Polymer additive and application thereof

Abstract

The invention relates to the field of additives, in particular to a polymer additive and application thereof, which are used for solving the problem that the existing dialkyl phosphinate is insufficient in flame retardant efficiency and contradictory in mechanical property in practical application. Diethyl phosphinate, dialkyl phosphinate, alkyl phosphinate, alkyl phosphinate and phosphite are reasonably compounded to prepare the polymer additive, so that the polymer additive has excellent and efficient flame retardance and also can be endowed with excellent compatibility, the polymer additive is used in a polymer material, and the flame retardance of the polymer material is improved. According to the present invention, with the flame retardant, the polymer material containing the flame retardant can have advantages of excellent flame retardant property, good toughness, high impact strength and excellent mechanical property under the condition of the small addition amount.

Description

Technical Field

[0001] This invention relates to the field of additives, and more specifically to a polymer additive and its application. Background Technology

[0002] Dialkylphosphinates (such as aluminum diethylphosphinate) are important halogen-free flame retardants. Due to their good flame retardant properties, low smoke, high CTI (tracking index), environmental friendliness, and relatively small impact on the physical and electrical properties of the matrix polymer, they are widely used in polymers such as polyamide (PA), polyester (such as PBT, PET), polyolefin, and polyurethane. In particular, the demand is strong in the fields of electrical appliances and energy storage.

[0003] Because dialkyl phosphines have low flame retardant efficiency when used alone, they usually need to be used in combination with other flame retardants. For example, CN109694568A discloses a halogen-free flame-retardant polyamide composite, comprising the following components: 40%-90% polyamide resin, 2%-25% organic phosphines flame retardant, 1%-40% melamine flame retardant, 1%-10% phosphate ester flame retardant, 0-45% reinforcing agent, and 0.1%-3% other additives. In this polyamide composite, phosphate ester flame retardants, melamine flame retardants, and organic phosphines flame retardants are used together to obtain good flame retardant properties. CN112724618A discloses a halogen-free flame-retardant reinforced PBT material, comprising the following components: PBT 45%-55%, coupling agent 0.1%-0.5%, composite toughening agent 2%-5%, composite flame retardant 15%-25%, antioxidant 0.3%-1.5%, and lubricant 0.1%-0.6%. The composite flame retardant is prepared by compounding a halogen-free flame retardant and a synergistic flame retardant in a certain proportion. The halogen-free flame retardant is aluminum diethylphosphinate and melamine polyphosphate, and the synergistic flame retardant is zinc borate. The compounding of the three flame retardants improves the flame retardant effect.

[0004] However, dialkylphosphinates face a dilemma in practical applications: insufficient flame retardant efficiency contradicts their mechanical properties. When used alone, their flame retardant efficiency is limited, typically requiring high addition levels (>15-25 wt%) or compounding with other flame retardants (such as melamine polyphosphate, phosphate esters, zinc borate, etc.) to achieve the desired flame retardant rating (e.g., UL94 V-0). Furthermore, dialkylphosphinates and other flame retardants exhibit poor compatibility with most organic polymers, resulting in weak interfacial bonding. This leads to uneven dispersion in the matrix, affecting not only flame retardant efficiency but also degrading mechanical properties, significantly worsening key polymer mechanical properties, particularly toughness, impact strength, and flowability. Summary of the Invention

[0005] In order to overcome the above-mentioned technical problems, the present invention aims to provide a polymer additive and its application, which solves the problem that existing dialkylphosphinates have insufficient flame retardant efficiency and contradictory mechanical properties in practical applications.

[0006] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a polymer additive comprising the following components in parts by weight: 35-90 parts of diethylphosphonate, 5-63 parts of dialkylphosphonate, 0.1-6.3 parts of alkylphosphonate, 0.1-2.0 parts of alkylphosphonate, and 0-25 parts of phosphite; The diethylphosphonate includes any one or a combination of at least two of the metal salts and non-metal salts of diethylphosphonate. The molecular structure of the dihydrophosphine salt is shown below: Wherein, R1 and R2 are any one of substituted or unsubstituted C2 and / or C4 straight-chain or branched alkyl groups, substituted or unsubstituted C6 cycloalkyl groups, and substituted or unsubstituted C6 aryl groups; M1 m+ This represents an ion with a +m valence, where m is an integer from 2 to 4; The molecular structure of the hydrocarbon-based phosphonate is shown below: Wherein, R3 is any one of substituted or unsubstituted C2 and / or C4 straight-chain or branched alkyl, substituted or unsubstituted C6 cycloalkyl, or substituted or unsubstituted C6 aryl; M2 n+ This represents an ion with a +n valence, where n is an integer from 2 to 4; The molecular structure of the hydrocarbon phosphonate is shown below: Wherein, R4 is any one of a substituted or unsubstituted C2 and / or C4 straight-chain or branched alkyl group, a substituted or unsubstituted C6 cycloalkyl group, or a substituted or unsubstituted C6 aryl group; M3 h+ This indicates an ion with a +h valence, where h is an integer between 2 and 4; The phosphite includes any one or a combination of at least two of aluminum phosphite, calcium phosphite, magnesium phosphite, copper phosphite, zinc phosphite, iron phosphite, and titanium phosphite.

[0007] In a preferred embodiment of the present invention, R1, R2, R3, and R4 are any one of ethyl, n-butyl, isobutyl, sec-butyl, cyclohexyl, and phenyl, and R1 and R2 are not both ethyl.

[0008] In a preferred embodiment of the present invention, the dialkylphosphonate is a mixture of two or more dialkylphosphonates with different molecular structures, and contains at least one dialkylphosphonate A with the same hydrocarbon molecular structure and at least one dialkylphosphonate B with a different hydrocarbon molecular structure.

[0009] In a preferred embodiment of the present invention, the dialkylphosphonate A includes any one or a combination of at least two of di-n-butylphosphonate, diisobutylphosphonate, disec-butylphosphonate, ditert-butylphosphonate, dicyclohexylphosphonate, and diphenylphosphonate.

[0010] In a preferred embodiment of the present invention, the dialkylphosphonate A is any one or a combination of at least two of di-n-butylphosphonate, diisobutylphosphonate, and dicyclohexylphosphonate.

[0011] In a preferred embodiment of the present invention, the dialkylphosphinate B comprises any one or a combination of at least two of the following: ethyl n-butylphosphinate, ethyl isobutylphosphinate, ethyl sec-butylphosphinate, ethyl tert-butylphosphinate, ethyl cyclohexylphosphinate, ethyl phenylphosphinate, n-butyl isobutylphosphinate, n-butyl tert-butylphosphinate, n-butyl sec-butylphosphinate, isobutyl sec-butylphosphinate, isobutyl tert-butylphosphinate, sec-butyl tert-butylphosphinate, n-butyl cyclohexylphosphinate, isobutyl cyclohexylphosphinate, sec-butyl cyclohexylphosphinate, tert-butyl cyclohexylphosphinate, n-butyl phenylphosphinate, isobutyl phenylphosphinate, sec-butyl phenylphosphinate, tert-butyl phenylphosphinate, and cyclohexylphenylphosphinate.

[0012] In a preferred embodiment of the present invention, the dialkylphosphinate B is any one or a combination of at least two of ethyl butylphosphinate, n-butyl isobutylphosphinate, n-butyl sec-butylphosphinate, isobutyl sec-butylphosphinate, and isobutyl tert-butylphosphinate.

[0013] In a preferred embodiment of the present invention, M1 is any one or a combination of at least two of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

[0014] In a preferred embodiment of the present invention, M1 is any one or a combination of two of Al and Zn.

[0015] In a preferred embodiment of the present invention, M2 is any one or a combination of at least two of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

[0016] In a preferred embodiment of the present invention, M2 is any one or a combination of two of Al and Zn.

[0017] In a preferred embodiment of the present invention, M3 is any one or a combination of at least two of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

[0018] In a preferred embodiment of the present invention, M3 is any one or a combination of two of Al and Zn.

[0019] In a preferred embodiment of the present invention, the method for preparing the polymer additive includes the following steps: Diethylphosphonate, dialkylphosphonate, alkylphosphonate, alkylphosphonate and phosphite are mixed evenly and then mixed in a mixer under an inert gas protective atmosphere and heated to 200-300℃ for 0.5-10 hours to obtain polymer additive.

[0020] Secondly, this application provides the use of the polymer additive as described in the first aspect as a flame retardant in polymer materials.

[0021] In a preferred embodiment of the present invention, the polymer material comprises the following components in parts by weight: 40-99.5 parts thermoplastic polymer, 5-35 parts polymer additives.

[0022] In a preferred embodiment of the present invention, the polymer material comprises the following components in parts by weight: The thermoplastic polymer consists of 40-99.5 parts, polymer additives of 5-35 parts, fillers of 0-45 parts, synergistic flame retardants of 0-15 parts, antioxidants of 0-1.5 parts, and lubricants of 0-1.5 parts.

[0023] In a preferred embodiment of the present invention, the thermoplastic polymer includes any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyketone, polyolefin, and polyacrylate.

[0024] In a preferred embodiment of the present invention, the polyamide includes any one or a combination of at least two of the following: condensation products of dicarboxylic acids and diamines, condensation products of ω-amino acids, and ring-opening polymerization products of lactams.

[0025] In a preferred embodiment of the present invention, the dicarboxylic acid includes, but is not limited to, any one or a combination of at least two of adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid.

[0026] In a preferred embodiment of the present invention, the diamine includes, but is not limited to, any one or a combination of at least two of hexamethylenediamine, decanediamine, dodecanediamine, butanediamine, p-phenylenediamine, and m-phenylenediamine.

[0027] In a preferred embodiment of the present invention, the ω-amino acid includes, but is not limited to, any one or a combination of at least two of the ω-amino acids formed by ring opening of cyclic lactams and aminobenzoic acid.

[0028] In a preferred embodiment of the present invention, the cyclic lactam includes, but is not limited to, any one or a combination of at least two of caprolactam, octyllactam, undecyllactam, and dodecalactam.

[0029] In a preferred embodiment of the present invention, the polyamide includes any one or a combination of at least two of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1212, polyamide 6T, and polyamide 10T.

[0030] In a preferred embodiment of the present invention, the polyester comprises a condensation product of a dicarboxylic acid and / or its derivatives with a diol.

[0031] In a preferred embodiment of the present invention, the dicarboxylic acid includes, but is not limited to, any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, and hydrogenated phthalic acid, and the derivatives include acyl halides (acyl chlorides), esters, and acid anhydrides formed from dicarboxylic acids.

[0032] In a preferred embodiment of the present invention, the diol includes, but is not limited to, any one or a combination of at least two of ethylene glycol, butanediol, and hexanediol.

[0033] In a preferred embodiment of the present invention, the polyester includes any one or a combination of at least two of PET and PBT.

[0034] In a preferred embodiment of the present invention, the polyurethane comprises the reaction product of a polyol and an isocyanate.

[0035] In a preferred embodiment of the present invention, the polyols include, but are not limited to, any one or a combination of at least two of polyether polyols, polyester polyols, polylactone polyols, and polycarbonate polyols.

[0036] In a preferred embodiment of the present invention, the styrene-based polymer includes any one or a combination of at least two of styrene homopolymer, styrene-acrylate copolymer, styrene-olefin copolymer, and styrene-olefin-acrylonitrile copolymer.

[0037] In a preferred embodiment of the present invention, the styrene-olefin copolymer includes, but is not limited to, any one or a combination of at least two of the following: styrene-(ethylene-propylene) diblock copolymer, styrene-(ethylene-butene)-ethylene triblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene-styrene triblock copolymer, and styrene-ethylene-isoprene terpolymer.

[0038] In a preferred embodiment of the present invention, the polyolefin includes any one or a combination of at least two of polyethylene, α-olefin homopolymer, α-olefin copolymer, ethylene-α-olefin copolymer, and ethylene-α-olefin-diolefin copolymer.

[0039] In a preferred embodiment of the present invention, the α-olefin includes, but is not limited to, any one or a combination of at least two of propylene, butene, pentene, hexene, hepten, and octene.

[0040] In a preferred embodiment of the present invention, the diene includes, but is not limited to, any one or a combination of at least two of isoprene, butadiene, and hexadiene.

[0041] In a preferred embodiment of the present invention, the filler includes any one or a combination of at least two of the reinforcing material and filler.

[0042] In a preferred embodiment of the present invention, the reinforcing material includes any one or a combination of at least two of glass fiber and carbon fiber.

[0043] In a preferred embodiment of the present invention, the filler includes any one or a combination of at least two of the following: silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass microspheres.

[0044] In a preferred embodiment of the present invention, the synergistic flame retardant includes any one or a combination of at least two of melamine polyphosphate, melamine polyphosphate salt, zinc borate, zinc stannate, zinc sulfide, and boehmite.

[0045] In a preferred embodiment of the present invention, the antioxidant includes any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, and phosphite antioxidants.

[0046] In a preferred embodiment of the present invention, the lubricant includes any one or a combination of at least two of the following: ester lubricants, alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, and metal soap lubricants.

[0047] In a preferred embodiment of the present invention, the polymer material comprises the following components in parts by weight: 50-85 parts thermosetting polymer, 5-35 parts polymer additives; The thermosetting polymer includes any one or a combination of at least two of phenolic resin, epoxy resin, urea-formaldehyde resin, polyurethane, and polyacrylate resin.

[0048] In a preferred embodiment of the present invention, the method for preparing the polymer material includes: The polymer material is obtained by extruding the melt-blended components of the polymer material.

[0049] In a preferred embodiment of the present invention, the melt blending is carried out in a screw extruder.

[0050] In a preferred embodiment of the present invention, the screw extruder is a twin-screw extruder.

[0051] In a preferred embodiment of the present invention, the temperature of the screw extruder is 180-330°C.

[0052] The beneficial effects of this invention are: The present invention discloses a polymer additive and its application. Through the design and synergistic compounding of various phosphonates, the flame retardant effect can be significantly improved, and the prepared polymer additive has excellent and efficient flame retardancy. When this polymer additive is used in polymer materials, the polymer materials containing it can have excellent flame retardant properties with a small amount of addition, as well as good toughness, high impact strength and excellent mechanical properties.

[0053] The short-chain alkyl structure in diethylphosphonate readily decomposes in the early stages of combustion, releasing phosphorus-containing active free radicals. These free radicals can quickly capture HO· and H· free radicals generated during polymer combustion, thus interrupting the combustion chain reaction. Dialkylphosphonates and alkylphosphonates have slightly higher thermal stability than diethylphosphonate, complementing it in decomposition temperature. They decompose at slightly higher temperatures, continuously replenishing phosphorus-containing free radicals in the gas phase, extending the gas-phase flame-retardant action time window, and preventing "flame-retardant failure" caused by premature depletion of diethylphosphonate. Moreover, the presence of long-chain alkyl groups provides better compatibility with the polymer matrix, avoiding adverse effects on the mechanical properties of the polymer matrix. The active hydrogen released by the breaking of the PH bond in the alkylphosphonate molecule can promote the dehydration of the polymer molecular chain to form char, while simultaneously converting itself into phosphonate, serving as a "crosslinking point" for the char layer, increasing the density of the char layer, thereby blocking heat transfer to the polymer interior and preventing the volatilization of combustible gases, forming a "self-extinguishing barrier." When heated, phosphites decompose to produce highly dehydrating products such as pyrophosphoric acid and metaphosphoric acid. These substances can react with polymers containing multiple hydroxyl groups, promoting their dehydration and forming a carbon layer, thereby isolating oxygen and combustible gases and reducing the combustion rate. Therefore, the rational blending of diethylphosphinate, dialkylphosphinate, alkylphosphinate, alkylphosphinate, and phosphites not only endows polymer additives with excellent flame retardant properties but also imparts excellent compatibility. Adding these additives to polymer materials can achieve high flame retardant effects with low dosages without significantly degrading the polymer's mechanical properties. Detailed Implementation

[0054] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0055] Preparation Example 1 500g of sodium hypophosphite monohydrate was dissolved in 1000g of water and added to a 316L stainless steel high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen. The reactor was heated to 100°C. Butene was continuously pumped in using a cryogenic pump to maintain the reaction pressure at 0.5MPa. An aqueous solution of 3g of sodium persulfate and 100g of water was continuously added at a uniform rate over 5 hours. When the flow rate of butene was greater than 590g, the pumping of butene was stopped, and the reactor was kept at the temperature for 2 hours. After cooling, the pressure was released and the material was discharged to obtain an aqueous solution of sodium dibutylphosphite. Sodium dibutylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 1.5h with stirring. After the addition was complete, the temperature was maintained for 0.5h. After the reaction was completed, the mixture was filtered and washed three times with water at 5 times the weight of the filter cake to obtain 801g of aluminum dibutylphosphonate. The product composition is as follows: aluminum dibutylphosphonate: 100mol%.

[0056] Preparation Example 2 500g of sodium hypophosphite monohydrate and 600g of water were stirred and dissolved, and then added to a 316L stainless steel high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen. The reactor was heated to 120°C, and n-butene was continuously pumped in using a cryogenic pump to maintain the reaction pressure at 1.0MPa. An aqueous solution of 4g of sodium persulfate and 36g of water was continuously added at a uniform rate over 5 hours. When the n-butene flow rate was greater than 590g, the pumping of n-butene was stopped, and the reactor was kept at the temperature for 2 hours. After cooling, the pressure was released and the material was discharged to obtain an aqueous solution of sodium dibutylphosphite. The sodium dibutylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 1.5h with stirring. After the addition was complete, the temperature was maintained for 0.5h. After the reaction was completed, the mixture was filtered and washed three times with water at five times the weight of the filter cake to obtain 796g of aluminum dibutylphosphonate. The product composition was as follows: aluminum di-n-butylphosphonate: 91.70 mol%, aluminum n-butylisobutylphosphonate: 8.3 mol%.

[0057] Preparation Example 3 500g of sodium hypophosphite monohydrate was dissolved in 1000g of water and added to a 316L stainless steel high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen. The reactor was heated to 97°C. Isobutylene was continuously pumped in using a cryogenic pump to maintain the reaction pressure at 0.5MPa. An aqueous solution of 3g of sodium persulfate and 100g of water was continuously added at a uniform rate over 5 hours. When the isobutylene flow rate was greater than 590g, the pumping of isobutylene was stopped, and the reactor was kept at this temperature for 2 hours. The reactor was then cooled, depressurized, and discharged to obtain an aqueous solution of sodium dibutylphosphite. Sodium dibutylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 1.5h with stirring. After the addition was complete, the temperature was maintained for 0.5h. After the reaction was completed, the mixture was filtered and washed three times with water at 5 times the weight of the filter cake to obtain 807g of aluminum dibutylphosphonate. The product composition is as follows: aluminum diisobutylphosphonate: 100mol%.

[0058] Preparation Example 4 500g of sodium hypophosphite monohydrate and 600g of water were stirred and dissolved, and then added to a 316L stainless steel high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen. The reactor was heated to 120°C. Isobutylene was continuously pumped in using a cryogenic pump to maintain the reaction pressure at 1.0MPa. An aqueous solution of 4g of sodium persulfate and 36g of water was continuously added at a uniform rate over 5 hours. When the isobutylene flow rate was greater than 590g, the pumping of isobutylene was stopped, and the reactor was kept at this temperature for 2 hours. After cooling and depressurization, the material was discharged to obtain an aqueous solution of sodium dibutylphosphite. Sodium dibutylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 1.5h with stirring. After the addition was complete, the temperature was maintained for 0.5h. After the reaction was completed, the mixture was filtered and washed three times with water at five times the weight of the filter cake to obtain 799g of aluminum dibutylphosphonate. The product composition was as follows: aluminum diisobutylphosphonate: 93.10 mol%, aluminum isobutyl-tert-butylphosphonate: 6.9 mol%.

[0059] Preparation Example 5 500g of sodium hypophosphite monohydrate was dissolved in 1000g of water and added to a 316L stainless steel high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen. The reactor was heated to 97°C. Butene was continuously pumped in using a cryogenic pump to maintain the reaction pressure at 0.5MPa. An aqueous solution of 3g of sodium persulfate and 100g of water was continuously added at a uniform rate over 5 hours. When the flow rate of butene exceeded 300g, the pumping of butene was stopped, and the reactor was kept at the temperature for 2 hours. After cooling, the pressure was released and the material was discharged to obtain an aqueous solution of sodium butyroxyphosphite. Sodium n-butylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 1.5h with stirring. After the addition was completed, the temperature was maintained for 0.5h. After the reaction was completed, the mixture was filtered and washed three times with water at 5 times the weight of the filter cake to obtain 602g of aluminum isobutylphosphonate. The product composition was as follows: aluminum n-butylphosphonate: 94.5mol%, aluminum di-n-butylphosphonate: 5.5mol%.

[0060] Preparation Example 6 500g of sodium hypophosphite monohydrate was dissolved in 1000g of water and added to a 316L stainless steel high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen. The reactor was heated to 97°C. Isobutylene was continuously pumped in using a cryogenic pump to maintain the reaction pressure at 0.5MPa. An aqueous solution of 3g of sodium persulfate and 100g of water was continuously added at a uniform rate over 5 hours. When the isobutylene flow rate was greater than 305g, the pumping of isobutylene was stopped, and the reactor was kept at the temperature for 2 hours. The reactor was then cooled, depressurized, and discharged to obtain an aqueous solution of sodium isobutylphosphite. Sodium isobutylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 1.5h with stirring. After the addition was complete, the temperature was maintained for 0.5h. After the reaction was completed, the mixture was filtered and washed three times with water at five times the weight of the filter cake to obtain 607g of aluminum isobutylphosphonate. The product composition was as follows: aluminum isobutylphosphonate: 97.2 mol%, aluminum diisobutylphosphonate: 2.8 mol%.

[0061] Preparation Example 7 500g of sodium hypophosphite monohydrate, 810g of cyclohexene, and 1000g of water were added to a high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen five times. The mixture was stirred and heated to 115℃, where it was kept at a constant temperature for 6 hours. During these 6 hours, an aqueous solution of 7g of sodium persulfate and 63g of water was continuously added at a uniform rate. The reactor was then kept at 115℃ for 1 hour, cooled, and the unreacted cyclohexane in the upper layer was removed to obtain an aqueous solution of sodium dicyclohexylphosphite. The sodium dicyclohexylphosphonate aqueous solution was diluted with water to a sodium salt content of 10%, heated to 70°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 3 hours with stirring. After the addition was complete, the reaction was maintained at this temperature for 0.5 hours. After the reaction was completed, the mixture was filtered and washed three times with water at a ratio of 5 times the weight of the filter cake to obtain 1033g of aluminum dicyclohexylphosphonate product.

[0062] Preparation Example 8 500g of sodium hypophosphite monohydrate, 410g of cyclohexene, and 1000g of water were added to a high-pressure reactor. 2g of sodium persulfate was added, and the reactor was purged with nitrogen five times. The mixture was stirred and heated to 115℃, where it was kept at a constant temperature for 4 hours. During these 4 hours, an aqueous solution of 4g sodium persulfate and 36g water was continuously added at a uniform rate. The reactor was then kept at 115℃ for 1 hour, cooled, and discharged to obtain an aqueous solution of sodium cyclohexylphosphite. The sodium cyclohexylphosphonate aqueous solution was diluted with water to a sodium salt content of 10%, heated to 70°C, and aluminum sulfate aqueous solution (prepared from 524g of aluminum sulfate octadecylhydrate and 2100g of water) was continuously added dropwise over 3 hours with stirring. After the addition was complete, the reaction was maintained at this temperature for 0.5 hours. After the reaction was completed, the mixture was filtered and washed three times with water at a ratio of 5 times the weight of the filter cake to obtain 512g of aluminum cyclohexylphosphonate product.

[0063] Preparation Example 9 246g of phosphorous acid and 300g of water were added to a high-pressure reactor, along with 1g of tert-butyl peroxide-2-ethylhexanoate. After purging with nitrogen five times, the reactor was sealed, and ethylene was introduced to a pressure of 1.2MPa. The reactor was stirred and heated to 95℃, maintaining the temperature at 95℃ for 5 hours. During these 5 hours, an aqueous solution of 3g sodium persulfate and 27g water was continuously and uniformly added. Throughout the reaction, a pressure regulator was used to maintain the reactor pressure at 1.2MPa. The reactor was then kept at 95℃ for 1 hour, cooled, and discharged. The solution was neutralized to pH 7 using a 20% sodium hydroxide solution to obtain an aqueous solution of sodium ethylphosphonate. Sodium ethylphosphonate aqueous solution was diluted with water to a sodium salt content of 25%, heated to 60°C, and aluminum sulfate aqueous solution (prepared from 666g of aluminum sulfate octadechydrate and 2665g of water) was continuously added dropwise over 2.5 hours with stirring. After the addition was complete, the mixture was kept at this temperature for 20 minutes. After the reaction was completed, the mixture was filtered and washed three times with water at a ratio of three times the weight of the filter cake to obtain aluminum ethylphosphonate product.

[0064] Preparation Example 10 Similar to Preparation Example 5, sodium phosphite was used instead of sodium hypophosphite to prepare aluminum n-butylphosphonate.

[0065] Preparation Example 11 Similar to Preparation Example 6, sodium phosphite was used instead of sodium hypophosphite to prepare aluminum isobutylphosphonate.

[0066] Preparation Example 12 Similar to Preparation Example 8, sodium phosphite was used instead of sodium hypophosphite to prepare aluminum cyclohexylphosphonate.

[0067] Preparation Example 13 Ethyl-n-butylphosphinate aluminum was prepared according to the method in Example 4 of CN103172670A.

[0068] The following are exemplary examples of several polymer additives described in this invention. In the following examples, the materials used are from Preparation Examples 1-13 and / or commercially available materials.

[0069] Examples 1-26 and Comparative Examples 1-6 are polymer additives. The types and amounts of each component of the polymer additives (by mass) are shown in Tables 1, 2 and 3. Table 1: Schematic diagram of the components of the polymer additives in Examples 1-13 Table 2: Schematic diagram of the components of the polymer additives in Examples 14-26 Among them, "dipropylphosphonic acid aluminum" in Table 2 is a mixture of di-n-propylphosphonic acid aluminum and n-propyl isopropylphosphonic acid aluminum in a molar ratio of 94.8:4.3; Table 3: Schematic diagram of the components of the polymer additives in Comparative Examples 1-6 The preparation methods of the polymer additives in Examples 1-26 and Comparative Examples 1-6 include the following steps: Diethylphosphonate, dialkylphosphonate, alkylphosphonate, alkylphosphonate and phosphite are mixed evenly and then mixed in a mixer under an inert gas protective atmosphere and heated to 250°C for 5 hours to obtain a polymer additive.

[0070] The following are exemplary examples of the application of the polymer additives described in this invention in polymer compositions. Specific information about the materials used in these examples is shown in Table 4: Table 4: Detailed Information on Each Component of the Polymer Material Application Examples 1-52 are compared with Application Examples 1-13, which use polymer materials, specifically polyamide-type polymer materials. The preparation method of the polymer materials is as follows: All components except glass fiber are placed in a mixer and mixed at 60 rpm for 20 minutes to obtain a premix. The premix is ​​then fed into a twin-screw extruder through the main feed port, and the glass fiber is fed into the twin-screw extruder through the side feed port for melt blending. The mixture is then extruded, granulated, dried, and cooled to obtain polyamide. The screw speed of the twin-screw extruder is 500 rpm, and the temperatures from the feed section to the die head are 90℃, 275℃, 270℃, 260℃, 260℃, 230℃, 230℃, 230℃, 220℃, 220℃, and 260℃. The testing methods for polymer materials are as follows: (1) Flame retardancy: Square plates of 125mm×13mm×1.6mm and 125mm×13mm×0.8mm were manufactured by injection molding and tested according to the method in standard ANSI / UL-94-1985; (2) Notched impact strength: The notched impact strength of the cantilever beam was tested according to the method in standard ISO 180 2019. It was injection molded into a strip of 80mm×10mm×4mm with an impact energy of 2.75J and a type A notch. The types and amounts of each component of the polymer material (by mass parts) implemented in Application Examples 1-52, compared with Application Examples 1-13, and the test results are shown in Tables 5, 6, 7, 8, and 9: Table 5: Schematic diagram of the components and test results of polymer materials in application examples 1-13 Table 6: Schematic diagram of the components and test results of polymer materials in application examples 14-26 Table 7: Schematic diagram of the components and test results of polymer materials in application examples 27-39 Table 8: Schematic diagram of the components and test results of polymer materials in application examples 40-52 Table 9: Comparative Table of Polymer Materials and Test Results in Application Examples 1-13 Combining the performance test data in Tables 5, 6, 7, 8, and 9, it can be seen that the polymer additives provided by the present invention, through the design and synergistic compounding of each component, exhibit excellent flame retardant effects. They can impart excellent flame retardancy to the polyamide composition containing them with relatively small amounts, achieving V0-V1 flame retardant levels for 1.6mm and 0.8mm sheets. Simultaneously, their notched impact strength is ≥8.9 J / m, demonstrating excellent toughness and impact resistance. However, when using polymer additives D1-D6 provided in Comparative Examples 1-6, because they do not contain the four types of phosphonates defined in the present invention, or the phosphonate dosage exceeds the scope of the present invention, the results of Comparative Application Examples 1-6 show that they are difficult to exert a synergistic flame retardant effect, leading to a decrease in the flame retardant performance of the polyamide composition containing them. In Comparative Application Examples 7-12, increasing the dosage of polymer additives D1-D6 improves the flame retardancy of the material, but reduces the notched impact strength of the polyamide composition and significantly deteriorates its mechanical properties such as toughness.

[0071] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0072] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A polymer additive, characterized in that, The components include the following mass parts: diethyl phosphinic acid salt 35-90 parts, dihydrocarbyl phosphinic acid salt 5-63 parts, hydrocarbyl phosphinic acid salt 0.1-6.3 parts, hydrocarbyl phosphinic acid salt 0.1-2.0 parts, and phosphite salt 0-25 parts; The diethyl phosphinic acid salt includes any one or a combination of at least two of metal diethyl phosphinic acid salt, non-metal diethyl phosphinic acid salt; The molecular structure of the dihydrocarbyl phosphinic acid salt is as follows: wherein R1, R2are any of substituted or unsubstituted C2 and / or C4 linear or branched alkyl, substituted or unsubstituted C6 cycloalkyl, substituted or unsubstituted C6 aryl; M1 m+ represents a +m-valent ion, m being an integer from 2 to 4; The molecular structure of the hydrocarbyl phosphinic acid salt is as follows: wherein R3is any one of a substituted or unsubstituted C2 and / or C4 linear or branched alkyl group, a substituted or unsubstituted C6 cycloalkyl group, a substituted or unsubstituted C6 aryl group; M2 n+ represents a +n-valent ion, n being an integer from 2 to 4; The molecular structure of the hydrocarbyl phosphinic acid salt is as follows: wherein R4 is any one of a substituted or unsubstituted C2 and / or C4 linear or branched alkyl group, a substituted or unsubstituted C6 cycloalkyl group, a substituted or unsubstituted C6 aryl group; M3 h+ represents an ion of +h valence, h being an integer from 2 to 4; The phosphite salt includes any one or a combination of at least two of aluminum phosphite, calcium phosphite, magnesium phosphite, copper phosphite, zinc phosphite, iron phosphite, and titanium phosphite.

2. A polymer additive according to claim 1, characterised in that The R1, R2, R3, and R4 are any one of ethyl, n-butyl, isobutyl, sec-butyl, cyclohexyl, and phenyl, and R1 and R2 are not ethyl at the same time.

3. The polymer additive of claim 1, wherein The dihydrocarbyl phosphinic acid salt is a mixture of two or more different molecular structures of dihydrocarbyl phosphinic acid salt, and at least one dihydrocarbyl phosphinic acid salt A with the same hydrocarbyl molecular structure and at least one dihydrocarbyl phosphinic acid salt B with a different hydrocarbyl molecular structure.

4. The polymer additive of claim 1, wherein The dihydrocarbyl phosphinic acid salt A includes any one or a combination of at least two of di-n-butyl phosphinic acid salt, diisobutyl phosphinic acid salt, di-sec-butyl phosphinic acid salt, di-tert-butyl phosphinic acid salt, dicyclohexyl phosphinic acid salt, and diphenyl phosphinic acid salt. The dihydrocarbyl phosphinic acid salt B includes any one or a combination of at least two of ethyl-n-butyl phosphinic acid salt, ethyl-isobutyl phosphinic acid salt, ethyl-sec-butyl phosphinic acid salt, ethyl-tert-butyl phosphinic acid salt, ethyl-cyclohexyl phosphinic acid salt, ethyl-phenyl phosphinic acid salt, n-butyl-isobutyl phosphinic acid salt, n-butyl-tert-butyl phosphinic acid salt, n-butyl-sec-butyl phosphinic acid salt, isobutyl-sec-butyl phosphinic acid salt, isobutyl-tert-butyl phosphinic acid salt, sec-butyl-tert-butyl phosphinic acid salt, n-butyl-cyclohexyl phosphinic acid salt, isobutyl-cyclohexyl phosphinic acid salt, sec-butyl-cyclohexyl phosphinic acid salt, tert-butyl-cyclohexyl phosphinic acid salt, n-butyl-phenyl phosphinic acid salt, isobutyl-phenyl phosphinic acid salt, sec-butyl-phenyl phosphinic acid salt, tert-butyl-phenyl phosphinic acid salt, and cyclohexyl-phenyl phosphinic acid salt.

5. The polymer additive of claim 1, wherein The M1 is any one or a combination of at least two of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

6. The polymer additive of claim 1, wherein The M2 is any one or a combination of at least two of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

7. The polymer additive of claim 1, wherein The M3 is any one or a combination of at least two of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

8. Use of the polymer additive according to any one of claims 1-7 as a flame retardant in a polymer material.

9. Use according to claim 8, characterized in that, The polymer material includes the following mass parts: thermoplastic polymer 40-99.5 parts, and the polymer additive according to any one of claims 1-7 5-35 parts; The thermoplastic polymer includes any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyketone, polyolefin, and polyacrylate.

10. Use according to claim 8, characterized in that, The polymer material includes the following mass parts: thermoset polymer 50-85 parts, polymer additive as described in any of claims 1-7 5-35 parts; the thermoset polymer comprises any one or a combination of at least two of a phenol formaldehyde resin, an epoxy resin, a urea formaldehyde resin, a polyurethane, a polyacrylate resin.

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