Polymer additives, flame retardants, polymer molding materials, methods for producing the same, and their applications

Abstract

The present invention provides polymer additives, methods for producing the same, flame retardants containing the polymer additives, polymer molding materials containing the polymer additives, and the like. [Solution] The polymer additive comprises aluminum diethylphosphinate and aluminum ethylbutylphosphinate, and the polymer additive satisfies the dual enthalpy ratio ΔH defined by the following formula (1): 0.90 ≤ ΔH ≤ 1.05, as well as 135℃ ≤ T1 ≤ 160℃, 165℃ ≤ T2 ≤ 185℃, and 180℃ ≤ T3 ≤ 200℃. ΔH = (H2 + H3) / H1 ... (1) The polymer additive according to the present invention has a specific crystal form transition state, and the polymer molding material to which the polymer additive is added has a lower molding shrinkage rate during molding applications.

Description

Technical Field

[0001] The present invention belongs to the technical field of flame retardants, and more specifically, relates to polymer additives, flame retardants, polymer molding materials, their manufacturing methods, and their applications.

Background Art

[0002] Aluminum diethylphosphinate is a halogen-free and environmentally friendly flame retardant. It has a white powder appearance, is insoluble in water and most organic solvents, but is soluble in strong acid and strong alkali solutions. It has characteristics such as high flame retardancy, high thermal stability, low smoke, small particle size, low specific gravity, excellent dispersibility, and compatibility. Aluminum diethylphosphinate is widely used as an efficient and environmentally friendly halogen-free flame retardant for flame retardant modification of products such as thermoplastic plastics (PA6T, PA10T, PA66, PBT, etc.), fibers, and fabrics.

[0003] The composite systems of aluminum diethylphosphinate are widely used in the field of halogen-free flame-retardant glass fiber reinforced engineering plastics. Examples of such composite systems include aluminum diethylphosphinate-melamine polyphosphate (MPP) composite system, aluminum diethylphosphinate-melamine cyanurate (MCA) composite system, and aluminum diethylphosphinate-aluminum phosphite composite system. These systems have advantages such as high flame retardant efficiency, high temperature resistance, and little reduction in the performance of the resin matrix, so they are widely used.

[0004] In the application process of modified polymer composite materials such as flame retardant modified thermoplastic plastics with aluminum diethylphosphinate, problems often occur such as excessive molding shrinkage rate of the material, inability to properly attach injection molded products, or loosening of assembly, which is particularly prominent in the field of precision injection molded products.

[0005] Chinese patent CN110407869A discloses a monotrifluoropropylphosphinate aluminum flame retardant that reduces the corrosiveness of aluminum diethylphosphinate to screws during the extrusion modification process by combining aluminum monotrifluoropropylphosphinate and aluminum diethylphosphinate. However, this flame retardant does not improve the problem of excessive molding shrinkage of the modified polymer composite material. Chinese patent CN113637193A discloses a nylon thermal insulation strip or reinforced nylon, glass fiber reinforced PA6 / PA66 composite material comprising nylon 6633, aluminum diethylphosphinate, antioxidant, glass fiber, lubricant, maleic anhydride grafted POE toughening agent and additives. The addition of glass fiber strengthens the nylon itself, thereby reducing the water absorption rate of the composite material, decreasing the molding shrinkage of the product, and improving dimensional stability. However, in this proposal, aluminum diethylphosphinate functions only as a flame retardant component, and in its application, it still causes the problem of excessive shrinkage during the molding of the modified polymer composite material. [Overview of the project]

[0006] In view of the above-mentioned conventional technical problems, the first object of the present invention is to provide a polymer additive having a special crystalline form and crystalline structure. When this polymer additive is applied to a polymer, the polymer exhibits a lower molding shrinkage rate.

[0007] To achieve the above objective, the present invention is realized by the following technical solution.

[0008] In the first embodiment, the polymer additive according to the present invention comprises aluminum diethylphosphinate and aluminum ethylbutylphosphinate. The polymer additive satisfies the dual enthalpy ratio ΔH: 0.90 ≤ ΔH ≤ 1.05 defined by the following formula (1), and also satisfies 135℃ ≤ T1 ≤ 160℃, 165℃ ≤ T2 ≤ 185℃, and 180℃ ≤ T3 ≤ 200℃. ΔH=(H2+H3) / H1 (1) The aforementioned H1, H2, H3, T1, T2, and T3 were measured by differential scanning calorimetry (DSC), and the measurement method includes heating the polymer additive from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min in a nitrogen gas atmosphere, maintaining this temperature for 3 minutes, then cooling it down to room temperature at a further rate of 20°C / min to obtain the cooling curve of the polymer additive, maintaining the polymer additive at room temperature for 3 minutes, and then heating it 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. H1 is the peak area formed by the start and end temperatures of the exothermic peak in the cooling curve, the two endothermic peaks in the second heating curve are defined as the first endothermic peak and the second endothermic peak, respectively, from the lower temperature to the higher temperature, H2 is the peak area formed by the start and end temperatures of the first endothermic peak in the second heating curve, and H3 is the peak area formed by the start and end temperatures of the second endothermic peak in the second heating curve. T1 is the peak temperature of the exothermic peak in the cooling curve, T2 is the peak temperature of the first endothermic peak in the second heating curve, and T3 is the peak temperature of the second endothermic peak in the second heating curve.

[0009] Differential scanning calorimetry (DSC) is one of the most commonly used thermal analysis instruments and can be used to represent the melting and crystallization processes of materials, reflecting the relationship between molecular chain structure and crystals. Even in substances that do not melt, clear endothermic and exothermic peaks may appear during DSC measurements, and the difference between these peaks is also related to changes in molecular structure and its crystalline properties. Changes in molecular structure or its crystalline structure directly determine the melting and crystallization behavior during heating or cooling in DSC measurements, as well as the difference between endothermic and exothermic peaks. Furthermore, differences in the molecular structure of a material also affect its workability and mechanical properties during processing, and consequently, its dimensional stability and molding shrinkage rate.

[0010] Research on the present invention has revealed that although the polymer additive according to the present invention does not exhibit melting during the measurement process at 30-300°C, there are significant differences in the endothermic and exothermic peaks depending on the polymer additive. According to the inventors' research, a specific dual-enthalpy ratio and specific peak temperatures (T1, T2, T3) formed in the endothermic and exothermic peaks influence a specific crystal transition state of the polymer additive. In this state, the polymer molding material exhibits a lower molding shrinkage rate, as it provides superior dimensional stability during polymer molding. Polymer molding materials manufactured using polymer additives having such specific crystal transition states have a lower molding shrinkage rate.

[0011] In some embodiments, the peak areas H1, H2, H3 and peak temperatures T1, T2, T3 may be obtained by peak marking and integral calculation of peak areas using conventional methods in the art. For example, they may be obtained by performing peak marking and integral calculation of peak areas using software attached to a DSC instrument. Specifically, in some embodiments, when measured by differential scanning calorimetry (DSC), the weight of the sample of the polymer additive to be measured may be 10 ± 0.5 mg.

[0012] Specifically, in some embodiments, peak areas H1, H2, H3 and peak temperatures T1, T2, T3 can be obtained as average values ​​after multiple integrations or markings (e.g., 1, 2, 3, 4, 5 times, etc.). More specifically, from the viewpoint of improving operational efficiency and ensuring data reproducibility and reliability, peak areas H1, H2, H3 and peak temperatures T1, T2, T3 can each be measured independently 2 to 4 times and obtained as average values.

[0013] In some embodiments, the polymer additive comprises, by weight percentage, 99.01 to 99.99% aluminum diethylphosphinate and 0.01 to 0.99% aluminum ethylbutylphosphinate. More specifically, the content of aluminum diethylphosphinate may be 99.10%, 99.20%, 99.30%, 99.40%, 99.50%, 99.60%, 99.70%, 99.80%, 99.90%, etc., or within a numerical range formed from any of the above values, such as 99.01 to 99.40%, 99.01 to 99.70%, 99.01 to 99.90%, 99.30 to 99.60%, 99.50 to 99.90%, 99.70 to 99.99%, 99.90 to 99.99%, but the present invention is not limited to these. More specifically, the content of aluminum ethylbutylphosphinate may 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 within a numerical range formed from any of 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%, but the present invention is not limited to these.

[0014] In some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist in the form of a physical combination; in some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist in the form of a chemical coprecipitation of ions of formula I and / or formula II; and in some embodiments, aluminum diethylphosphinate and aluminum ethylbutylphosphinate may exist simultaneously in the form of a physical combination and in the form of a chemical coprecipitation of ions of formula I and / or formula II. JPEG2026109610000001.jpg7672

[0015] More specifically, in the present invention, the dual enthalpy ratio ΔH may be 0.92, 0.94, 0.96, 0.98, 0.99, 1.00, 1.02, 1.04, 1.05, or within a numerical range formed from any of the above values, such as 0.92 to 0.98 or 0.96 to 1.05, but the present invention is not limited to these.

[0016] More specifically, in the present invention, T1 may be 135°C, 138°C, 140°C, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C, or within a numerical range formed from any of the above values, such as 140°C to 150°C or 146°C to 154°C, but the present invention is not limited to these.

[0017] More specifically, in the present invention, T2 may be 168°C, 170°C, 172°C, 174°C, 176°C, 178°C, 180°C, 183°C, or within a numerical range formed from any of the above values, such as 174°C to 178°C, but the present invention is not limited to these.

[0018] More specifically, in the present invention, T3 may be 182°C, 184°C, 186°C, 188°C, 190°C, 192°C, 194°C, 196°C, 198°C, etc., or it may be a numerical range formed from any of the above values ​​such as 184°C to 188°C or 190°C to 192°C, but the present invention is not limited to these.

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

[0020] In some embodiments, the polymer additive satisfies the following conditions: 140°C ≤ T1 ≤ 156°C, 172°C ≤ T2 ≤ 178°C, and 184°C ≤ T3 ≤ 192°C.

[0021] In a second aspect, the method for producing the polymer additive according to the present invention is: Under the protection of a nitrogen gas atmosphere, the water-soluble salt of hypophosphorous acid or the acid itself is reacted with an olefin so that 2.00 to 2.05 molecules of olefin are added to the P atom, and step S1 of obtaining an intermediate aqueous solution containing diethylphosphate by reacting the water-soluble salt or acid of hypophosphorous acid with an initiator and an olefin; Step S2 of reacting the intermediate aqueous solution of step S1 with a surfactant and an aluminum salt solution to obtain the polymer additive is included.

[0022] In some embodiments, in step S1, the reaction temperature is 80 to 120 °C.

[0023] In some embodiments, in step S1, the reaction pressure is 0.6 to 2.0 MPa.

[0024] In some embodiments, in step S1, the reaction temperature is adjusted in two stages. In the first stage, the reaction temperature is heated to 80 to 90 °C and maintained for 3.5 to 4.5 hours, and the initiator is continuously replenished during the temperature maintenance process. Subsequently, in the second stage, the reaction temperature is raised to 90 to 100 °C and maintained for 0.5 to 1.5 hours. Or, the reaction temperature is adjusted in two stages. In the first stage, the reaction temperature is heated to 105 to 115 °C and maintained for 3.5 to 4.5 hours, and the initiator is continuously replenished during the temperature maintenance process. Subsequently, in the second stage, the temperature is continuously maintained at 105 to 115 °C for 0.5 to 1.5 hours.

[0025] In some embodiments, in step S2, the mass concentration of diethylphosphate in the intermediate aqueous solution is 15 to 25%, and / or in step S2, the mass concentration of the water-soluble aluminum salt in the aluminum salt solution is 20 to 24%.

[0026] In some embodiments, in step S2, the surfactant is one or more selected from the group consisting of alkyl phosphate esters, alkyl phosphate ester salts, ether alcohol phosphate esters, and ether alcohol phosphate ester salts.

[0027] Specifically, the alkyl phosphate ester or alkyl phosphate ester salt may be selected from alkyl phosphate esters or alkyl phosphate ester salts having 8 to 18 carbon atoms. More specifically, the alkyl phosphate ester includes, but is not limited to, monododecyl phosphate, etc. The alkyl phosphate ester salt includes, but is not limited to, potassium monododecyl phosphate, etc. Specifically, the ether alcohol phosphate ester or ether alcohol phosphate ester salt may be selected from ether alcohol phosphate esters or ether alcohol phosphate ester salts having 8 to 18 carbon atoms. More specifically, the ether alcohol phosphate ester includes, but is not limited to, laureth phosphate, etc. The ether alcohol phosphate ester salt includes, but is not limited to, potassium laureth phosphate, etc.

[0028] In some embodiments, the addition amount of the surfactant is 0.001 to 0.10% by weight of the weight of the intermediate aqueous solution. More preferably, the addition amount of the surfactant is 0.01 to 0.08% by weight of the weight of the intermediate aqueous solution.

[0029] In some embodiments, before adding the surfactant, an alkali solution is further added to the intermediate aqueous solution for neutralization to remove the free acid in the solution. More specifically, it is neutralized until the pH reaches 5 to 6.5.

[0030] In some embodiments, in step S2, the usage amounts of the intermediate aqueous solution and the aluminum salt solution are the same.

[0031] In some embodiments, the aluminum salt solution is added at one time, the reaction temperature is raised to 50 to 60 °C during the addition process of the aluminum salt solution, the addition time of the aluminum salt solution is 90 to 110 minutes, and / or In step S2, the aluminum salt solution is added in two parts: firstly, 15-35% equivalent of the aluminum salt solution is added for 30-40 minutes at a reaction temperature of 35-45°C; and secondly, 65-85% equivalent of the aluminum salt solution is added for 30-40 minutes at a reaction temperature of 55-60°C.

[0032] In some embodiments, the water-soluble salt of hypophosphate may be potassium hypophosphate and / or sodium hypophosphate.

[0033] In some embodiments, the water-soluble aluminum salt may be one or more selected from the group consisting of aluminum oxides, hydroxides, peroxides, sulfates, bisulfates, hydrated sulfates, persulfates, phosphates, and phosphites.

[0034] In a third aspect, a method for producing another polymer additive according to the present invention is: Step S1 involves reacting hypophosphorous acid and an initiator with an olefin such that, under the protection of a nitrogen gas atmosphere, 2.00 to 2.05 molecules of olefin are added to the P atom in one hypophosphorous acid molecule, thereby obtaining an intermediate aqueous solution containing diethylphosphinic acid. Step S2 for producing aluminum hydroxide gel, The process includes step S3, in which an aqueous intermediate solution from step S1 is added dropwise to an aluminum hydroxide gel from step S2 to allow the reaction to proceed, the temperature is raised to 50-60°C and maintained for 0.1-0.5 hours, and then the temperature is further raised to 90-120°C and maintained for 0.5-5 hours to obtain a polymer additive.

[0035] In some embodiments, in step S1, the reaction temperature is adjusted in two stages. In the first stage, the reaction temperature is heated to 75-85°C for 2.5-3.5 hours, during which the initiator is continuously replenished while the temperature is maintained. During the temperature maintenance, a portion of the reactants in the autoclave is introduced into a venturi ejector, and the olefin introduced into the venturi ejector, such as ethylene, is thoroughly mixed with the reactants and then returned to the autoclave via external circulation. Subsequently, in the second stage, the temperature is maintained at 75-85°C for 0.5-1.5 hours.

[0036] In some embodiments, the reaction temperature for manufacturing in step S2 is 10 to 20°C.

[0037] In some embodiments, in step S3, the temperature is raised to 50-60°C at a heating rate of 2-10°C / h, and / or In some embodiments, in step S3, the temperature is raised to 90-120°C at a heating rate of 11-25°C / h.

[0038] In some embodiments, in step S3, the molar ratio of diethylphosphinic acid to aluminum ions in the aluminum hydroxide gel is 3:1 to 1.01.

[0039] In some embodiments, the olefin may be at least one selected from the group consisting of ethylene, propylene, 1-butylene, 2-butylene, 1-pentene, 1-hexene, or 1-octene.

[0040] In some embodiments, the initiator is one or more selected from the group consisting of organic peroxides, inorganic peroxides, and azo compounds. More specifically, the inorganic peroxide may be one or more selected from the group consisting of sodium persulfate, ammonium persulfate, and potassium persulfate. The organic peroxide may be one or more selected from the group consisting of perbenzoic acid, perlauric acid, di-tert-butyl peroxide, percarbonate ester, peracetic acid, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, and tert-butyl peroxy 2-ethylhexanoate. The azo compound may be one or more selected from the group consisting of azobisisobutyronitrile and azobisisoheptanitrile.

[0041] In a fourth aspect, the present invention provides the use of the above-mentioned polymer additive in reducing the shrinkage rate of the polymer.

[0042] In a fifth aspect, the present invention provides the use of the polymer additive as a reactive or non-reactive flame retardant in at least one polymer, varnish, foaming paint, wood, and other cellulose-containing products, or the use of the polymer additive in the manufacture of flame-retardant polymer molding materials or flame-retardant polymer molded articles, or for imparting flame retardancy to polyester fabrics and / or pure cellulose fabrics and / or blended cellulose fabrics by impregnation.

[0043] In some embodiments, the polymer additive is used in combination with a synergist, the synergist being one or more selected from the group consisting of 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, melam polyphosphate, melem polyphosphate, and melon polyphosphate; or the synergist being melamine condensation products, melam, melem, and / or melon; or the synergist being one or more selected from the group consisting of oligoesters of tri(hydroxyethyl) isocyanurate / salt and aromatic polycarboxylic acid, benzoguanamine, tri(hydroxyethyl) isocyanurate / salt, allantoin, glycoluryl, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, and guanidine; or the synergist being of formula (NH4) y H 3-y PO4 and / or (NH4PO3) z The synergistic agent is a nitrogen-containing phosphate represented by the formula (wherein y is 1 to 3 and z is 1 to 10000), or the synergistic agent is aluminum phosphite and / or aluminum pyrosphite, or the synergistic agent is one or more selected from the group consisting of zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, and magnesium carbonate, or the synergistic agent is one or more selected from the group consisting of salts of ethylphosphonic acid, salts of butylphosphonic acid, salts of n-butylphosphonic acid, salts of sec-butylphosphonic acid, and salts of hexylphosphonic acid.

[0044] In some embodiments, the polymer additive is used in combination with other additives, the other additive being at least one selected from the group consisting of antioxidants, UV stabilizers, gamma-ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact resistance modifiers, dyes, and pigments.

[0045] In some embodiments, 0.0001 to 99.7999% by weight of the polymer additive, 0.1 to 40% by weight of a synergistic agent, and 0.1 to 40% by weight of other additives are used.

[0046] In a sixth aspect, the present invention provides a flame-retardant thermoplastic or thermosetting polymer composite material, which is at least one selected from the group consisting of flame-retardant thermoplastic or thermosetting polymer molding materials, flame-retardant thermoplastic or thermosetting polymer molded articles, flame-retardant thermoplastic or thermosetting polymer films, flame-retardant thermoplastic or thermosetting polymer yarns, and flame-retardant thermoplastic or thermosetting polymer fibers, comprising 0.5 to 45% by weight of the polymer additive, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of a synergistic agent, and 0 to 55% by weight of a filler or reinforcing material.

[0047] In some embodiments, the thermoplastic or thermosetting polymer is one or more selected from the group consisting of polyester, polyamide, thermoplastic elastomer, thermoplastic polyurethane, thermoplastic polyester elastomer, styrene polymer, polyketone, polyolefin, and polyacrylate.

[0048] In some embodiments, the polyolefin may be a polymer of monoenes and / or dienes such as polypropylene, polyisobutylene, poly-1-butylene, poly-4-methyl-1-pentene, polyisoprene, or polybutadiene, or the polyolefin may be a polymer of cycloolefins such as cyclopentene or norbornene. Specifically, the polyolefin may be polyethylene (crosslinkable as needed), such as high-density polyethylene (HDPE), high-density-high molecular weight polyethylene (HDPE-HMW), high-density-ultra-high molecular weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), and mixtures thereof.

[0049] Polyolefins may also be copolymers of monoenes and dienes, or copolymers of other ethylenic monomers, such as ethylene-propylene copolymers, copolymers of linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE), propylene-1-butylene copolymers, propylene-isobutylene copolymers, ethylene-1-butylene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and copolymers thereof with carbon monoxide, ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene, propylene, and dienes (e.g., hexadiene, dicyclopentadiene, or ethylidene norbornene). Furthermore, the polyolefin may be a mixture of the aforementioned polymers or copolymers, for example, polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer, LDPE / ethylene-acrylic acid copolymer, LLDPE / ethylene-vinyl acetate copolymer, LLDPE / ethylene-acrylic acid copolymer, and alternating or statistically configured polyalkylene / carbon monoxide copolymer. Alternatively, the polyolefin may be a mixture of the aforementioned polymers or copolymers with other polymers such as polyamides.

[0050] In some embodiments, the styrene-based polymer may be a copolymer of styrene or α-methylstyrene with a diene or acrylic acid derivative, such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-alkyl methacrylate copolymer, styrene-butadiene-alkyl acrylate copolymer, styrene-butadiene-alkyl methacrylate copolymer, styrene-maleic anhydride copolymer, or styrene-acrylonitrile-methyl acrylate copolymer. Alternatively, the styrene-based polymer may be a high-impact mixture of the styrene copolymer and another polymer (e.g., polyacrylate, a diene polymer, or an ethylene-propylene-diene ternary copolymer). Furthermore, the styrene-based polymer may be a block copolymer of styrene, such as styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, or styrene-ethylene / propylene-styrene block copolymer.

[0051] In some embodiments, the styrene-based polymer may be a graft copolymer of styrene or α-methylstyrene, or a mixture thereof. For example, the styrene-based polymer may be a graft copolymer in which styrene is grafted onto polybutadiene, a graft copolymer in which styrene is grafted onto polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, a graft copolymer in which styrene and acrylonitrile (or methylacrylonitrile) are grafted onto polybutadiene, a graft copolymer in which styrene, acrylonitrile and methyl methacrylate are grafted onto polybutadiene, a graft copolymer in which styrene and maleic anhydride are grafted onto polybutadiene, a graft copolymer in which styrene, acrylonitrile and maleic anhydride or maleimide are grafted onto polybutadiene, These may be graft copolymers in which styrene and alkyl acrylate or alkyl methacrylate are grafted onto polybutadiene, graft copolymers in which styrene and acrylonitrile are grafted onto ethylene-propylene-diene ternary copolymer, graft copolymers in which styrene and acrylonitrile are grafted onto polyalkyl acrylate or polyalkyl methacrylate, graft copolymers in which styrene and acrylonitrile are grafted onto acrylate-butadiene copolymer, acrylonitrile-butadiene-styrene (ABS) polymer, methyl methacrylate-butadiene-styrene (MBS) polymer, acrylonitrile-styrene-butyl acrylate (ASA) polymer, or acrylonitrile-ethylene-styrene (AES) polymer.

[0052] In some embodiments, the polyamide may be (1) a polyamide or copolyamide derived from a diamine and a dicarboxylic acid, and / or (2) a polyamide or copolyamide derived from an aminocarboxylic acid and a corresponding lactam, for example, polycaprolactam (PA6), poly(hexamethyleneadipamide) (PA66), and polytetramethyleneadipamide (polyamide 46 or PA46). Furthermore, the polyamide may be an aromatic polyamide derived from m-xylene, diamine, and adipic acid, or a polyamide produced from hexamethylenediamine, isophthalic acid and / or terephthalic acid, and an elastomer as an optional modifier (e.g., poly(hexamethylene isophthalamide), poly(hexamethylene teraphthalamide), poly-2,4,4-trimethylhexamethylene terephthalamide, or poly(m-phenylene isophthalamide)). The polyamide may also be a block copolymer of a polyamide with a polyolefin, olefin copolymer, ionomer, or chemically bonded or grafted elastomer, or a block copolymer of a polyamide with a polyether such as polyethylene glycol, polypropylene glycol, or polybutylene glycol.

[0053] In some embodiments, the polyester may be a polyester derived from dicarboxylic acids and diols, and / or from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dihydroxymethylcyclohexane terephthalate, and polyhydroxybenzoic acid esters. Alternatively, the polyester may be a block polyether ester derived from a polyether containing a hydroxy-terminated group, or a polyester modified from polycarbonate or methyl butadiene styrene ternary copolymer (MBS).

[0054] In some embodiments, the filler or reinforcing material may be (1) a silicon-oxygen-containing compound, (2) a compound of a metal in Group 2 of the periodic table, specifically a magnesium compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrotalcite, magnesium carbonate or magnesium calcium carbonate, or a calcium compound such as calcium hydroxide, calcium oxide or hydrocalmite, (3) an aluminum compound such as aluminum oxide, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, and / or (4) red phosphorus, a zinc compound, or glass fiber. [Effects of the Invention]

[0055] Compared to the prior art, the present invention has the following beneficial effects.

[0056] The present invention provides a polymer additive having specific ΔH, T1, T2, and T3. When the above parameters are within the above specific range, the polymer additive has a specific crystal form transition state, and the polymer molding material to which the polymer additive is added has a lower molding shrinkage rate during molding applications. [Modes for carrying out the invention]

[0057] The present invention will be further described below with reference to the drawings and specific examples, but these examples are not intended to limit the present invention. Unless otherwise specified, the reagents, methods, and apparatus used in the present invention are common reagents, methods, and apparatus in the art.

[0058] The raw materials used in the examples and comparative examples are as follows: Glass fiber: ECS10-03-568H, manufactured by Jushi Gufun Co., Ltd. Base resin 1: PA66, EPR24, manufactured by Henan Jinba Co., Ltd. Base resin 2: PBT, GX121, manufactured by Yizheng Chemical Co., Ltd. Base resin 3: PA6, M2000, manufactured by Guangdong Xinhui Meida Co., Ltd. Synergistic agent 1: Melamine polyphosphate, MPP, Budit 3141, Budenheim. Synergist 2: Zinc borate, ZB-503, manufactured by Anhui Shitong Material Technology Co., Ltd. Synergistic agent 3: Aluminum phosphite, commercially available. Sodium hypophosphate monohydrate, commercially available product. Sodium persulfate, commercially available. Aluminum sulfate, commercially available. Dodecyl phosphate, commercially available. Laureth phosphate, commercially available product. Potassium laureth phosphate, commercially available product.

[0059] Unless otherwise specified, all components used in each parallel example and comparative example are the same commercially available products.

[0060] Example 1: Polymer Additive (1) 318 g of solid sodium hypophosphate monohydrate, 400 g of water, and 2 g of tert-butyl=2-ethylperoxyhexanoate were placed in an autoclave. The air in the autoclave was replaced five times with nitrogen gas to introduce ethylene into the autoclave. The ethylene in the autoclave was kept at a constant pressure of 0.6 MPa using a vacuum valve, heated to 85°C, and maintained at this temperature for 4 hours. During this 4-hour temperature maintenance, 4 g of tert-butyl=2-ethylperoxyhexanoate was continuously added. After that, the temperature was maintained at 95°C for 1 hour, cooled, and evacuated to obtain an intermediate aqueous solution containing sodium diethylphosphinate. (2) In the intermediate aqueous solution containing sodium diethylphosphinate obtained in step (1), a 20% by weight sodium hydroxide aqueous solution was added to neutralize the free acid until the pH was 6, water was added to dilute the solution so that the mass concentration of sodium diethylphosphinate was 20%, and 0.03% (amount added based on the weight of the diluted sodium diethylphosphinate aqueous solution) of dodecyl phosphate was added, and 1 / 6 equivalent (based on the molar amount of sodium diethylphosphinate) of a 20% mass aqueous aluminum sulfate aqueous solution was added dropwise at 40°C for 40 minutes. The temperature was raised to 55°C, and the remaining 5 / 6 equivalent (based on the molar amount of sodium diethylphosphinate) of a 20% mass aqueous aluminum sulfate aqueous solution was added dropwise for 40 minutes. Furthermore, cooling and filtration were carried out sequentially, the filtered cake was washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until it reached a constant weight to obtain the polymer additive.

[0061] Example 2 Polymer Additive (1) 318 g of solid sodium hypophosphite monohydrate, 400 g of water, and 2 g of sodium persulfate were placed in an autoclave. The air in the autoclave was replaced five times with nitrogen gas to introduce ethylene into the autoclave. The ethylene in the autoclave was kept at a constant pressure of 1.5 MPa using a vacuum valve, and the autoclave was heated to 110°C and maintained at that temperature for 4 hours. During this 4-hour period, a solution consisting of 4 g of sodium persulfate and 36 g of water was continuously added. After that, the temperature was maintained at 110°C for 1 hour, cooled, and evacuated to obtain an intermediate aqueous solution containing sodium diethylphosphinate. (2) Adding a 20% by weight sodium hydroxide aqueous solution to the intermediate aqueous solution containing sodium diethylphosphinate obtained in step (1) neutralizes the free acid to pH=6, and dilutes with water to a mass concentration of 20% sodium diethylphosphinate. Add 0.02% (amount added based on the weight of the diluted sodium diethylphosphinate aqueous solution) of laureth phosphate, and add 1 / 6 equivalent (based on the molar amount of sodium diethylphosphinate) of a 20% by mass aqueous solution of aluminum sulfate dropwise at 35°C for 40 minutes. The temperature is raised to 55°C, and the remaining 5 / 6 equivalent (based on the molar amount of sodium diethylphosphinate) of a 20% by mass aqueous solution of aluminum sulfate dropwise for 30 minutes. Further cooling and filtration are carried out sequentially, the filtered cake is washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until it reaches a constant weight to obtain the polymer additive.

[0062] Example 3 Polymer Additive This embodiment differs from Embodiment 1 in step (2). Step (2) of Embodiment 3 was as follows: (2) Adding a 20% by weight sodium hydroxide aqueous solution to the intermediate aqueous solution containing sodium diethylphosphinate obtained in step (1) neutralizes the free acid to pH=6, and dilutes with water to a mass concentration of 20% sodium diethylphosphinate. Add 0.04% (amount added on a weight basis of the diluted sodium diethylphosphinate aqueous solution) of laureth phosphate, and add 1 / 3 equivalent (on a molar basis of sodium diethylphosphinate) of a 20% by mass aqueous solution of aluminum sulfate dropwise at 35°C for 40 minutes. The temperature is raised to 55°C, and the remaining 2 / 3 equivalent (on a molar basis of sodium diethylphosphinate) of a 20% by mass aqueous solution of aluminum sulfate dropwise for 20 minutes. Further cooling and filtration are carried out sequentially, the filtered cake is washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until it reaches a constant weight to obtain the polymer additive.

[0063] Example 4 Polymer Additive This embodiment differs from Embodiment 2 in step (2). Step (2) of Embodiment 4 was as follows: (2) To the intermediate aqueous solution containing sodium diethylphosphinate obtained in step (1), a 20% by weight sodium hydroxide aqueous solution was added to neutralize the free acid until the pH was 6. Water was added to dilute the solution so that the mass concentration of sodium diethylphosphinate was 22%, and 0.05% (amount added on a weight basis of the diluted sodium diethylphosphinate aqueous solution) of potassium laureth phosphate was added. At 30°C, 1 equivalent (on a molar basis of sodium diethylphosphinate) of a 22% mass concentration aluminum sulfate aqueous solution was added dropwise, and the temperature was slowly raised to 60°C at a heating rate of 4°C / 10 minutes, with a total adding time of 100 minutes. Further cooling and filtration were carried out sequentially, the filtered cake was washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until a constant weight was obtained to obtain the polymer additive.

[0064] Example 5 Polymer Additive (1) 396 g of a 50% mass phosphinic acid aqueous solution was placed in an autoclave, the air inside the autoclave was replaced five times with nitrogen gas at 0.6 MPa, and ethylene was introduced so that the ethylene pressure inside the autoclave reached 1.0 MPa. The mixture was heated to 80°C while stirring and maintained at this temperature for 3 hours. During this 3-hour temperature maintenance, 40 g of a 10% mass sodium persulfate aqueous solution was continuously replenished. Also, during the temperature maintenance, the substance was introduced into the liquid inlet of the venturi ejector by centrifugal pump through a valve at the bottom of the tank, and ethylene gas from the upper layer of the autoclave was introduced from the gas inlet of the venturi ejector. Both the gas phase and the liquid phase were thoroughly mixed and entered the autoclave by external circulation. Ethylene was introduced from the gas inlet of the venturi ejector, and the ethylene consumed in the reaction was replenished to stabilize the autoclave pressure at 1.0 MPa. After the initiator replenishment was complete, the temperature was maintained at 80°C for 1 hour, then cooled and evacuated to obtain an aqueous solution containing diethylphosphinic acid. (2) At 20°C, an aqueous sodium hydroxide solution was prepared using 60 g of sodium hydroxide and 1140 g of water. Over 1.5 hours, the aqueous sodium hydroxide solution was slowly added dropwise to an aqueous aluminum sulfate solution consisting of 333 g of aluminum sulfate 18-hydrate and 777 g of water to obtain an aluminum hydroxide gel. (3) Over 3 hours, aluminum hydroxide gel was continuously added dropwise to an aqueous solution containing diethylphosphinic acid (molar ratio of diethylphosphinic acid to aluminum ions: 3:1). The temperature was then raised to 60°C at a rate of 5°C / h and maintained for 0.5 hours. The temperature was then raised to 100°C at a rate of 20°C / h and maintained for 0.5 hours. Cooling and filtration were then carried out sequentially. The filtered cake was washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until a constant weight was obtained to obtain the polymer additive.

[0065] Example 6 Polymer Additive This embodiment differs from Embodiment 5 in steps (2) and (3). Steps (2) and (3) of Embodiment 6 were as follows: (2) At 10°C, an aqueous sodium hydroxide solution was prepared using 60 g of sodium hydroxide and 1140 g of water. Over 1.5 hours, the aqueous sodium hydroxide solution was slowly added dropwise to an aqueous aluminum sulfate solution consisting of 333 g of aluminum sulfate 18-hydrate and 777 g of water to obtain an aluminum hydroxide gel. (3) Over 3 hours, aluminum hydroxide gel was continuously added dropwise to an aqueous solution containing diethylphosphinic acid (molar ratio of diethylphosphinic acid to aluminum ions: 3:1). The temperature was then raised to 60°C at a rate of 10°C / h and maintained for 0.5 hours. The temperature was then raised to 100°C at a rate of 20°C / h and maintained for 0.5 hours. Cooling and filtration were then carried out sequentially. The filtered cake was washed three times with water equal to three times the weight of the filtered cake, and then dried at 120°C until a constant weight was obtained to obtain the polymer additive.

[0066] Comparative Example 1 Conventional polymer additive 1 (XHPFR-1040, manufactured by Zhejiang Xinhua Chemical Co., Ltd.) was used.

[0067] Comparative Example 2 Conventional polymer additive 2 (ADP-30, manufactured by Lanzhou Ruipu Technology Co., Ltd.) was used.

[0068] Measurement example (1) Dissolve the polymer additives produced in Examples 1 to 6 and the polymer additives of Comparative Examples 1 to 2 in a sodium hydroxide aqueous solution, 31 The P-NMR spectrum was measured. (i) Equipment: Nuclear magnetic resonance spectrometer (Bruker 400M). (ii) Reagent: 10% by weight sodium hydroxide aqueous solution. (iii) Experimental method: Approximately 0.1 g (with an accuracy of 0.0001 g) of the sample to be measured was weighed, 5 g of sodium hydroxide aqueous solution was added, and it was dissolved by ultrasound. The solution was transferred to an NMR tube, and the NMR tube was placed in a nuclear magnetic resonance spectrometer and scanned to obtain an NMR spectrum. The integral values ​​of aluminum diethylphosphinate and aluminum ethylbutylphosphinate in the NMR spectrum were determined, and the molar percentages of each were obtained. After conversion, the mass percentages of each were determined.

[0069] The measurement results for polymer additives are shown in Table 1 below, expressed as mass percentages.

[0070] Table 1 JPEG2026109610000002.jpg40167

[0071] (2) The polymer additives produced in Examples 1 to 6 and the polymer additives of Comparative Examples 1 to 2 were measured by differential scanning calorimetry (DSC) (DSC 214, NETZSCH DSC 204 F1, Germany). The measurement method was 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, maintained at this temperature for 3 minutes, and then cooled back down to room temperature at a further rate of 20°C / min to obtain the cooling curve of the polymer additive. The polymer additive was maintained at room temperature for 3 minutes, and then 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.

[0072] Here, H1 is the peak area formed by the start and end temperatures of the exothermic peak in the cooling curve, the two endothermic peaks in the second heating curve are defined as the first endothermic peak and the second endothermic peak, respectively, from the lower temperature to the higher temperature, H2 is the peak area formed by the start and end temperatures of the first endothermic peak in the second heating curve, and H3 is the peak area formed by the start and end temperatures of the second endothermic peak in the second heating curve. In Table 2 below, ΔH = (H2 + H3) / H1, T1 is the peak temperature of the exothermic peak in the cooling curve, T2 is the peak temperature of the first endothermic peak in the second heating curve, and T3 is the peak temperature of the second endothermic peak in the second heating curve.

[0073] The peak temperatures and peak areas mentioned above were marked and calculated using the software included with the NETZSCH DSC 204 F1.

[0074] The measurement data for the polymer additives in Examples 1-6 and Comparative Examples 1-2 are shown in Table 2 below.

[0075] Table 2 JPEG2026109610000003.jpg102160

[0076] (3) The polymer additives of Examples 1-6 and Comparative Examples 1-2 were used as flame retardants, kneaded with synergistic agents, glass fibers, and base resins, and extruded to obtain polymer molding materials. The amounts of each component used in Examples 7-16 and Comparative Examples 3-5 are shown in Table 3.

[0077] Table 3 JPEG2026109610000004.jpg114165

[0078] The molding shrinkage rates of the polymer molding materials produced in Examples 7-16 and Comparative Examples 3-5 were measured. The measurement method followed GB / T 15585-1995, measuring the shrinkage rate 48 hours after the completion of molding. The measurement results are shown in Table 4 below.

[0079] Table 4 JPEG2026109610000005.jpg81128

[0080] From the data of Examples 7-16 and Comparative Examples 3-5, it was found that polymer molding materials with the polymer additive of the present invention have lower molding shrinkage rates during molding and application. The lateral shrinkage rate of the polymer molding materials with the polymer additive of the present invention was ≤0.81%, and the longitudinal shrinkage rate was ≤0.29%.

[0081] Examples 7, 13, and 14 show that even when different synergistic agents are used in the polymer molding material, good molding shrinkage rates can be achieved in all cases. Examples 7, 15, and 16 show that polymer molding materials manufactured using different base resins can all achieve good molding shrinkage rates.

[0082] From Examples 7-12, Comparative Examples 3 and 4, it was found that when the dual enthalpy ratio ΔH of the polymer additive of the present invention, and T1, T2, and T3 are within a specific range, the lateral and longitudinal shrinkage rates of the polymer molding material to which the polymer additive of the present invention is added are significantly reduced.

[0083] The embodiments described above are merely illustrative and are used to illustrate some features of the method of the present invention. The appended claims are intended to cover as broad a range as possible, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Accordingly, the applicant's intent is that the appended claims are not limited by the selection of embodiments to illustrate the features of the invention. Certain numerical ranges used in the claims include subranges therewith, and any changes within these ranges should be interpreted as being covered by the appended claims as far as possible.

Claims

1. A polymer additive comprising aluminum diethylphosphinate and aluminum ethylbutylphosphinate, The polymer additive satisfies the dual enthalpy ratio ΔH defined by the following formula (1): 0.90 ≤ ΔH ≤ 1.05, and also satisfies 135°C ≤ T1 ≤ 160°C, 165°C ≤ T2 ≤ 185°C, and 180°C ≤ T3 ≤ 200°C. ΔH=(H2+H3) / H1 (1) The aforementioned H1, H2, H3, T1, T2, and T3 were measured by differential scanning calorimetry (DSC), and the measurement method includes heating the polymer additive in a nitrogen atmosphere from room temperature to a maximum temperature of 300°C at a heating rate of 20°C / min, maintaining this temperature for 3 minutes, then cooling it down to room temperature at a further rate of 20°C / min to obtain the cooling curve of the polymer additive, maintaining the polymer additive at room temperature for 3 minutes, and then heating it 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. H1 is the peak area formed by the start and end temperatures of the exothermic peak in the cooling curve, the two endothermic peaks in the second heating curve are defined as the first endothermic peak and the second endothermic peak, respectively, from the lower temperature to the higher temperature, H2 is the peak area formed by the start and end temperatures of the first endothermic peak in the second heating curve, and H3 is the peak area formed by the start and end temperatures of the second endothermic peak in the second heating curve. T1 is the peak temperature of the exothermic peak in the cooling curve, T2 is the peak temperature of the first endothermic peak in the second heating curve, and T3 is the peak temperature of the second endothermic peak in the second heating curve. A polymer additive characterized by the following features.

2. The polymer additive according to claim 1, characterized by containing 99.01 to 99.99% by weight of aluminum diethylphosphinate and 0.01 to 0.99% of aluminum ethylbutylphosphinate.

3. Aluminum diethylphosphinate and aluminum ethylbutylphosphinate exist in the form of a physical combination, and / or Aluminum diethylphosphinate and aluminum ethylbutylphosphinate exist in the form of chemical coprecipitations of ions of formula I and / or formula II. The polymer additive according to claim 1, characterized in that

4. The polymer additive satisfies the dual enthalpy ratio ΔH: 0.92 ≤ ΔH ≤ 1.05, and / or The polymer additive according to claim 1, characterized in that the polymer additive satisfies 140°C ≤ T1 ≤ 156°C, 172°C ≤ T2 ≤ 178°C, and 184°C ≤ T3 ≤ 192°C.

5. A method for producing a polymer additive according to any one of claims 1 to 4, wherein the production method is the first method or the second method. Among them, the first method is, Step S1 involves reacting a water-soluble salt of hypophosphorous acid or an acid, an initiator, with an olefin such that 2.00 to 2.05 molecules of olefin are added to one P atom of the water-soluble salt of hypophosphorous acid or the acid itself, under the protection of a nitrogen gas atmosphere, to obtain an intermediate aqueous solution containing diethylphosphinate. Step S2 involves reacting the intermediate aqueous solution and surfactant from step S1 with an aluminum salt solution to obtain the polymer additive, Includes, The second method is, Step S1 involves reacting hypophosphorous acid and an initiator with an olefin such that, under the protection of a nitrogen gas atmosphere, 2.00 to 2.05 molecules of olefin are added to the phosphorus atom of one hypophosphorous acid molecule, thereby obtaining an intermediate aqueous solution containing diethylphosphinic acid. Step S2 for producing aluminum hydroxide gel, Step S3 involves adding the intermediate aqueous solution from step S1 dropwise to the aluminum hydroxide gel from step S2 and allowing it to react, raising the temperature to 50-60°C and maintaining the temperature for 0.1-0.5 hours, then raising the temperature further to 90-120°C and maintaining the temperature for 0.5-5 hours to obtain a polymer additive. A manufacturing method characterized by including

6. In step S1 of the first method, the reaction temperature is 80 to 120°C, and / or In step S1 of the first method, the reaction pressure is 0.6 to 2.0 MPa, and / or In step S2 of the first method, the mass concentration of diethylphosphinate in the intermediate aqueous solution is 15-25%, and / or, In step S2 of the first method, the mass concentration of the water-soluble aluminum salt in the aluminum salt solution is 20-24%, and / or In step S2 of the first method, the surfactant is one or more selected from the group consisting of alkyl phosphate esters, alkyl phosphate salts, ether alcohol phosphate esters, and / or ether alcohol phosphate salts. In step S2 of the first method, the aluminum salt solution is added all at once, the temperature is raised to 50-60°C during the addition process, and the addition time is 90-110 minutes; or, in step S2, the aluminum salt solution is added in two parts: firstly, 15-35% equivalent of the aluminum salt solution is added, the addition time is 30-40 minutes, and the temperature is 35-45°C; and secondly, 65-85% equivalent of the aluminum salt solution is added, the addition time is 30-40 minutes, and the temperature is 55-60°C. The manufacturing method according to claim 5, characterized in that

7. An anti-shrinkage agent for reducing the shrinkage rate of a polymer, comprising a polymer additive according to any one of claims 1 to 4.

8. A flame retardant comprising a polymer additive according to any one of claims 1 to 4, wherein the flame retardant is used in at least one of the following: (1) Flame retardant to at least one of polymers, varnishes, foamed paints, wood and other cellulose-containing products, as reactive and / or non-reactive; (2) Manufacturing flame-retardant polymer molding materials or flame-retardant polymer molded articles; (3) To impart flame retardancy to polyester fabrics and / or pure cellulose fabrics and / or blended cellulose fabrics by impregnation.

9. A flame retardant according to claim 8, The aforementioned polymer additive is used in combination with a synergistic agent. The synergistic agent is one or more selected from the group consisting of 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, melam polyphosphate, melem polyphosphate, and melon polyphosphate, or The synergistic agent is a melamine condensation product, which is melam, melem, and / or melon, or The synergistic agent is one or more selected from the group consisting of tri(hydroxyethyl) isocyanurate / salt oligoesters of aromatic polycarboxylic acids, benzoguanamine, tri(hydroxyethyl) isocyanurate / salt, allantoin, glycoluryl, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, and guanidine, or The synergistic agent is given by formula (NH ４ ) ｙ H ３－ｙ PO ４ and / or (NH ４ PO ３ ) ｚ A nitrogen-containing phosphate represented by (wherein y is 1 to 3 and z is 1 to 10000), or The synergistic agent is aluminum phosphite and / or aluminum pyrosphite, or The synergistic agent is one or more selected from the group consisting of zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, magnesium hydroxide, hydrotalcite, and magnesium carbonate, or The synergistic agent is one or more selected from the group consisting of salts of ethylphosphonic acid, butylphosphonic acid, n-butylphosphonic acid, sec-butylphosphonic acid, and hexylphosphonic acid, and / or The polymer additive is used in combination with other additives, the other additive being at least one selected from the group consisting of antioxidants, UV stabilizers, gamma-ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, softeners, processing aids, impact resistance modifiers, dyes, and pigments, and / or Using 0.0001 to 99.7999% by weight of the polymer additive, 0.1 to 40% by weight of a synergistic agent, and 0.1 to 40% by weight of other additives, A flame retardant characterized by the following features.

10. A flame-retardant thermoplastic or thermosetting polymer composite material, The flame-retardant thermoplastic or thermosetting polymer composite material is at least one selected from the group consisting of flame-retardant thermoplastic or thermosetting polymer molding materials, flame-retardant thermoplastic or thermosetting polymer molded articles, flame-retardant thermoplastic or thermosetting polymer films, flame-retardant thermoplastic or thermosetting polymer yarns, and flame-retardant thermoplastic or thermosetting polymer fibers. A polymer additive according to any one of claims 1 to 4 in an amount of 0.5 to 45% by weight, a thermoplastic or thermosetting polymer or a mixture thereof in an amount of 0.5 to 95% by weight, a synergistic agent in an amount of 0 to 55% by weight, and a filler or reinforcing material in an amount of 0 to 55% by weight. A flame-retardant thermoplastic or thermosetting polymer composite material characterized by the above.

11. A flame-retardant thermoplastic or thermosetting polymer composite material according to claim 10, A flame-retardant thermoplastic or thermosetting polymer composite material, characterized in that the thermoplastic or thermosetting polymer is at least one selected from the group consisting of polyester, polyamide, thermoplastic elastomer, thermoplastic polyurethane, thermoplastic polyester elastomer, styrene-based polymer, polyketone, polyolefin, and polyacrylate.

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