flame retardants can prevent or delay the combustion of polymer materials and are important additives used in polymer materials. With increasing environmental awareness, flame retardants, while possessing flame-retardant properties, must also meet the development trends of environmental protection and ecological safety. Against this backdrop, some traditional halogen-containing flame retardants have gradually withdrawn from the market. Organophosphorus flame retardants, as halogen-free and environmentally friendly flame retardants, have high flame-retardant efficiency, low toxicity, low corrosiveness, and good compatibility, making them a research hotspot in recent years.

[0003] Alkylphosphonates are a novel type of organophosphorus flame retardant with excellent flame retardant properties, low smoke density, high CTI (tracking index), and environmental friendliness. They have minimal impact on the physical and electrical properties of the base polymer and are widely used in polyamide, polyester, and polyurethane material systems to impart high mechanical and electrical properties to flame-retardant polymer products containing them. However, with the widespread use of alkylphosphonates, it has been gradually discovered that these flame retardants have poor dispersion properties in polymer systems, are difficult to shear disperse, or are prone to agglomeration, leading to problems such as easy precipitation of the flame retardant, decreased mechanical properties, and surface defects in the products.

[0004] To improve the dispersibility of alkylphosphinates, the main method in the industry is to add other additives for modification. For example, CN118240373A discloses a flame-retardant PA10T material, the raw materials of which include: 100 parts by weight of PA10T, 5-50 parts by weight of modified flame retardant, 1-20 parts by weight of additives, and 0-100 parts by weight of filler; the modified flame retardant is diethylaluminum hypophosphite and magnesium hydroxide modified with long-chain amides with 8-12 carbon atoms. Because long-chain amides with good compatibility with PA10T are used as surface modifiers, the modified flame retardant is less prone to agglomeration and is easier to disperse in the matrix, reducing the agglomeration of raw materials. CN115353732A discloses a flame retardant composition for PA10T, comprising 5-50 parts by weight of melamine polyphosphate, 5-70 parts by weight of aluminum diethylphosphite, and 5-20 parts by weight of chitosan oligosaccharide. Melamine polyphosphate synergistically retards with aluminum diethylphosphite, and the addition of chitosan oligosaccharide promotes the dispersion of the flame retardant in PA10T, allowing it to better exert its synergistic flame retardant effect. CN111961340A discloses a halogen-free flame-retardant bio-based nylon 56 composite material, comprising 50-75 parts of bio-based PA56, 0.1-1 parts of antioxidant, 0.1-1 parts of lubricant, 15-20 parts of halogen-free flame retardant, 10-30 parts of reinforcing material, and 0.3-0.8 parts of flow dispersant. The halogen-free flame retardant is aluminum diethylphosphite, and the flow dispersant is CF-201 micro powder, a flow modifier specifically for nylon, which improves the dispersion and precipitation of aluminum diethylphosphite.

[0005] Although the addition of modifying and dispersing agents can improve the dispersibility of alkyl phosphinates to some extent, the types of agents need to be adjusted according to the polymer matrix and other components. That is, different types of agents need to be selected for different product formulations, which is difficult in practical applications. Moreover, the addition of agents usually causes varying degrees of decline in the mechanical properties and stability of polymer products. The agent modification scheme does not fundamentally solve the problem of poor dispersion of alkyl phosphinates in the polymer matrix.

[0006] Therefore, how to fundamentally solve the dispersibility problem of alkylphosphinates and how to improve the appearance defects of polymer products using them are the focus of research in this field. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the present invention aims to provide a polymer additive, its preparation method and application. The polymer additive has specific particle size distribution parameters to achieve uniform dispersion in the polymer system, so that the polymer composition containing it is free from appearance defects such as discoloration spots, and greatly improves the quality of flame retardant polymer products.

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

[0009] In a first aspect, the present invention provides a polymer additive comprising aluminum diethylphosphinate, wherein the particle size of the polymer additive satisfies the relationship shown in Formulas I and II:

[0010] 1.1≤100×(D 75 - D 25 ) / (D 50 ) 2 ≤1.8 Formula I;

[0011] 0.5≤(D 97 ×D 50 ) / (D 10 (×100)≤2.0 Equation II;

[0012] Among them, D 10 D 25 D 50 D 75 D 97 The particle sizes represent the particle sizes corresponding to a cumulative volume distribution percentage of 10%, 25%, 50%, 75%, and 97% for the polymer additive, respectively.

[0013] The polymer additive's D 50 The particle size is 25-50μm.

[0014] This invention has found that excessively fine particle size in flame retardants can easily lead to agglomeration, while excessively large particle size makes it difficult for large particles to be sheared and dispersed, resulting in uneven dispersion in polymer applications. This can cause problems such as white discoloration spots (i.e., undispersed flame retardants) or precipitation in polymer products. Therefore, the polymer additive provided by this invention has a particle size distribution that satisfies the relationship between Formulas I and II. It possesses specific particle size distribution parameters, enabling uniform dispersion in the polymer system. This ensures that the polymer composition containing it is free of discoloration spots (white spots) and other appearance defects, significantly improving the quality of flame-retardant polymer products.

[0015] Specifically, Formula I of this invention reflects the overall particle width of the polymer additive, while Formula II balances extreme particles and takes into account the influence of middle and tail particles, solving the problem of neglecting the tail distribution in traditional particle size distribution parameters. By combining Formulas I and II, this invention defines the distribution characteristics of the polymer additive particle system from multiple dimensions, reducing extreme particles and thereby controlling the uniformity, stability, and functionality of the particles. This increases the particle packing density, facilitates dispersion, improves flowability, helps reduce processing safety hazards, and avoids surface defects in the polymer composition caused by additive inhomogeneity and the resulting adverse effects on mechanical properties.

[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] It should be noted that the polymer additives of the present invention include aluminum diethylphosphinate, and optionally also include trace amounts of aluminum ethylbutylphosphinate, and optionally trace amounts of aluminum ethyl phosphite, etc.

[0018] In this invention, the D of the polymer additive 10 D 25 D 50 D 75 D 97 The particle size distribution can be determined using a laser particle size analyzer by referring to the standard GB / T19077-2016, Laser Diffraction Method. For example, the determination method is a wet method using water as the dispersion medium.

[0019] In formula I, 1.1 ≤ 100 × (D 75 -D 25 ) / (D 50 ) 2 ≤1.8, 100×(D) 75 -D 25 ) / (D 50 ) 2 The values ​​can be 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, or 1.75, as well as specific values ​​between these 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. Preferably, 1.2 ≤ 100 × (D) 75 -D 25 ) / (D 50 ) 2 ≤1.7.

[0020] In Equation II, 0.5 ≤ (D 97 ×D 50 ) / (D 10 (×100)≤2.0,(D) 97 ×D 50 ) / (D 10 (×100) can be 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.95, or 1.98, as well as specific point values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range. Preferably, 0.8 ≤ (D 97 ×D 50 ) / (D10 (×100)≤1.55.

[0021] The polymer additive's D 50 The particle size is 25-50μm, for example, it can be 26μm, 28μm, 30μm, 32μm, 35μm, 38μm, 40μm, 42μm, 45μm or 48μm, 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.

[0022] Preferably, the D of the polymer additive 25 The particle size is 20-40μm, for example, it can be 22μm, 24μm, 25μm, 28μm, 30μm, 32μm, 35μm or 38μm, 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, and 21-30μm is further preferred.

[0023] And / or, preferably, the D of the polymer additive 75 The particle size is 30-70μm, for example, it can be 32μm, 35μm, 38μm, 40μm, 42μm, 45μm, 48μm, 50μm, 52μm, 55μm, 58μm, 60μm, 62μm, 65μm or 68μm, 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, and 35-60μm is further preferred.

[0024] Preferably, the D of the polymer additive 10 The particle size is 10-25μm, for example, it can be 12μm, 15μm, 18μm, 20μm, 22μm or 24μm, 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, and 15-20μm is further preferred.

[0025] And / or, preferably, the D of the polymer additive 97 The particle size is 40-90μm, for example, it can be 42μm, 45μm, 48μm, 50μm, 52μm, 55μm, 58μm, 60μm, 62μm, 65μm, 68μm, 70μm, 72μm, 75μm, 78μm, 80μm, 82μm, 85μm or 88μm, 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, and 45-80μm is further preferred.

[0026] Preferably, the molar percentage of aluminum diethylphosphinic acid in the polymer additive is ≥90%, for example, it can be 91%, 92%, 94%, 95%, 96%, 98%, 99%, 99.5%, 99.7%, 99.8%, 99.9%, 99.99%, or 100%, 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 93-99.7% is further preferred.

[0027] Preferably, the polymer additive further includes aluminum ethyl butylphosphinate and / or aluminum ethyl phosphite.

[0028] Preferably, the molar percentage of aluminum ethyl butylphosphinate in the polymer additive is ≤4%, for example, it can be 0, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, or 3.5%, 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, and it is further preferred to be ≤3%.

[0029] Preferably, the molar percentage of aluminum ethylphosphonite in the polymer additive is ≤1%, for example, it can be 0, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, or 0.9%, 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 it is further preferred to be ≤0.7%.

[0030] In this invention, the structure of aluminum diethylphosphinate is as follows: The structure of aluminum ethyl butylphosphinate is as follows: The structure of aluminum ethylphosphonite is

[0031]

[0032] It should be noted that the polymer additive may also include other homologues, such as any one or a combination of at least two of aluminum dibutylphosphinate, aluminum ethylhexylphosphinate, aluminum dihexylphosphinate, etc.

[0033] Preferably, the sum of the molar contents of aluminum diethylphosphinate, aluminum ethylbutylphosphinate (if any), and aluminum ethylphosphite (if any) in the polymer additive is ≥99.5%, for example, it can be 99.55%, 99.6%, 99.65%, 99.7%, 99.75%, 99.8%, 99.85%, 99.9%, 99.95%, 99.99%, or 100%.

[0034] In a second aspect, the present invention provides a method for preparing a polymer additive as described in the first aspect, the method comprising:

[0035] A dispersion solution is provided, the dispersion solution comprising a combination of water and a soluble flocculant;

[0036] The polymer additive is obtained by metathesis reaction of soluble diethylphosphonate and soluble aluminum salt in the presence of the dispersion solution using a continuous salt-forming process.

[0037] In the preparation method of the polymer additive provided by the present invention, the metathesis reaction of soluble diethylphosphonate and soluble aluminum salt is carried out in the presence of a soluble flocculant. The addition of the soluble flocculant can control the particle distribution, so that the formed polymer additive is not too large or too small, and the crystallization process of the product is more compact and the particle distribution is more uniform, thereby achieving a polymer additive with specific particle size parameters of Formula I and Formula II.

[0038] Preferably, the soluble flocculant includes polyaluminum sulfate and / or polyaluminum chloride.

[0039] Preferably, the mass ratio of water to soluble flocculant in the dispersion solution is 1:(0.002-0.01), for example, it can be 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, etc.

[0040] Preferably, the soluble diethylphosphonate includes any one or a combination of at least two of sodium diethylphosphonate, potassium diethylphosphonate, and ammonium diethylphosphonate, more preferably sodium diethylphosphonate.

[0041] Preferably, the soluble aluminum salt includes aluminum sulfate and / or aluminum sulfate hydrate.

[0042] Preferably, the molar ratio of the soluble aluminum salt to the soluble diethylphosphonate is 1:(5.8-6.2), for example, it can be 1:5.82, 1:5.85, 1:5.88, 1:59, 1:5.92, 1:5.95, 1:5.98, 1:6, 1:6.02, 1:6.05, 1:6.08, 1:6.1, 1:6.12, 1:6.15, or 1:6.18, etc.

[0043] Preferably, the preparation method employs a continuous salt formation method, which includes the following steps:

[0044] The dispersion solution is placed in a reaction apparatus, and then a soluble diethylphosphonate aqueous solution and a soluble aluminum salt aqueous solution are simultaneously and continuously injected into the reaction apparatus to carry out a metathesis reaction, thereby obtaining the polymer additive.

[0045] Preferably, the mass ratio of the soluble diethylphosphonate aqueous solution to the soluble flocculant in the dispersion solution is 1:(0.0001-0.002), for example, it can be 1:0.0002, 1:0.0004, 1:0.0005, 1:0.0008, 1:0.0001, 1:0.0011, 1:0.0012, 1:0.0013, 1:0.0014, 1:0.0015, 1:0.0016, 1:0.0017, 1:0.0018, or 1:0.0019, etc.

[0046] Preferably, the concentration of soluble diethylphosphonic acid salt in the aqueous solution of soluble diethylphosphonic acid salt is 1-2 mol / kg, for example, it can be 1.1 mol / kg, 1.2 mol / kg, 1.3 mol / kg, 1.4 mol / kg, 1.5 mol / kg, 1.6 mol / kg, 1.7 mol / kg, 1.8 mol / kg or 1.9 mol / kg, 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.

[0047] Preferably, the concentration of the soluble aluminum salt in the aqueous solution is 0.3-0.6 mol / kg, for example, it can be 0.32 mol / kg, 0.35 mol / kg, 0.38 mol / kg, 0.4 mol / kg, 0.42 mol / kg, 0.45 mol / kg, 0.48 mol / kg, 0.5 mol / kg, 0.52 mol / kg, 0.55 mol / kg or 0.58 mol / kg, 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.

[0048] Preferably, the soluble aluminum salt includes aluminum sulfate and / or aluminum sulfate hydrate, and the feed molar ratio of the soluble aluminum salt to the soluble diethylphosphonate is 1:(5.8-6.2), for example, it can be 1:5.82, 1:5.85, 1:5.88, 1:59, 1:5.92, 1:5.95, 1:5.98, 1:6, 1:6.02, 1:6.05, 1:6.08, 1:6.1, 1:6.12, 1:6.15 or 1:6.18, etc., and more preferably 1:(5.9-6.1).

[0049] Preferably, the temperature of the metathesis reaction is 20-90℃, for example, it can be 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃ or 85℃, 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, but 40-85℃ is further preferred.

[0050] Preferably, the metathesis reaction method includes: simultaneously and continuously feeding a soluble diethylphosphonate aqueous solution and a soluble aluminum salt aqueous solution into a first-stage reaction, followed by a second-stage feeding and a second-stage reaction to obtain the polymer additive.

[0051] As a preferred embodiment of the present invention, a soluble diethylphosphonate aqueous solution and a soluble aluminum salt aqueous solution are first fed simultaneously and continuously in a first stage and kept at a certain temperature for a period of time to form pre-formed particles. During this stage, the presence of a soluble flocculant controls the distribution of the pre-formed particles. Then, a second stage of simultaneous and continuous feeding of the soluble diethylphosphonate aqueous solution and the soluble aluminum salt aqueous solution is carried out for a metathesis salt formation reaction. The presence of the soluble flocculant helps to prevent the particles formed in the subsequent reaction from being too large or too small, resulting in a more compact crystallization process and a more uniform particle distribution, thereby achieving the polymer additive that meets specific particle size parameters.

[0052] Preferably, the feeding time is 5-30 min, for example, it can be 6 min, 8 min, 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min or 28 min, 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, and 10-20 min is further preferred.

[0053] Preferably, the temperature of the first stage of the reaction is 20-90℃, for example, it can be 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃ or 85℃, 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, but 40-85℃ is further preferred.

[0054] Preferably, the reaction time is 10-60 min, for example, it can be 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min or 55 min, 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 20-40 min is further preferred.

[0055] Preferably, the feeding time for the two stages is 1-3 hours, for example, it can be 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours or 2.8 hours, 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.

[0056] Preferably, the temperature of the two-stage reaction is 20-90℃, for example, it can be 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃ or 85℃, 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, but 40-85℃ is further preferred.

[0057] Preferably, the residence time of the two-stage reaction is 10-50 min, for example, it can be 12 min, 15 min, 18 min, 20 min, 22 min, 25 min, 28 min, 30 min, 32 min, 35 min, 38 min, 40 min, 42 min, 45 min or 48 min, 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 20-40 min is further preferred.

[0058] In this invention, whether it is a single-stage or two-stage feed, the soluble diethylphosphonate aqueous solution and the soluble aluminum salt aqueous solution are added to the reaction device simultaneously and continuously, and the feed molar ratio of soluble aluminum salt to soluble diethylphosphonate is 1:(5.8-6.2).

[0059] It is understood that the preparation method of the present invention adopts a continuous salt formation process. First, all the dispersion solution is added to the reaction device. Then, the soluble diethylphosphonate aqueous solution and the soluble aluminum salt aqueous solution are fed simultaneously and continuously for 5-30 minutes, and the reaction is carried out at 20-90°C for 10-60 minutes. Then, the diethylphosphonate aqueous solution and the soluble aluminum salt aqueous solution are fed simultaneously and continuously for 1-3 hours and a two-stage reaction is carried out. During this stage, the residence time of the liquid in the reaction device is 10-50 minutes. The liquid is then discharged to obtain a slurry containing the polymer additive.

[0060] Preferably, the metathesis reaction further includes a post-processing step, which includes filtration, washing, and drying.

[0061] Preferably, the washing process includes water.

[0062] Preferably, the number of washing cycles is 1-5 times, for example, 2 times, 3 times, 4 times, etc.

[0063] Preferably, the drying temperature is 120-200℃, for example, it can be 130℃, 140℃, 150℃, 160℃, 170℃, 180℃ or 190℃, 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.

[0064] It should be noted that the preparation of the polymer additive described in the first aspect is not limited to the preparation method provided in the second aspect of the present invention. Those skilled in the art can also select other methods or routes to obtain the polymer additive proposed in the present invention. For example, aluminum diethylphosphinate particles (particle size distribution of aluminum diethylphosphinate particles that does not meet the requirements of the present invention) can be sieved to obtain the polymer additive with specific particle size distribution parameters.

[0065] Preferably, the sieving device includes an air classifier, and more preferably a two-stage air classifier.

[0066] Thirdly, the present invention provides the application of the polymer additive as described in the first aspect in polymer materials.

[0067] Preferably, the polymer additive is used as a flame retardant in the polymer material.

[0068] Preferably, the polymer material includes general-purpose plastics, general-purpose engineering plastics, special engineering plastics, or elastomers.

[0069] Fourthly, the present invention provides a polymer composition comprising a polymer matrix and polymer additives as described in the first aspect.

[0070] Preferably, the polymer composition comprises, by weight, the following components:

[0071] 40-99 parts of polymer matrix

[0072] The polymer additive is 2-35 parts.

[0073] Preferably, the polymer matrix has a mass fraction of 40-99 parts, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 98 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.

[0074] Preferably, the polymer additive is in the range of 2-35 parts by weight, for example, 4 parts, 5 parts, 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 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.

[0075] Preferably, the polymer matrix comprises any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyolefin, and polyacrylate.

[0076] Preferably, the polyamide includes any one or a combination of at least two of polyamide resin and polyamide elastomer.

[0077] 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.

[0078] For example, 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), and polyamide 10T (polydecyl terephthalamide).

[0079] For example, the polyamide elastomer includes hard segments from polyamide and soft segments from polyols, the polyols including polyether polyols and / or polyester polyols, preferably polyether polyols.

[0080] Preferably, the polyester comprises a condensation product of a dicarboxylic acid and / or its derivatives with a diol, wherein the dicarboxylic acid includes, but is not limited to, any one or a combination of at least two of the following: terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, and hydrogenated phthalic acid; and the derivatives include acyl halides (acyl chlorides), esters, and anhydrides formed from the dicarboxylic acid. The diol includes, but is not limited to, any one or a combination of at least two of the following: ethylene glycol, butanediol, and hexanediol.

[0081] For example, the polyester includes polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

[0082] Preferably, the polyurethane comprises polyurethane resin and / or polyurethane elastomer.

[0083] Preferably, the polyurethane comprises the reaction product of a polyol and an isocyanate, wherein the polyol is exemplary, including but not limited to, any one or a combination of at least two of polyether polyols, polyester polyols, polylactone polyols, and polycarbonate polyols.

[0084] Preferably, the styrene-based polymer includes any one or a combination of at least two of styrene homopolymer (PS), styrene-acrylate copolymer, styrene-olefin copolymer, and styrene-olefin-acrylonitrile copolymer; the styrene-olefin copolymer includes, but is not limited to, any one or a combination of at least two of styrene-(ethylene-propylene) diblock copolymer, styrene-(ethylene-butene)-ethylene triblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene-styrene triblock copolymer, and styrene-ethylene-isoprene terpolymer.

[0085] Preferably, the polyolefin includes any one or a combination of at least two of polyethylene, α-olefin homopolymer, α-olefin copolymer, ethylene-α-olefin copolymer, and ethylene-α-olefin-diolefin copolymer; wherein the α-olefin is exemplary including, but not limited to, any one or a combination of at least two of propylene, butene, pentene, hexene, heptene, and octene; and the diolefin is exemplary including, but not limited to, any one or a combination of at least two of butadiene, isoprene, and hexadiene.

[0086] It should be noted that the polymer composition of the present invention may also include any other additives that are motivated to be added in the art.

[0087] Preferably, the polymer composition further comprises 0-45 parts by weight of reinforcing material, wherein the parts by weight of the reinforcing material can be 0, 0.5, 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 42, or 44, 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.

[0088] Preferably, the reinforcing material comprises glass fiber and / or carbon fiber.

[0089] Preferably, the polymer composition further comprises 0-40 parts of filler by weight, wherein the parts of filler by weight can be 0, 0.5, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, or 38 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.

[0090] Preferably, the filler comprises any one or a combination of at least two of the following: silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass microspheres.

[0091] Preferably, the polymer composition further includes 0-15 parts by weight of other additives, wherein the parts by weight of the other additives may be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14, 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.

[0092] Preferably, the other additives include any one or a combination of at least two of antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, and colorants.

[0093] Preferably, the mass fractions of the antioxidant, ultraviolet absorber, lubricant, and nucleating agent in the polymer composition are each 0.01-2 parts, for example, 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, 0.9 parts, 1 part, 1.2 parts, 1.5 parts, or 1.8 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.

[0094] In a preferred embodiment, the polymer composition comprises the following components in parts by weight:

[0095] 40-99 parts of polymer matrix

[0096] 2-35 parts of the polymer additive

[0097] 0-45 parts of reinforcing material.

[0098] Preferably, the polymer matrix in the polymer composition has a mass percentage content of 40%-99%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%, and 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.

[0099] The polymer additive has a flame-retardant effect. Preferably, the polymer additive in the polymer composition has a mass percentage of 2%-35%, for example, 4%, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, or 34%, 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. More preferably, it is 6%-20%.

[0100] For example, the method for preparing the polymer composition includes: melting and blending the components of the polymer composition and then extruding them to obtain the polymer composition.

[0101] Preferably, the polymer matrix, polymer additives, optional reinforcing materials, optional fillers, and optional other auxiliaries are first premixed to obtain a premix; then the premix is ​​melt-blended and extruded to obtain the polymer composition.

[0102] Preferably, the melt blending is carried out in a screw extruder.

[0103] Preferably, the screw extruder is a twin-screw extruder.

[0104] Preferably, the temperature of the screw extruder is 180-340℃, 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.

[0105] Preferably, the extrusion process further includes granulation and drying steps.

[0106] Compared with the prior art, the present invention has the following beneficial effects:

[0107] The polymer additive provided by this invention has a particle size distribution that satisfies the relationship between Formula I and Formula II. It has specific particle size distribution parameters, which realizes the uniform dispersion of the polymer additive in the polymer system. This makes the polymer composition containing it free from appearance defects such as discoloration spots and white spots, and greatly improves the quality of flame-retardant polymer products. Detailed Implementation

[0108] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0109] 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.

[0110] The polymer additives and their preparation methods described in this invention will be detailed below using several examples, but the polymer additives and their preparation methods are not limited to these examples.

[0111] In the following specific embodiments, the D of the polymer additive 10 D 25 D 50 D 75 D 97 Particle size data were obtained according to the standard GB / T19077-2016 Particle Size Distribution Laser Diffraction Method, using a laser particle size analyzer (model LS-609, Omec). The specific method is as follows: Wet method test: Take 0.2g of the sample to be tested, add 2mL of ethanol to wet the sample, then add 10g of water, and disperse under ultrasonic assistance for 2min to obtain a dispersion; The dispersion is tested by the laser particle size analyzer, with the instrument parameters set as follows: sample refractive index 1.6, dispersion medium refractive index 1.33, and occlusion 10%.

[0112] The contents of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, and aluminum ethylphosphite in the polymer additive were determined by phosphorus nuclear magnetic resonance (P-NMR) spectroscopy. The specific method included using a Bruker AVANCENEO 400MHz NMR spectrometer. The sample was digested into a liquid state using a deuterated sodium hydroxide aqueous solution, with an addition ratio of 10 mg / g. The NMR frequency was 160 MHz, and the number of scans was 1024. The peak positions of different components were determined from the NMR results, and the mass content of each component was calculated by integration.

[0113] Example 1

[0114] A polymer additive A1 is prepared by the following method:

[0115] (1) Preparation of dispersion solution: Add 1 / 5 of the container volume of deionized water to the bottom of the reaction vessel, add polyaluminum sulfate to it, so that the mass ratio of deionized water to polyaluminum sulfate is 1:0.01, mix evenly to obtain dispersion solution;

[0116] (2) Prepare a sodium diethylphosphonate aqueous solution with a concentration of 1.5 mol / kg and an aluminum sulfate aqueous solution with a concentration of 0.45 mol / kg. Using a continuous salt formation method, start stirring and simultaneously and continuously inject the sodium diethylphosphonate aqueous solution and the aluminum sulfate aqueous solution into the reaction vessel containing the dispersion solution. After feeding for 15 min, keep the temperature at 60℃ for 30 min. Then simultaneously and continuously inject the sodium diethylphosphonate aqueous solution and the aluminum sulfate aqueous solution and react. The feeding time is 2 h and the reaction residence time is 20 min to obtain a slurry. The temperature is controlled at 60℃ throughout the reaction process. The feed molar ratio of aluminum sulfate to sodium diethylphosphonate is 1:6. The mass ratio of sodium diethylphosphonate aqueous solution to polyaluminum sulfate in the dispersion solution is 1:0.0015.

[0117] The slurry was heated to 80°C and held for 5 minutes. The slurry was filtered, washed three times with three times the amount of water, and dried at 150°C to obtain the polymer additive A1, which contains 2.62 mol% of aluminum ethyl butyl phosphonate and 0.49 mol% of aluminum ethyl phosphonite. The particle size-related parameters are shown in Table 1.

[0118] Example 2

[0119] A polymer additive A2 is prepared in a manner that differs from that of Example 1 only in that the mass of polyaluminum sulfate in step (1) is adjusted so that the mass ratio of deionized water to polyaluminum sulfate in the dispersion solution is 1:0.008; the mass ratio of sodium diethylphosphonate aqueous solution to polyaluminum sulfate in the dispersion solution is 1:0.0012. The amounts of other materials, process steps and parameters are the same as in Example 1. Polymer additive A2 is obtained, which contains 2.95 mol% of ethylbutylphosphonate aluminum and 0.21 mol% of ethylphosphonite aluminum. The particle size-related parameters are shown in Table 1.

[0120] Example 3

[0121] A polymer additive A3 is prepared in a method that differs from that of Example 1 only in that the mass of polyaluminum sulfate in step (1) is adjusted so that the mass ratio of deionized water to polyaluminum sulfate in the dispersion solution is 1:0.006; the mass ratio of sodium diethylphosphonate aqueous solution to polyaluminum sulfate in the dispersion solution is 1:0.0009; and the amounts of other materials, process steps and parameters are the same as in Example 1. Polymer additive A3 is obtained, which contains 2.78 mol% of ethylbutylphosphonate aluminum and 0.43 mol% of ethylphosphonite aluminum; the particle size-related parameters are shown in Table 1.

[0122] Example 4

[0123] A polymer additive A4 is prepared in a method that differs from that of Example 1 only in that the mass of polyaluminum sulfate in step (1) is adjusted so that the mass ratio of deionized water to polyaluminum sulfate in the dispersion solution is 1:0.004; the mass ratio of sodium diethylphosphonate aqueous solution to polyaluminum sulfate in the dispersion solution is 1:0.0006; and the amounts of other materials, process steps and parameters are the same as in Example 1. Polymer additive A4 is obtained, which contains 2.86 mol% of ethylbutylphosphonate aluminum and 0.34 mol% of ethylphosphonite aluminum; the particle size-related parameters are shown in Table 1.

[0124] Example 5

[0125] A polymer additive A5 is prepared in a method that differs from that of Example 1 only in that the mass of polyaluminum sulfate in step (1) is adjusted so that the mass ratio of deionized water to polyaluminum sulfate in the dispersion solution is 1:0.002; the mass ratio of sodium diethylphosphonate aqueous solution to polyaluminum sulfate in the dispersion solution is 1:0.0003. The amounts of other materials, process steps and parameters are the same as in Example 1. Polymer additive A5 is obtained, which contains 2.58 mol% of ethylbutylphosphonate aluminum and 0.57 mol% of ethylphosphonite aluminum. The particle size-related parameters are shown in Table 1.

[0126] Example 6

[0127] A polymer additive A6 is prepared in a method that differs from that of Example 1 only in that the flocculant in step (1) is adjusted to be polyaluminum chloride, while the dosage of other materials, process steps and parameters are the same as in Example 1, to obtain polymer additive A6, which contains 2.86 mol% of aluminum ethyl butyl phosphonate and 0.36 mol% of aluminum ethyl phosphonite; the particle size-related parameters are shown in Table 1.

[0128] Example 7

[0129] A polymer additive A7 is prepared in a method that differs from that of Example 1 only in that the concentration of sodium diethylphosphite aqueous solution in step (2) is adjusted to 1.2 mol / kg. The dosage of other materials, process steps and parameters are the same as those in Example 1. The polymer additive A7 is obtained, which contains 2.9 mol% of aluminum ethyl butylphosphite and 0.34 mol% of aluminum ethyl phosphite. The particle size-related parameters are shown in Table 1.

[0130] Example 8

[0131] A polymer additive A8 is prepared in a method that differs from that of Example 1 only in that the concentration of aluminum sulfate aqueous solution in step (2) is adjusted to 0.35 mol / kg. The dosage of other materials, process steps and parameters are the same as those in Example 1. The polymer additive A8 is obtained, which contains 2.42 mol% of ethyl butyl phosphite aluminum and 0.64 mol% of ethyl phosphite aluminum. The particle size-related parameters are shown in Table 1.

[0132] Example 9

[0133] A polymer additive A9 is prepared differently from that in Example 1 in step (2), as follows:

[0134] A sodium diethylphosphonate aqueous solution with a concentration of 1.5 mol / kg and an aluminum sulfate aqueous solution with a concentration of 0.45 mol / kg were prepared. A continuous salt-forming method was used, with stirring started. The sodium diethylphosphonate aqueous solution and the aluminum sulfate aqueous solution were simultaneously and continuously injected into the reaction vessel containing the dispersion solutions. The feeding was direct and continuous for 2 hours, and the reaction residence time was 20 minutes, after which a slurry was obtained. The temperature was controlled at 60℃ throughout the reaction process, and the molar ratio of aluminum sulfate to sodium diethylphosphonate was 1:6. The mass ratio of the sodium diethylphosphonate aqueous solution to the polyaluminum sulfate in the dispersion solution was 1:0.0015.

[0135] The slurry was heated to 80°C and held for 5 minutes. The slurry was filtered, washed three times with three times the amount of water, and dried at 150°C to obtain the polymer additive A9, which contains 2.37 mol% aluminum ethyl butyl phosphonate and 0.60 mol% aluminum ethyl phosphonite. The particle size-related parameters are shown in Table 1.

[0136] Comparative Example 1

[0137] A polymer additive D1 is prepared in a method that differs from that in Example 1 in step (2), as follows:

[0138] A 1.5 mol / kg aqueous solution of sodium diethylphosphonate and a 0.45 mol / kg aqueous solution of aluminum sulfate were prepared. Using an intermittent salt-forming method, 1 mol of the sodium diethylphosphonate aqueous solution was directly added to the reaction vessel, followed by a trace amount of polyaluminum sulfate, to achieve a mass ratio of 1:0.0015 between the sodium diethylphosphonate aqueous solution and the polyaluminum sulfate in the dispersion. Stirring was started, and the prepared aluminum sulfate solution was continuously and constantly fed into the reaction vessel to allow the reaction to proceed. The temperature of the reaction vessel was controlled at 60°C during the feeding period, and the feeding time was 2.5 h, ultimately achieving a total molar ratio of aluminum sulfate to sodium diethylphosphonate of 1:6. After feeding, a slurry was obtained. The slurry was heated to 80°C and held for 5 min. The slurry was filtered, washed three times with three times the amount of water, and dried at 150°C to obtain the polymer additive D1, which contains 2.73 mol% ethylbutylaluminum phosphonate and 0.39 mol% ethylaluminum phosphonite. Particle size-related parameters are shown in Table 1.

[0139] Example 10

[0140] A polymer additive A10 is prepared as follows: Polymer additive A1 provided in Example 1 and polymer additive D1 provided in Comparative Example 1 are mixed at a mass ratio of 1:1 and then processed using a two-stage air classifier. The rotation speed of the first stage is 3000 rpm and the time is 30 min; the rotation speed of the second stage is 5000 rpm and the time is 60 min. Ultrafine powder and coarse particles are removed step by step to obtain polymer additive A10. The particle size-related parameters are shown in Table 1.

[0141] Comparative Example 2

[0142] A polymer additive D2 is prepared as follows:

[0143] (1) Add 1 / 5 of the container volume of deionized water to the bottom of the reaction vessel;

[0144] (2) Prepare a sodium diethylphosphonate aqueous solution with a concentration of 1.5 mol / kg and an aluminum sulfate aqueous solution with a concentration of 0.45 mol / kg; using a continuous salt formation method, simultaneously and continuously inject the sodium diethylphosphonate aqueous solution and the aluminum sulfate aqueous solution into a reaction vessel containing deionized water, with a feeding time of 2.5 h, to obtain a slurry; the temperature is controlled at 60℃ throughout the reaction process, and the feed molar ratio of aluminum sulfate to sodium diethylphosphonate is 1:6;

[0145] The slurry was heated to 80°C and held for 5 minutes. The slurry was filtered, washed three times with three times the amount of water, and dried at 150°C to obtain the polymer additive D2, which contains 2.69 mol% of aluminum ethyl butyl phosphonate and 0.42 mol% of aluminum ethyl phosphonite. The particle size-related parameters are shown in Table 1.

[0146] Comparative Example 3

[0147] A polymer additive D3 was prepared in a method that differed from Comparative Example 2 only in that the temperature was controlled at 30°C during the reaction process. The amount of materials, process steps, and other parameters were the same as those in Comparative Example 2. The polymer additive D3 contained 2.46 mol% of aluminum ethyl butyl phosphite and 0.68 mol% of aluminum ethyl phosphite. The particle size-related parameters are shown in Table 1.

[0148] Comparative Example 4

[0149] A polymer additive D4 is prepared as follows:

[0150] (1) Add 1 / 5 of the container volume of deionized water to the bottom of the reaction vessel;

[0151] (2) Prepare a sodium diethylphosphonate aqueous solution with a concentration of 1.5 mol / kg and an aluminum sulfate aqueous solution with a concentration of 0.45 mol / kg. Using a continuous salt formation method, sodium diethylphosphonate aqueous solution and aluminum sulfate aqueous solution are simultaneously and continuously injected into a reaction vessel containing deionized water. After feeding for 15 min, the reaction is kept at 60℃ for 20 min. Then, sodium diethylphosphonate aqueous solution and aluminum sulfate aqueous solution are continuously injected and reacted. The feeding time is 2 h and the reaction residence time is 20 min to obtain a slurry. The temperature is controlled at 60℃ throughout the reaction process, and the feed molar ratio of aluminum sulfate to sodium diethylphosphonate is 1:6.

[0152] The slurry was heated to 80°C and held for 5 minutes. The slurry was filtered, washed three times with three times the amount of water, and dried at 150°C to obtain the polymer additive D4, which contains 2.53 mol% of aluminum ethyl butyl phosphonate and 0.55 mol% of aluminum ethyl phosphonite. The particle size-related parameters are shown in Table 1.

[0153] Table 1

[0154]

[0155]

[0156] The application of the polymer additives described in this invention will be detailed below using application examples, but the application of the polymer additives is not limited to these application examples.

[0157] Application examples

[0158] A polyamide composition comprising, by weight, the following components:

[0159] Polyamide 10T 61 parts

[0160] 15 parts glass fiber

[0161] 14 parts flame retardant additive;

[0162] Among them, the polyamide 10T is graded G-KFHP611A (Jinfa); the glass fiber is graded E7CS10-03-568H (China Jushi); and the flame retardant additives are polymer additives provided in Examples 1-9 and Comparative Examples 1-4.

[0163] The preparation method of the polyamide composition is as follows: Polyamide 10T, glass fiber and flame retardant additive are mixed according to the formula to obtain a premix; the premix is ​​added to a twin-screw extruder with a screw speed of 400 rpm and a processing temperature of 320°C, and after melt mixing and extrusion granulation, polyamide composition particles are obtained.

[0164] The obtained polyamide composition particles were subjected to a discolored spot test, as follows: 100g of the particles to be tested were taken, and the presence of white spots on the surface of the extruded particles was observed visually. These are discolored spots formed by uneven dispersion of the additive. The general control standard is: the size of the discolored spots ≤ 0.2mm and less than 6 spots. The test results are shown in Table 2.

[0165] Table 2

[0166] polymer additives <![CDATA[100×(D 75 -D 25 ) / (D 50 ) 2 ]]> <![CDATA[(D 97 ×D 50 ) / (D 10 ×100)]]> Case of different colored dots Example 1 1.64 1.04 No discoloration Example 2 1.35 0.88 No discoloration Example 3 1.27 1.16 No discoloration Example 4 1.72 1.60 ≤0.2mm 1 piece Example 5 1.71 1.96 ≤0.2mm 4 pieces Example 6 1.66 1.08 No discoloration Example 7 1.59 1.31 No discoloration Example 8 1.61 1.34 No discoloration Example 9 1.80 1.32 ≤0.2mm 5 pieces Example 10 1.55 1.20 No discoloration Comparative Example 1 1.82 1.56 ≤0.2mm 8 pieces Comparative Example 2 1.54 2.40 ≤0.2mm 15 pieces Comparative Example 3 1.21 1.84 ≤0.2mm 14 pieces Comparative Example 4 1.93 1.47 ≤0.2mm>15 pieces

[0167] According to the data in Table 2, the particle size of the polymer additives provided in Examples 1-10 of this invention satisfies 1.1 ≤ 100 × (D 75 -D 25 ) / (D 50 ) 2 ≤1.8 and 0.5≤(D) 97 ×D 50 ) / (D 10With a particle size distribution of (×100)≤2.0, it has a specific particle size distribution and excellent dispersion effect in polyamide systems, making the discolored spots of the polyamide composition qualified, and even making the white discolored spots disappear completely.

[0168] The polymer additives in Comparative Examples 1-2 and 4 could not simultaneously satisfy Formula I and Formula II, resulting in the polyamide compositions containing them failing to effectively improve the white spot condition. In contrast, the D-type polymer additive in Comparative Example 3... 50 Particles larger than 50 μm, even if they satisfy Formula I and Formula II, can still cause white spots in polyamide compositions.

[0169] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the polymer additive, its preparation method, and its application. However, 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, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polymer additive, characterized in that, The polymer additives include aluminum diethylphosphinate, aluminum ethylbutylphosphinate, and aluminum ethylphosphite, and the particle size of the polymer additives satisfies the relationship shown in Formula I and Formula II: 1.1≤100×(D 75 -D 25 ) / (D 50 ) 2 ≤1.8 Formula I; 0.5≤(D 97 ×D 50 ) / (D 10 (×100)≤2.0 Equation II; Among them, D 10 D 25 D 50 D 75 D 97 The particle sizes represent the particle sizes corresponding to a cumulative volume distribution percentage of 10%, 25%, 50%, 75%, and 97% for the polymer additive, respectively. The polymer additive's D 50 Particle size is 25-50 μm; The polymer additive's D 25 Particle size is 20-40 μm; The polymer additive's D 75 The particle size is 30-70 μm; The polymer additive's D 10 Particle size is 10-25 μm; The polymer additive's D 97 Particle size is 40-90 μm; The molar percentage of aluminum diethylphosphinate in the polymer additive is ≥90%; The total molar content of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, and aluminum ethylphosphite in the polymer additive is ≥99.5%.

2. The polymer additive according to claim 1, characterized in that, The molar percentage of ethyl butylphosphinate aluminum in the polymer additive is ≤4%.

3. The polymer additive according to claim 1, characterized in that, The molar percentage of aluminum ethyl phosphonite in the polymer additive is ≤1%.

4. A method for preparing a polymer additive as described in any one of claims 1-3, characterized in that, The preparation method includes: A dispersion solution is provided, the dispersion solution comprising a combination of water and a soluble flocculant; The polymer additive is obtained by metathesis reaction of soluble diethylphosphonate and soluble aluminum salt in the presence of the dispersion solution using a continuous salt-forming process.

5. The preparation method according to claim 4, characterized in that, The soluble flocculant includes polyaluminum sulfate and / or polyaluminum chloride.

6. The preparation method according to claim 4, characterized in that, The mass ratio of water to soluble flocculant in the dispersion solution is 1:(0.002-0.01).

7. The preparation method according to claim 4, characterized in that, The preparation method includes the following steps: The dispersion solution is placed in a reaction apparatus, and then a soluble diethylphosphonate aqueous solution and a soluble aluminum salt aqueous solution are simultaneously and continuously injected into the reaction apparatus to carry out a metathesis reaction, thereby obtaining the polymer additive.

8. The preparation method according to claim 4, characterized in that, The mass ratio of the soluble diethylphosphonate aqueous solution to the soluble flocculant in the dispersion solution is 1:(0.0001-0.002).

9. The preparation method according to claim 4, characterized in that, The concentration of soluble diethylphosphonate in the aqueous solution is 1-2 mol / kg.

10. The preparation method according to claim 4, characterized in that, The concentration of soluble aluminum salt in the aqueous solution is 0.3-0.6 mol / kg.

11. The preparation method according to claim 4, characterized in that, The soluble aluminum salt includes aluminum sulfate and / or aluminum sulfate hydrate, and the feed molar ratio of the soluble aluminum salt to the soluble diethylphosphonate is 1:(5.8-6.2).

12. The preparation method according to claim 4, characterized in that, The temperature for the metathesis reaction is 20-90℃.

13. The preparation method according to claim 7, characterized in that, The metathesis reaction method includes: simultaneously and continuously feeding a soluble diethylphosphonate aqueous solution and a soluble aluminum salt aqueous solution into a first stage and carrying out a first stage reaction, followed by a second stage feeding and carrying out a second stage reaction to obtain the polymer additive.

14. The preparation method according to claim 13, characterized in that, The feeding time for one stage is 5-30 minutes.

15. The preparation method according to claim 13, characterized in that, The temperature of the first stage of the reaction is 20-90℃, and the time is 10-60 min.

16. The preparation method according to claim 13, characterized in that, The feeding time for the two stages is 1-3 hours.

17. The preparation method according to claim 13, characterized in that, The temperature of the two-stage reaction is 20-90℃, and the residence time is 10-50 min.

18. The preparation method according to claim 4, characterized in that, The metathesis reaction is further followed by a post-processing step, which includes washing and drying.

19. The use of a polymer additive as described in any one of claims 1-3 in a polymer material.

20. The application according to claim 19, characterized in that, The polymer additive is used as a flame retardant in the polymer material.

21. A polymer composition, characterized in that, The polymer composition comprises a polymer matrix and a polymer additive as described in any one of claims 1-3.

22. The polymer composition according to claim 21, characterized in that, The polymer composition comprises the following components in parts by weight: 40-99 parts of polymer matrix The polymer additive is 2-35 parts.

23. The polymer composition according to claim 21, characterized in that, The polymer matrix includes any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyolefin, and polyacrylate.

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