Polymer additives, flame retardants, polymer molding materials, their preparation methods and applications

Abstract

This invention discloses polymer additives, flame retardants, polymer molding materials, their preparation methods, and applications. The polymer additives include aluminum diethylphosphinate and aluminum ethylbutylphosphinate; the polymer additives satisfy the dual enthalpy ratio ΔH defined by formula (1): 0.90≤ΔH≤1.05; and satisfy 135℃≤T1≤160℃, 165℃≤T2≤185℃, 180℃≤T3≤200℃; formula (1) ΔH=(H2+H3) / H1. The polymer additives provided by this invention have specific crystal transformation states, and the polymer molding materials containing the polymer additives exhibit lower molding shrinkage during molding applications.

Description

Technical Field

[0001] This invention belongs to the technical field of flame retardants, and more specifically, relates to polymer additives, flame retardants, polymer molding materials, their preparation methods and applications. Prior Technology

[0002] Aluminum diethylphosphonate is a halogen-free, environmentally friendly flame retardant. It is a white powder that is insoluble in water and most organic solvents, but readily soluble in strong acid and alkali solutions. It features high flame retardancy, high thermal stability, low smoke, fine particle size, low specific gravity, good dispersibility, and good compatibility. As a highly efficient, environmentally friendly, halogen-free flame retardant, aluminum diethylphosphonate is widely used in the flame retardancy of thermoplastic plastics (such as PA6T, PA10T, PA66, PBT), fibers, and textiles.

[0003] The compound systems of aluminum diethylphosphonate are widely used in the field of halogen-free flame-retardant glass fiber reinforced engineering plastics, such as the aluminum diethylphosphonate compound system with melamine polyphosphate (MPP), the aluminum diethylphosphonate compound system with melamine cyanuric acid (MCA), and the aluminum diethylphosphonate compound system with aluminum phosphite. These systems have the advantages of high flame retardancy, high temperature resistance, and low loss of resin matrix performance, and are therefore widely used.

[0004] In the application of modified polymer composite materials such as aluminum diethylphosphinate flame-retardant modified thermoplastics, problems often occur, such as excessive material molding shrinkage, which leads to problems such as inability to match and install injection molded parts or loose assembly, especially in some precision injection molded parts fields.

[0005] Patent CN110407869A discloses a monotrifluoropropyl aluminum phosphinate flame retardant, which uses a compound of monotrifluoropropyl aluminum phosphinate and diethyl aluminum phosphinate to reduce the corrosiveness of diethyl aluminum phosphinate to the screw during extrusion modification. However, it does not improve the problem of excessive molding shrinkage of the modified polymer composite material. Patent CN113637193A discloses a nylon thermal insulation strip or reinforced nylon, glass fiber reinforced PA6 / PA66 composite material, including nylon 6633, diethyl aluminum phosphinate, antioxidant, glass fiber, lubricant, maleic anhydride grafted POE toughening agent, and additives. By adding glass fiber to reinforce the nylon itself, the water absorption rate of the composite material is reduced, and the molding shrinkage rate of the product is reduced, and the dimensional stability is improved. However, in this solution, diethyl aluminum phosphinate is only used as a flame retardant component. In the application process, diethyl aluminum phosphinate still causes excessive shrinkage of the modified polymer composite material during molding. Summary of the Invention

[0006] To address the aforementioned technical problems, the primary objective of this invention is to provide a polymer additive that has a unique crystalline morphology and structure, resulting in lower molding shrinkage during polymer application.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solution: This invention claims protection for a polymer additive comprising: aluminum diethylphosphinate and aluminum ethylbutylphosphinate; the polymer additive satisfies the following dual enthalpy ratio ΔH defined by formula (1): 0.90≤ΔH≤1.05; and satisfies 135℃≤T1≤160℃, 165℃≤T2≤185℃, 180℃≤T3≤200℃; formula (1) ΔH=(H2+H3) / H1; the polymer additive is tested by differential scanning calorimetry (DSC) as follows: under a nitrogen atmosphere, the polymer additive is heated from room temperature to a maximum temperature of 300℃ at a heating rate of 20℃ / min, held at this temperature for 3min, and then... The polymer additive was cooled to room temperature at a rate of 20℃ / min to obtain a cooling curve. The polymer additive was then kept at room temperature for 3 minutes, and then heated again to a maximum temperature of 300℃ at a rate of 20℃ / min to obtain a second heating curve. H1 is the peak area formed by the starting and ending temperatures of the exothermic peak on the cooling curve. Two endothermic peaks on the second heating curve were selected, with temperatures ranging from low to high. H2 is the peak area formed by the starting and ending temperatures of the first endothermic peak on the second heating curve, and H3 is the peak area formed by the starting and ending temperatures of the second endothermic peak on the second heating curve.

[0008] T1 is the peak temperature of the exothermic peak on the cooling curve, T2 is the peak temperature of the first endothermic peak on the second heating curve, and T3 is the peak temperature of the second endothermic peak on the second heating curve.

[0009] Differential scanning calorimetry (DSC) is one of the most commonly used thermal analysis instruments. It can be used to characterize the melting and crystallization process of materials, reflecting the relationship between molecular chain structure and crystallization. Furthermore, for some substances that do not exhibit melting phenomena, distinct endothermic and exothermic peaks will appear during DSC testing. The differences between these endothermic and exothermic peaks are related to changes in molecular structure or crystallinity. Changes in molecular structure or crystal form directly determine the melting or crystallization behavior during DSC heating or cooling, as well as the differences in endothermic and exothermic peaks. Furthermore, differences in the molecular structure of materials also affect their processing fluidity and mechanical properties during processing, thereby influencing the material's dimensional stability and molding shrinkage.

[0010] This invention, through research, has discovered that although the polymer additives provided by this invention do not exhibit melting during testing at 30–300°C, the endothermic and exothermic peaks of different polymer additives show significant differences. The inventors found that the specific enthalpy ratio formed in the endothermic and exothermic peaks, as well as the specific peak temperatures (T1, T2, T3), affect the specific crystallization transformation state of the polymer additives. This state imparts better dimensional stability to the polymer molding material during polymer molding processing, thus resulting in a lower molding shrinkage rate. Polymer molding materials prepared using polymer additives possessing this specific crystallization transformation state exhibit even lower molding shrinkage rates.

[0011] In some embodiments, the peak areas H1, H2, H3 and peak positions T1, T2, T3 can be obtained by peak labeling and integration calculation using methods existing in the art, such as using software built into the DSC device. Specifically, in some embodiments, when using differential scanning calorimetry (DSC) for testing, the weight of the polymer additive test sample can be 10 ± 0.5 mg.

[0012] Specifically, in some implementations, the peak areas H1, H2, H3 and peak positions T1, T2, T3 can be obtained by multiple integrations or labeling and then averaging the results, such as once, twice, three times, four times, or five times. More specifically, from the perspective of saving operations and maintaining data reproducibility and reliability, the peak areas H1, H2, H3 and peak positions T1, T2, T3 can be obtained by 2-4 tests and averaging the results.

[0013] In some embodiments, the polymer additive comprises, by weight percentage: 99.01-99.99% aluminum diethylphosphinate and 0.01-0.99% aluminum ethylbutylphosphinate. More specifically, the content of aluminum diethylphosphinate can be 99.10%, 99.20%, 99.30%, 99.40%, 99.50%, 99.60%, 99.70%, 99.80%, 99.90%, etc., or any range formed by the above values, such as 99.01-99.40%, 99.01-99.70%, 99.01-99.90%, 99.30-99.60%, 99.50-99.90%, 99.70-99.99%, 99.90-99.99%, etc., and the present invention is not limited thereto. More specifically, the content of aluminum ethylbutylphosphonate can be 0.03%, 0.05%, 0.08%, 0.10%, 0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90%, 0.93%, 0.95%, 0.97%, etc., or any range formed by the above values, such as 0.01~0.10%, 0.01~0.30%, 0.01~0.70%, 0.10~0.80%, 0.30~0.90%, 0.70~0.93%, 0.80~0.99%, 0.90~0.99%, etc., and the present invention is not limited thereto.

[0014] In some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist in a physical combination; in some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist in an ionic chemical coprecipitation of Formula I and Formula II; in some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist simultaneously in a physical combination and in an ionic chemical coprecipitation of Formula I and Formula II.

[0015] Formula I Formula II More specifically, in this invention, the dual enthalpy ratio ΔH can be 0.92, 0.94, 0.96, 0.98, 0.99, 1.00, 1.02, 1.04, 1.05, or any range formed by the above values, such as 0.92~0.98, 0.96~1.05, etc., and this invention is not limited thereto.

[0016] More specifically, in this invention, T1 can be 135℃, 138℃, 140℃, 142℃, 144℃, 146℃, 148℃, 150℃, 152℃, 154℃, 156℃, 158℃, etc., or any range formed by the above values, such as 140℃~150℃, 146℃~154℃, etc., and this invention is not limited to this.

[0017] More specifically, in this invention, T2 can be 168℃, 170℃, 172℃, 174℃, 176℃, 178℃, 180℃, 183℃, etc., or any range formed by the above values, such as 174℃~178℃, etc., and this invention is not limited thereto.

[0018] More specifically, in this invention, T3 can be 182℃, 184℃, 186℃, 188℃, 190℃, 192℃, 194℃, 196℃, 198℃, etc., or any range formed by the above values, such as 184℃~188℃, 190℃~192℃, etc., and this invention is not limited thereto.

[0019] In some embodiments, the polymer additive satisfies a dienthalpy ratio ΔH: 0.92 ≤ ΔH ≤ 1.05.

[0020] In some embodiments, the polymer additive satisfies 140℃≤T1≤156℃, 172℃≤T2≤178℃, and 184℃≤T3≤192℃.

[0021] In some embodiments, this invention claims protection for a method for preparing a polymer additive, comprising the following steps:

[0022] S1. Under nitrogen protection, a water-soluble salt or acid of hypophosphite, an initiator, and an olefin are reacted, with 2.00 to 2.05 molecules of olefin added relative to the phosphorus content of each water-soluble salt or acid of hypophosphite, to give an aqueous intermediate containing diethylphosphite.

[0023] S2. The intermediate aqueous solution, surfactant, and aluminum salt solution from step S1 are reacted to obtain the polymer additive.

[0024] In the above implementation scheme, the reaction temperature in step S1 is 80~120℃.

[0025] In the above implementation scheme, the reaction pressure in step S1 is 0.6~2.0 MPa.

[0026] In the above implementation scheme, step S1 involves two heat preservation steps: first, heating to 80-90°C for 3.5-4.5 hours, with initiator continuously added during the heat preservation process; then, heat preservation continues at 90-100°C for 0.5-1.5 hours; or heat preservation involves two heat preservation steps: first, heating to 105-115°C for 3.5-4.5 hours, with initiator continuously added during the heat preservation process; then, heat preservation continues at 105-115°C for 0.5-1.5 hours.

[0027] In the above implementation scheme, in step S2, the mass concentration of diethylphosphonate in the intermediate aqueous solution is 15-25%; in step S2, the mass concentration of water-soluble aluminum salt in the aluminum salt solution is 20-24%.

[0028] In the above implementation scheme, in step S2, the surfactant is selected from one or more of alkyl phosphates, alkyl phosphate salts, ether alcohol phosphates, and ether alcohol phosphate salts.

[0029] Specifically, alkyl phosphates or alkyl phosphate salts may be selected from alkyl phosphates or alkyl phosphate salts with 8 to 18 carbon atoms; more specifically, alkyl phosphates include, but are not limited to, monolaurate phosphate; alkyl phosphate salts include, but are not limited to, potassium monododecyl phosphate. Specifically, ether alcohol phosphates or ether alcohol phosphate salts may be selected from ether alcohol phosphates or ether alcohol phosphate salts with 8 to 18 carbon atoms; more specifically, ether alcohol phosphates include, but are not limited to, lauryl ether phosphate; ether alcohol phosphate salts include, but are not limited to, potassium lauryl phosphate.

[0030] In the above embodiments, the amount of surfactant added is 0.001 to 0.10% of the weight of the intermediate aqueous solution. More preferably, the amount of surfactant added is 0.01 to 0.08% of the weight of the intermediate aqueous solution.

[0031] In the above implementation scheme, before adding the surfactant, an alkaline solution is added to the intermediate aqueous solution for neutralization to remove free acid from the solution system. More specifically, the solution is neutralized to a pH of 5-6.5.

[0032] In the above implementation scheme, in step S2, the amounts of the intermediate aqueous solution and the aluminum salt solution are equal.

[0033] In the above implementation scheme, the aluminum salt solution is added in one go, the temperature of the aluminum salt solution is raised to 50-60°C during the addition process, and the addition time is controlled to be 90-110 minutes; and / or

[0034] In step S2, the aluminum salt solution is added in two parts. The first part is 15-35% equivalent of aluminum salt solution, with the addition time controlled at 30-40 minutes and the temperature controlled at 35-45°C. The second part is 65-85% equivalent of aluminum salt solution, with the addition time controlled at 30-40 minutes and the temperature controlled at 55-60°C.

[0035] In some embodiments, the present invention claims protection for a method for preparing another polymer additive, comprising the following preparation steps: S1. Under nitrogen protection, an aqueous solution of hypophosphite, an initiator, and an olefin are reacted, with 2.00 to 2.05 molecules of olefin added relative to the phosphorus content of each hypophosphite, to obtain an aqueous intermediate containing diethylphosphinoic acid; S2. Preparation of aluminum hydroxide gel solution; S3. The intermediate aqueous solution from step S1 is added dropwise to the aluminum hydroxide gel solution from step S2 to carry out the reaction. The temperature is raised to 50~60℃ and kept at that temperature for 0.1~0.5h; then the temperature is raised to 90~120℃ and kept at that temperature for 0.5~5h to obtain the polymer additive.

[0036] In the above implementation scheme, step S1 involves two heat preservation steps. The first heat preservation temperature is 75~85℃ and the time is 2.5~3.5h. During the heat preservation process, the initiator is continuously added. During the heat preservation process, part of the reactants in the reactor are passed into the Venturi jet and fully mixed with the ethylene passed into the Venturi jet. After the mixture is circulated back into the reactor, it is then kept at the same temperature for another 0.5~1.5h.

[0037] In the above implementation scheme, the reaction temperature in step S2 is 10~20℃.

[0038] In the above implementation scheme, in step S3, the temperature is increased to 50-60°C at a heating rate of 2-10°C / h; and / or

[0039] In the above implementation scheme, in step S3, the temperature is increased to 90-120°C at a heating rate of 11-25°C / h.

[0040] In the above implementation scheme, in step S3, the molar ratio of diethylphosphonic acid to aluminum ions in the aluminum hydroxide gel solution is 3:1~1.01.

[0041] In some embodiments, the olefin may be at least one of ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, or 1-octene.

[0042] In some implementations, the water-soluble salt of hypophosphite may be potassium hypophosphite or sodium hypophosphite.

[0043] In some implementations, the water-soluble aluminum salt can be an oxide, hydroxide, peroxide, sulfate, bisulfate, hydrated sulfate, persulfate, phosphate, and / or phosphite of aluminum.

[0044] In some embodiments, the initiator is selected from one or more of organic peroxides, inorganic peroxides, and azo compounds. More specifically, the inorganic peroxide may be one or more of sodium persulfate, ammonium persulfate, or potassium persulfate. The organic peroxide may be one or more of benzoic acid peroxide, lauric acid peroxide, di-tert-butyl peroxide, carbonate peroxide, acetic acid peroxide, tert-butyl peroxide isobutyrate, tert-butyl peroxypentanoate, tert-butyl peroxy-2-ethylhexanoate, or tert-pentanoate peroxide; the azo compound may be one or more of azobisisobutyronitrile or azobisisoheptanenitrile.

[0045] Furthermore, the present invention claims protection for the use of the above-mentioned polymer additive in reducing the shrinkage rate of polymers.

[0046] Furthermore, the present invention claims protection for the above-mentioned polymer additives as reactive and / or non-reactive flame retardants for polymers, as flame retardants for varnishes and foamed coatings, as flame retardants for wood and other cellulose-containing products, for use in the preparation of flame-retardant polymer molding materials, for use in the preparation of flame-retardant polymer molded articles, and / or for use in imparting flame retardancy to polyester and pure and blended cellulose fabrics by impregnation.

[0047] In some embodiments, the polymer additive is used in conjunction with a synergist; the synergist is melamine phosphate, bis(melamine) phosphate, penta(melamine) triphosphate, tri(melamine) diphosphate, tetra(melamine) triphosphate, hexa(melamine) pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, and / or melamine polyphosphate; a melamine condensation product such as melamine, melamine, and / or melamine polyphosphate; a low polyester of tri(hydroxyethyl) isocyanurate / salt and aromatic polycarboxylic acid, benzoguanidine, tri(hydroxyethyl) isocyanurate / salt, benzoguanidine, tri(hydroxyethyl) isocyanurate / salt, and / or melamine polyphosphate. Ethyl) isocyanurate / salt, allantoin, glycourea, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and / or guanidine; nitrogen-containing phosphates of the formula (NH4)yH3-yPO4 or (NH4PO3)z, wherein y is 1 to 3 and z is 1 to 10000; aluminum phosphite, aluminum pyrophosphite; zinc borate, zinc carbonate, zinc stannate, zinc basic stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, magnesium carbonate; salts of ethylphosphonic acid, salts of butylphosphonic acid, salts of n-butylphosphonic acid, salts of sec-butylphosphonic acid and / or salts of hexylphosphonic acid.

[0048] In some embodiments, the polymer additive is used in conjunction with other additives selected from at least one of antioxidants, UV stabilizers, gamma-ray stabilizers, hydrolytic stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact modifiers, dyes, or pigments.

[0049] In some embodiments, 0.0001 to 99.7999 wt% of the polymer additive, 0.1 to 40 wt% of the synergist and 0.1 to 40 wt% of other additives are used.

[0050] In some embodiments, the present invention claims protection for flame-retardant thermoplastic or thermosetting polymer molding materials, polymer molded articles, polymer films, polymer filaments and / or polymer fibers, comprising: 0.5 to 45 wt% of the polymer additive, 0.5 to 95 wt% of the thermoplastic or thermosetting polymer or mixtures thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.

[0051] In some embodiments, the polymer is selected from polyesters, polyamides, thermoplastic elastomers, thermoplastic polyurethanes, thermoplastic polyester elastomers, styrene polymers, polyketides, polyolefins, polyacrylates, and / or polymer blends containing polyamides or polyesters.

[0052] In some embodiments, the polyolefin can be a polymer of monoolefins and dienes, such as polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene, or polybutadiene, and a polymer of cyclic olefins such as cyclopentene or norbornene; in addition, it can be polyethylene (optionally crosslinked), such as high-density polyethylene (HDPE), high-density and high-molar-weight polyethylene (HDPE-HMW), high-density and ultra-high-molar-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), branched low-density polyethylene (VLDPE), and mixtures thereof.

[0053] Polyolefins can also be copolymers of monoolefins and dienes with each other or with other vinyl monomers, such as ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-1-butene copolymers, propylene-isobutene copolymers, ethylene-1-butene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methylpropionate copolymers, and ethylene-vinyl acetate copolymers. Polymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene norbornene; in addition, mixtures of such copolymers with each other, such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or statistically constructed polyalkylene / carbon monoxide copolymers and mixtures with other polymers such as polyamides.

[0054] In some embodiments, the styrene polymer can be a copolymer of styrene or α-methylstyrene with a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; a high-impact mixture of a styrene copolymer and another polymer such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and a block copolymer of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butene-styrene or styrene-ethylene / propylene-styrene.

[0055] In some embodiments, the styrene-based polymer can be a graft copolymer of styrene or α-methylstyrene, such as styrene grafted onto polybutadiene, styrene grafted onto a polybutadiene-styrene copolymer or a polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted onto polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted onto polybutadiene; styrene and maleic anhydride grafted onto polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide grafted onto polybutadiene; styrene and maleimide grafted onto polybutadiene, styrene and alkyl acrylate or alkyl methacrylate grafted onto polybutadiene, styrene and acrylonitrile grafted onto an ethylene-propylene-diene terpolymer, styrene and acrylonitrile grafted onto an alkyl polyacrylate or polyalkyl methacrylate, styrene and acrylonitrile grafted onto an acrylate-butadiene copolymer, and mixtures thereof, such as ABS polymers, MBS polymers, ASA polymers or AES polymers.

[0056] In some embodiments, the polyamide can be a polyamide and copolyamide derived from diamines and dicarboxylic acids and / or derived from aminocarboxylic acids or corresponding endolamines, such as PA6, PA66, PA46, etc.; aromatic polyamides derived from m-xylene, diamines, and adipic acid; polyamides (polyhexamethylene isophthalamide, polyhexamethylene terephthalamide) prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid and optionally as a modifier and an elastomer, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; or a block copolymer of polyamide with polyolefins, olefin copolymers, ionomers, or chemically bonded or grafted elastomers; or a block copolymer with polyethers, such as with polyethylene glycol, polypropylene glycol, or polybutanediol.

[0057] In some embodiments, the polyester can be a polyester derived from dicarboxylic acids and diols and / or derived from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, and block polyether esters derived from polyethers having hydroxyl-terminated groups; as well as polyesters modified with polycarbonate or MBS.

[0058] In some embodiments, the filler or reinforcing material may be an oxygen-containing silicon compound, a magnesium compound, such as a metal carbonate of a Group 2 metal in the periodic table, magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrotalcite, magnesium carbonate or magnesium calcium carbonate; a calcium compound such as calcium hydroxide, calcium oxide, hydrated calcium silicate; an aluminum compound such as aluminum oxide, aluminum hydroxide, boehmite, hydrated gibbsite or aluminum phosphate, red phosphorus, zinc compounds, or glass fiber.

[0059] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a polymer additive having specific ΔH, T1, T2, and T3. The polymer additive within the above-mentioned specific range has a specific crystal transformation state. The polymer molding material with the addition of the polymer additive has a lower molding shrinkage rate during molding applications. Implementation

[0060] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0061] The raw materials used in the examples and comparative examples are described below:

[0062] Fiberglass, ECS10-03-568H, Jushi Group.

[0063] Base resin 1: PA66, EPR24, Henan Shenma.

[0064] Base resin 2: PBT, GX121, Yizheng Chemical.

[0065] Base resin 3: PA6, M2000, Guangdong Xinhui Meida.

[0066] Synergist 1: Melamine polyphosphate, MPP, Bubit 3141, Budenheim.

[0067] Synergist 2: Zinc borate, ZB-503, Anhui Yishitong Materials.

[0068] Synergist 3: Aluminum phosphite, commercially available.

[0069] Sodium hypophosphite monohydrate, commercially available.

[0070] Sodium persulfate, commercially available.

[0071] Aluminum sulfate, commercially available.

[0072] Monolauryl phosphate, commercially available.

[0073] Lauryl ether phosphate, commercially available.

[0074] Potassium lauryl phosphate, commercially available.

[0075] Unless otherwise specified, all components used in the parallel embodiments and comparative examples are the same commercially available products.

[0076] Example 1: A polymer additive

[0077] (1) 318g of solid sodium hypophosphite monohydrate, 400g of water and 2g of tert-butyl peroxide-2-ethylhexanoate were placed in a high-pressure reactor. The air in the reactor was replaced with nitrogen five times. Ethylene was introduced into the high-pressure reactor. The pressure of ethylene in the high-pressure reactor was kept constant at 0.6MPa by a pressure reducer. The reactor was heated to 85℃ and kept at that temperature for 4h. 4g of tert-butyl peroxide-2-ethylhexanoate was continuously added during the 4h holding period. The reactor was then kept at 95℃ for 1h and cooled and vented to obtain an aqueous solution containing sodium diethylphosphite.

[0078] (2) Add 20wt% sodium hydroxide aqueous solution to the aqueous solution containing sodium diethylphosphonate obtained in step (1) to neutralize the free acid to pH=6, dilute with water to a mass concentration of sodium diethylphosphonate of 20%, add 0.03% (the amount added is based on the weight of the diluted sodium diethylphosphonate aqueous solution) of monolaurate phosphate, and add 1 / 6 equivalent (based on the molar amount of sodium diethylphosphonate) of 20% aluminum sulfate aqueous solution at 40°C for 40 minutes; raise the temperature to 55°C, and add the remaining 5 / 6 equivalent (based on the molar amount of sodium diethylphosphonate) of 20% aluminum sulfate aqueous solution for 40 minutes; then cool and filter in sequence, wash the filter cake three times with water three times the weight of the filter cake, and then dry at 120°C to constant weight to obtain polymer additive.

[0079] Example 2 A polymer additive

[0080] (1) 318g of solid sodium hypophosphite monohydrate, 400g of water and 2g of sodium persulfate were placed in an autoclave. The air in the autoclave was replaced with nitrogen five times. Ethylene was introduced into the autoclave. The pressure of ethylene in the autoclave was kept constant at 1.5MPa by a pressure reducer. The autoclave was heated to 110℃ and kept at that temperature for 4h. A solution prepared by 4g of sodium persulfate and 36g of water was continuously added during the 4h holding period. The autoclave was then kept at 110℃ for 1h, cooled and vented to obtain an aqueous solution containing sodium diethylphosphite.

[0081] (2) The aqueous solution containing sodium diethylphosphonate obtained in step (1) was added to a 20wt% sodium hydroxide aqueous solution to neutralize the free acid to pH=6, and diluted with water to a mass concentration of sodium diethylphosphonate of 20%. 0.02% (the amount added is based on the weight of the diluted sodium diethylphosphonate aqueous solution) of lauryl ether phosphate was added, and 1 / 6 equivalent (based on the molar amount of sodium diethylphosphonate) of a 20% aluminum sulfate aqueous solution was added dropwise at 35°C for 40 minutes. The temperature was raised to 55°C, and the remaining 5 / 6 equivalent (based on the molar amount of sodium diethylphosphonate) of a 20% aluminum sulfate aqueous solution was added dropwise for 30 minutes. The solution was then cooled and filtered in sequence. The filter cake was washed three times with water at a weight of three times the filter cake and then dried at 120°C to constant weight to obtain the polymer additive.

[0082] Example 3 A polymer additive

[0083] The difference between this embodiment and Embodiment 1 is:

[0084] (2) The aqueous solution containing sodium diethylphosphonate obtained in step (1) was added to a 20wt% sodium hydroxide aqueous solution to neutralize the free acid to pH=6, and diluted with water to a mass concentration of sodium diethylphosphonate of 20%. 0.04% (the amount added is based on the weight of the diluted sodium diethylphosphonate aqueous solution) of lauryl ether phosphate was added, and 1 / 3 equivalent (based on the molar amount of sodium diethylphosphonate) of a 20% aluminum sulfate aqueous solution was added dropwise at 35°C for 40 minutes. The temperature was raised to 55°C, and the remaining 2 / 3 equivalent (based on the molar amount of sodium diethylphosphonate) of a 20% aluminum sulfate aqueous solution was added dropwise for 20 minutes. The solution was then cooled and filtered in sequence. The filter cake was washed three times with water at a weight of three times the filter cake and then dried at 120°C to constant weight to obtain the polymer additive.

[0085] Example 4 A polymer additive

[0086] The difference between this embodiment and Embodiment 2 is:

[0087] (2) The aqueous solution containing sodium diethylphosphonate obtained in step (1) was added to a 20wt% sodium hydroxide aqueous solution to neutralize the free acid to pH=6, and diluted with water to a mass concentration of sodium diethylphosphonate of 22%. 0.05% (the amount added is based on the weight of the diluted sodium diethylphosphonate aqueous solution) of potassium lauryl phosphate was added, and 1 equivalent (based on the molar amount of sodium diethylphosphonate) of aluminum sulfate aqueous solution with a mass concentration of 22% was added dropwise at 30°C, while the temperature was slowly increased to 60°C at a rate of 4°C / 10 minutes. The total dropwise addition time was 100 minutes. Then, the mixture was cooled and filtered. The filter cake was washed three times with water at a weight of 3 times the filter cake and then dried at 120°C to constant weight to obtain the polymer additive.

[0088] Example 5 A polymer additive

[0089] (1) 396 kg of a 50% phosphonic acid aqueous solution was added to a high-pressure reactor. The air in the reactor was replaced five times with nitrogen at 0.6 MPa. Ethylene was then introduced into the reactor until the ethylene pressure reached 1.0 MPa. The reactor was stirred and heated to 80°C and kept at that temperature for 3 hours. 40 g of a 10% sodium persulfate aqueous solution was continuously added during the 2-hour heat preservation period. During the heat preservation process, the material was pumped into the liquid inlet of the Venturi ejector through the bottom valve of the reactor via a centrifugal pump. The ethylene gas from the upper layer of the reactor entered through the gas inlet of the Venturi ejector, and the gas and liquid phases were thoroughly mixed and circulated back into the reactor. Ethylene entered through the gas inlet of the Venturi ejector to replenish the ethylene consumed in the reaction and maintain the reactor pressure at 1.0 MPa. After the initiator was replenished, the reactor was kept at that temperature for 1 hour, cooled, and vented to obtain an aqueous solution containing diethylphosphonic acid.

[0090] (2) At 20°C, a sodium hydroxide aqueous solution was prepared by using 60g sodium hydroxide and 1140g water. The sodium hydroxide aqueous solution was slowly added dropwise to an aluminum sulfate aqueous solution prepared by 333g aluminum sulfate octadecahydrate and 777g water within 1.5h to obtain an aluminum hydroxide gel solution.

[0091] (3) The aluminum hydroxide gel solution was continuously dripped into an aqueous solution containing diethylphosphonic acid (the molar ratio of diethylphosphonic acid to aluminum ions was 3:1) over 3 hours. Then, the temperature was increased to 60°C at a rate of 5°C / h and held for 0.5 hours. The temperature was then increased to 100°C at a rate of 20°C / h and held for 0.5 hours. The mixture was then cooled and filtered. The filter cake was washed three times with water at a rate of three times its weight and then dried at 120°C to constant weight to obtain the polymer additive.

[0092] Example 6 A polymer additive

[0093] The difference between this embodiment and embodiment 5 is: (2) At 10℃, a sodium hydroxide aqueous solution was prepared by using 60g sodium hydroxide and 1140g water. The sodium hydroxide aqueous solution was slowly added dropwise to an aluminum sulfate aqueous solution prepared by 333g aluminum sulfate octadecahydrate and 777g water within 1.5h to obtain an aluminum hydroxide gel solution. (3) The aluminum hydroxide gel solution was continuously dripped into an aqueous solution containing diethylphosphonic acid (the molar ratio of diethylphosphonic acid to aluminum ions was 3:1) over 3 hours. Then, the temperature was increased to 60°C at a rate of 10°C / h and held for 0.5 hours. Then, the temperature was increased to 100°C at a rate of 20°C / h and held for 0.5 hours. Then, the mixture was cooled and filtered. The filter cake was washed three times with water at a rate of three times its weight and then dried at 120°C to constant weight to obtain the polymer additive.

[0094] Comparative Example 1 Existing polymer additive 1, XHPFR-1040, from Zhejiang Xinhua Chemical Co., Ltd., was used.

[0095] Comparative Example 2 Existing polymer additive 2, ADP-30, Lanzhou Ruipu Technology Co., Ltd.

[0096] Test case (1) The polymer additives prepared in Examples 1-6 and Comparative Examples 1-2 were dissolved in a deuterated sodium hydroxide aqueous solution and their NMR phosphorus spectra were tested.

[0097] (1) Instrument: Nuclear magnetic resonance spectrometer (Bruker 400M).

[0098] (2) Reagent: 10wt% sodium hydroxide deuterated aqueous solution.

[0099] (3) Experimental method: Weigh about 0.1g of the sample to be tested (accurate to 0.0001g) and add 5g of sodium hydroxide deuterated aqueous solution. Dissolve it by sonication. Transfer it to an NMR tube and place the NMR tube in the NMR analyzer. Scan it to obtain the NMR spectrum. Integrate the aluminum diethylphosphonate and aluminum ethylbutylphosphonate in the NMR spectrum to obtain their molar percentages. After conversion, obtain their mass percentages.

[0100] The test results of the polymer additives, expressed as a percentage by weight, are shown in Table 1 below. Table 1 Components Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Aluminum diethylphosphinate 99.3% 99.1% 99.6% 99.1% 99.9% 99.9% 98.4% 99.6% Aluminum ethyl butylphosphinate 0.7% 0.9% 0.4% 0.9% 0.1% 0.1% 1.6% 0.4%

[0101] (2) The polymer additives prepared in Examples 1-6 and Comparative Examples 1-2 were tested by differential scanning calorimetry (DSC 214, NETZSCH DSC 204 F1, Germany). The test method is as follows: Under a nitrogen atmosphere, the polymer additive was heated from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min. After holding at this temperature for 3 min, it was cooled to room temperature at a rate of 20°C / min to obtain the cooling curve of the polymer additive. After holding the polymer additive at room temperature for 3 min, it was heated again to a maximum temperature of 300°C at a heating rate of 20°C / min to obtain the second heating curve of the polymer additive.

[0102] Where H1 is the peak area formed by the starting and ending temperatures of the exothermic peak in the cooling curve; two endothermic peaks are selected on the second heating curve, with temperatures ranging from low to high. H2 is the peak area formed by the starting and ending temperatures of the first endothermic peak on the second heating curve, and H3 is the peak area formed by the starting and ending temperatures of the second endothermic peak on the second heating curve.

[0103] In Table 2 below, ΔH = (H2 + H3) / H1;

[0104] T1 is the peak temperature of the exothermic peak on the cooling curve, T2 is the peak temperature of the first endothermic peak on the second heating curve, and T3 is the peak temperature of the second endothermic peak on the second heating curve.

[0105] The peak temperature and peak area were obtained through calibration or calculation using the software included in the NETZSCH DSC 204 F1.

[0106] The test data of the polymer additives in Examples 1-6 and Comparative Examples 1-2 are shown in Table 2 below. Table 2 H1 H2 H3 ΔH T1 (°C) T2 (°C) T3 (°C) Example 1 24.38 8.38 15.69 0.99 155.3 175.9 190.1 Example 2 20.89 7.96 13.27 1.02 140.6 177.3 184.0 Example 3 25.14 7.82 15.31 0.92 153.4 177.6 191.9 Example 4 21.44 9.04 13.47 1.05 151.3 172.0 184.9 Example 5 22.33 8.34 14.45 0.98 144.8 174.6 186.3 Example 6 23.96 9.15 16.07 0.95 147.3 179.9 188.2 Comparative Example 1 19.99 7.81 14.91 0.88 132 174 186 Comparative Example 2 24.05 9.21 16.52 1.07 142 179 195

[0107] (3) The polymer additives of Examples 1-6 and Comparative Examples 1-2 were used as flame retardants and co-extruded with synergists, glass fibers, and base resins to obtain polymer molding materials. The amounts of each component in Examples 7-16 and Comparative Examples 3-5 by weight are shown in Table 3. Table 3 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 3 Comparative Example 4 Comparative Example 5 Base Resin 1 58 58 58 58 58 58 58 58 / / 58 58 / Base Resin 2 / / / / / / / / 58 / / / 58 Base Resin 3 / / / / / / / / / 58 / / / Fiberglass 30 30 30 30 30 30 30 30 30 30 30 30 30 Synergist 1 3 3 3 3 3 3 1.5 / 3 3 3 3 3 Synergist 2 / / / / / / 1.5 / / / / / / Synergist 3 / / / / / / / 3 / / / / / polymer additives Example 1 9 / / / / / 9 9 9 9 / / / Example 2 / 9 / / / / / / / / / / / Example 3 / / 9 / / / / / / / / / / Example 4 / / / 9 / / / / / / / / / Example 5 / / / / 9 / / / / / / / / Example 6 / / / / / 9 / / / / / / / Comparative Example 1 / / / / / / / / / / 9 / 9 Comparative Example 2 / / / / / / / / / / / 9 /

[0108] The molding shrinkage rate of the polymer molding materials prepared in Examples 7-16 and Comparative Examples 3-5 was tested using GB / T 15585-1995, and the shrinkage rate after 48 hours was measured. The test results are shown in Table 4 below. Table 4 Performance indicators Lateral shrinkage rate (%) Longitudinal shrinkage rate (%) Example 7 0.66 0.23 Example 8 0.63 0.27 Example 9 0.70 0.29 Example 10 0.66 0.27 Example 11 0.63 0.25 Example 12 0.60 0.21 Example 13 0.69 0.28 Example 14 0.55 0.19 Example 15 0.81 0.23 Example 16 0.68 0.21 Comparative Example 3 0.80 0.32 Comparative Example 4 0.92 0.36 Comparative Example 5 0.97 0.30

[0109] As can be seen from the examples, polymer molding materials with added polymer additives exhibit lower molding shrinkage during molding applications. The transverse shrinkage of polymer molding materials with added polymer additives is ≤0.81%, and the longitudinal shrinkage is ≤0.29%.

[0110] As shown in Examples 7, 13, and 14, using different synergists in polymer molding materials can achieve good molding shrinkage rates. As shown in Examples 7, 15, and 16, using different base resins to prepare polymer molding materials can also achieve good molding shrinkage rates.

[0111] As can be seen from the examples, comparative examples 3 and 4, when the enthalpy ratio ΔH of the polymer additive and T1, T2 and T3 are within a specific range, the transverse shrinkage and longitudinal shrinkage of the polymer molding material with the polymer additive are significantly reduced.

[0112] The foregoing embodiments are merely illustrative, used to explain some features of the methods described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Therefore, the applicant intends that the appended claims are not limited to the selection of examples illustrating the features of the invention. Some numerical ranges used in the claims also include subranges within them, and variations within these ranges should be interpreted as being covered by the appended claims where possible.

Claims

1. A polymer additive, comprising: Aluminum diethylphosphines and aluminum ethylbutylphosphines; the polymer additives satisfy the dual enthalpy ratio ΔH defined by the following formula (1): 0.90≤ΔH≤1.05; and satisfy 135℃≤T1≤160℃, 165℃≤T2≤185℃, 180℃≤T3≤200℃; Formula (1) ΔH=(H2+H3) / H1; the polymer additives are tested by differential scanning calorimetry (DSC) as follows: under nitrogen atmosphere, the polymer additives are heated from room temperature to a maximum temperature of 300℃ at a heating rate of 20℃ / min, held at this temperature for 3min, and then cooled to room temperature at a rate of 20℃ / min to obtain the cooling curve of the polymer additives; The polymer additive was left at room temperature for 3 minutes, and then heated again to a maximum temperature of 300℃ at a heating rate of 20℃ / min to obtain the second heating curve of the polymer additive; H1 is the peak area formed by the starting and ending temperatures of the exothermic peak on the cooling curve; two endothermic peaks on the second heating curve were selected, with temperatures from low to high, H2 is the peak area formed by the starting and ending temperatures of the first endothermic peak on the second heating curve, and H3 is the peak area formed by the starting and ending temperatures of the second endothermic peak on the second heating curve; T1 is the peak temperature of the exothermic peak on the cooling curve, T2 is the peak temperature of the first endothermic peak on the second heating curve, and T3 is the peak temperature of the second endothermic peak on the second heating curve; The polymer additive comprises, by weight percentage: 99.01 to 99.99% aluminum diethylphosphinate and 0.01 to 0.99% aluminum ethylbutylphosphinate.

2. The polymer additive according to claim 1, wherein, Aluminum diethylphosphonate and aluminum ethylbutylphosphonate exist in a physical combination; and / or aluminum diethylphosphonate and aluminum ethylbutylphosphonate exist in the form of ionic chemical coprecipitation of Formula I and Formula II; Formula I Formula II 3. The polymer additive according to claim 1, wherein, The polymer additive satisfies the dual enthalpy ratio ΔH: 0.92≤ΔH≤1.05; and / or the polymer additive satisfies 140℃≤T1≤156℃, 172℃≤T2≤178℃, and 184℃≤T3≤192℃.

4. A method for preparing the polymer additive according to any one of claims 1 to 3, wherein, The preparation method is either Method 1 or Method 2; Method 1 includes the following steps: S1. Under nitrogen protection, a water-soluble salt or acid of hypophosphite, an initiator, and an olefin are reacted, with 2.00 to 2.05 molecules of olefin added relative to the phosphorus content of each water-soluble salt or acid of hypophosphite, to obtain an aqueous intermediate containing diethylphosphite; S2. The aqueous intermediate from step S1, a surfactant, and an aluminum salt solution are reacted to obtain the polymer additive; and Method 2 includes the following preparation steps: S1. Under nitrogen protection, an aqueous hypophosphite solution, an initiator, and an olefin are reacted, with 2.00 to 2.05 molecules of olefin added relative to the phosphorus content of each hypophosphite acid, to obtain an aqueous intermediate containing diethylphosphite; S2. An aluminum hydroxide gel solution is prepared; S3. The intermediate aqueous solution from step S1 is added dropwise to the aluminum hydroxide gel solution from step S2 to carry out the reaction. The temperature is raised to 50-60°C and kept at that temperature for 0.1-0.5 hours. Then the temperature is raised to 90-120°C and kept at that temperature for 0.5-5 hours to obtain the polymer additive.

5. The preparation method according to claim 4, wherein, In step S1 of method one, the reaction temperature is 80–120°C; and / or in step S1 of method one, the reaction pressure is 0.6–2.0 MPa; and / or in step S2 of method one, the mass percentage concentration of diethylphosphonate in the intermediate aqueous solution is 15–25%; in step S2, the mass percentage concentration of water-soluble aluminum salt in the aluminum salt solution is 20–24%; and / or in step S2 of method one, the surfactant is selected from alkyl phosphates, alkyl phosphate salts, ether alcohol phosphates, and ether alcohol phosphates. One or more of the following: ester salts; and / or in step S2 of method one, the aluminum salt solution is added all at once, with the temperature raised to 50–60°C during the addition process, and the addition time controlled at 90–110 min; or, in step S2, the aluminum salt solution is added in two parts: the first part is 15–35% equivalent aluminum salt solution, with the addition time controlled at 30–40 min and the temperature controlled at 35–45°C; the second part is 65–85% equivalent aluminum salt solution, with the addition time controlled at 30–40 min and the temperature controlled at 55–60°C.

6. Use of the polymer additive described in any one of claims 1 to 3 in reducing the shrinkage rate of a polymer.

7. The polymer additive described in any one of claims 1 to 3 is used as a reactive and / or non-reactive flame retardant for polymers, as a flame retardant for varnishes and foamed coatings, as a flame retardant for wood and other cellulose-containing products, for the preparation of flame-retardant polymer molding materials, for the preparation of flame-retardant polymer molded articles, and / or for imparting flame retardancy to polyester and pure and blended cellulose fabrics by impregnation.

8. As described in claim 7, wherein, The polymer additive is used in conjunction with a synergist; the synergist is melamine phosphate, di(melamine) phosphate, penta(melamine) triphosphate, tri(melamine) diphosphate, tetra(melamine) triphosphate, hexa(melamine) pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, and / or melamine polyphosphate; a melamine condensation product; a low polyester of tris(hydroxyethyl) isocyanurate / salt and aromatic polycarboxylic acids, benzoguanidine, tris(hydroxyethyl) isocyanurate / salt, allantoin, glycourea, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and / or guanidine; a nitrogen-containing phosphate of formula (NH4)yH3-yPO4 or (NH4PO3)z, wherein y is 1 to 3 and z is 1. ~10000; is aluminum phosphite, aluminum metaphosphite; is zinc borate, zinc carbonate, zinc stannate, zinc basic stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, magnesium carbonate; is a salt of ethylphosphonic acid, a salt of butylphosphonic acid, a salt of n-butylphosphonic acid, a salt of sec-butylphosphonic acid and / or a salt of hexylphosphonic acid; and / or the polymer additive is used with other additives selected from at least one of antioxidants, UV stabilizers, γ-ray stabilizers, hydrolytic stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact modifiers, dyes or pigments; and / or uses 0.0001~99.7999 wt% of the polymer additive, 0.1~40 wt% of a synergist and 0.1~40 wt% of other additives.

9. A flame-retardant thermoplastic or thermosetting polymer molding material, wherein, It comprises: 0.5 to 45 wt% of the polymer additive described in any one of claims 1 to 3, 0.5 to 95 wt% of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.

10. A flame-retardant thermoplastic or thermosetting polymer molded article, wherein, It comprises: 0.5 to 45 wt% of the polymer additive described in any one of claims 1 to 3, 0.5 to 95 wt% of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.

11. A flame-retardant thermoplastic or thermosetting polymer film, wherein, It comprises: 0.5 to 45 wt% of the polymer additive described in any one of claims 1 to 3, 0.5 to 95 wt% of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.

12. A flame-retardant thermoplastic or thermosetting polymer filament, wherein, It comprises: 0.5 to 45 wt% of the polymer additive described in any one of claims 1 to 3, 0.5 to 95 wt% of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.

13. A flame-retardant thermoplastic or thermosetting polymer fiber, wherein, It comprises: 0.5 to 45 wt% of the polymer additive described in any one of claims 1 to 3, 0.5 to 95 wt% of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55 wt% of a synergist and 0 to 55 wt% of a filler or reinforcing material.