A polymer additive and its application

Abstract

The present invention provides a kind of polymer additive and application thereof, and the polymer additive includes the following components in parts by mass: 30 90 parts of diethyl phosphinate, 0.01 3 parts of ethyl phosphonate, 5 67 parts of dialkyl phosphinate, 0.01 5.5 parts of alkyl phosphinate; the dialkyl phosphinate has a structure as shown in Formula I, and the alkyl phosphinate has a structure as shown in Formula II. The present invention can significantly improve the flame retardant effect by the design and compounding synergy of various phosphonates, so that the polymer additive has excellent and efficient flame retardancy. The polymer additive is used in polymer materials, and can make the polymer composition comprising it have excellent flame retardant properties when the addition amount is small, and has good toughness, high impact strength, and excellent mechanical properties and resistance to moisture and heat.

Description

Technical Field

[0001] The invention belongs to the technical field of flame retardant materials, and particularly relates to a polymer additive and application thereof. Background Art

[0002] As a general halogen-free flame retardant, dialkyl phosphinates have the characteristics of good flame retardancy, low smoke emission during combustion, high CTI (Current Tracking Index), and environmental protection. They have little effect on the physical and electrical properties of the base polymer and are widely used in polymer systems such as polyamide, polyester, polyolefin, and polyurethane. They can make the material system containing them have high mechanical and electrical properties, which can meet the application needs of industries such as electrical appliances and energy storage. They are especially favored by manufacturers in the electrical appliance industry and have a very broad market prospect.

[0003] Because dialkyl phosphinates have low flame retardancy when used alone, they are typically 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 phosphinate flame retardant, 1%-40% melamine flame retardant, 1%-10% phosphate flame retardant, 0-45% reinforcing agent, and 0.1%-3% other additives. The phosphate flame retardant, melamine flame retardant, and organic phosphinate flame retardant are used together in the polyamide composite to achieve excellent flame retardancy. 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, wherein the halogen-free flame retardant is aluminum diethylphosphinate and melamine polyphosphate, and the synergistic flame retardant is zinc borate. The three flame retardants are compounded to achieve improved flame retardant effect.

[0004] Although the combination of dialkyl phosphinates and other flame retardants can improve flame retardant properties, a larger amount is required to achieve a better flame retardant effect. Excessive addition of flame retardant additives will lead to a decrease in the mechanical properties of the material (such as toughness, impact resistance, etc.).

[0005] Therefore, there is an urgent need in this field to develop a polymer additive with excellent flame retardant properties, which can give polymer materials excellent flame retardancy while having excellent mechanical properties with a small addition amount. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a polymer additive and its application. Through the design and compounding of various types of phosphonates, the polymer additive has excellent flame retardant effect. When used in polymer materials, it can impart excellent flame retardant properties when added in small amounts while maintaining excellent mechanical properties.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a polymer additive, wherein the polymer additive comprises the following components in parts by mass:

[0009] 30-90 parts of diethylphosphinate

[0010] 0.01-3 parts of ethylphosphonate

[0011] 5-67 parts of dialkyl phosphinate

[0012] 0.01-5.5 parts of hydrocarbyl phosphinate.

[0013] The dialkyl phosphinate has a structure as shown in Formula I, and the alkyl phosphinate has a structure as shown in Formula II:

[0014] Formula I; Formula II.

[0015] Wherein, R1, R2, and R3 are each independently selected from any one of a substituted or unsubstituted C2-C8 straight chain or branched alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, and a substituted or unsubstituted C6-C18 aryl group.

[0016] In formula I, the total number of carbon atoms in R1 and R2 is ≥6.

[0017] The substituents in R1, R2 and R3 are each independently selected from at least one of a C1-C8 straight or branched chain alkyl group and a C6-C18 aryl group.

[0018] M1 and M2 are each independently a cationic moiety; specifically, M1 m+ Indicates +m ion, M2 n+ Indicates an ion with a +n valence.

[0019] m and n are each independently selected from integers of 2-4, for example, 2, 3 or 4.

[0020] The polymer additive provided by the present invention can synergistically enhance the flame retardant effect through the design and compounding of four types of specific phosphonates, so that the polymer additive has excellent and efficient flame retardancy and is not easy to migrate and precipitate under hot and humid conditions. When used in polymer materials, the polymer composition containing the polymer additive can have excellent flame retardant properties with a small addition amount, while having excellent mechanical properties such as toughness and impact resistance, and excellent resistance to hot and humid aging.

[0021] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0022] In the polymer additive of the present invention, the mass fraction of the diethyl phosphinate is 30-90 parts, for example, it can be 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 parts, as well as specific values ​​between the above points, or for example, it can be in the range of 30-40 parts, 41-50 parts, 51-60 parts, 61-70 parts, 71-90 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0023] The mass fraction of the ethyl phosphonate is 0.01-3 parts, for example, it can be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts or 2.8 parts, as well as specific point values ​​between the above point values, or for example, it can be in the range of 0.01-0.05 parts, 0.06-0.5 parts, 0.51-1.5 parts, 1.51-2.5 parts, 2.51-3 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0024] The mass parts of the dialkyl phosphinate are 5-67 parts, for example, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or 65 parts, as well as specific point values ​​between the above point values, or for example, can be in the range of 5-10 parts, 10.1-20 parts, 20.1-40 parts, 40.1-55 parts, 55.1-65 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0025] The mass fraction of the hydrocarbyl phosphinate is 0.01-5.5 parts, for example, it can be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts or 5.4 parts, and specific point values ​​between the above point values, or for example, it can be in the range of 0.01-0.5 parts, 0.51-1.5 parts, 1.51-3 parts, 3.1-4 parts, 4.1-5 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0026] In the present invention, the diethylphosphinate has a structure as shown in Formula A, and the ethylphosphonate has a structure as shown in Formula B:

[0027] Formula A; Formula B.

[0028] In formula A, M A x+ represents an ion with a valence of +x, where x is selected from an integer of 2-4, for example, 2, 3 or 4. A is the cation portion of diethylphosphinate, which may be a metal or a non-metal (such as an amine cation, a cation corresponding to melamine and its derivatives), preferably a metal; the M A More preferably, it is any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, and more preferably, Al.

[0029] In formula B, M B y+ represents an ion with a valence of +y, where y is selected from an integer of 2-4, for example, 2, 3 or 4. B is the cation portion of ethylphosphonate, which may be a metal or a non-metal (such as an amine cation, a cation corresponding to melamine and its derivatives), preferably a metal; the M B More preferably, it is any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, and more preferably, Al.

[0030] In the present invention, the C2-C8 straight chain or branched alkyl group can be a straight chain or branched alkyl group of C2, C3, C4, C5, C6, C7, or C8, illustratively including but not limited to: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, neohexyl, 2-methylhexyl, 2-ethylhexyl, heptyl, octyl, etc.

[0031] In the present invention, the C3-C8 cycloalkyl groups can be C3, C4, C5, C6, C7, C8 cycloalkyl groups, including monocyclic alkyl groups, bridged cyclic groups, polycyclic alkyl groups, etc., illustratively including but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0032] In the present invention, the C6-C18 aromatic groups can be aromatic groups such as C6, C9, C10, C11, C12, C13, C14, C15, C16, C17, and C18, including monocyclic aromatic groups and condensed-ring aromatic groups, illustratively including but not limited to phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, and fluorenyl.

[0033] In the present invention, the C1-C8 straight chain or branched alkyl group can be a straight chain or branched alkyl group of C1, C2, C3, C4, C5, C6, C7, or C8, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, neohexyl, 2-methylhexyl, 2-ethylhexyl, heptyl, octyl, etc.

[0034] In the present invention, "substituted or unsubstituted" groups may be substituted with one or more substituents. When there are multiple substituents (at least two), they may be the same or different. The same expressions used below have the same meaning. Unless otherwise specified, substituents may be selected from at least one of C1-C8 linear or branched alkyl groups and C6-C18 aryl groups. These are not further detailed.

[0035] Preferably, in Formula I, R1 and R2 are each independently selected from any one of a substituted or unsubstituted C2-C8 straight chain or branched alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, and a substituted or unsubstituted phenyl group.

[0036] Preferably, the substituents in R1 and R2 are each independently selected from at least one of a C1-C6 straight-chain or branched alkyl group and a phenyl group.

[0037] Preferably, R1 and R2 are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl.

[0038] In Formula I, the total number of carbon atoms in R1 and R2 is ≥6, for example, it can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc. Preferably, the total number of carbon atoms in R1 and R2 is 6-14, more preferably 8-12.

[0039] Preferably, the dialkyl phosphinate comprises a combination of a dialkyl phosphinate A having a structure shown in formula IA and an ethylbutyl phosphinate having a structure shown in formula IB;

[0040] Formula IA; Formula IB.

[0041] wherein M1 and m have the same definitions as in formula I.

[0042] In Formula IA, R1' and R2' are each independently selected from any one of a substituted or unsubstituted C2-C8 (e.g., C3, C4, C5, C6, C7, etc.) linear or branched alkyl group, a substituted or unsubstituted C3-C8 (e.g., C4, C5, C6, C7, etc.) cycloalkyl group, and a substituted or unsubstituted C6-C18 (e.g., C6, C9, C10, C12, C14, C15, C16, C17, C18, etc.) aryl group.

[0043] In Formula IA, the total number of carbon atoms in R1' and R2' is ≥6, and when one of R1' and R2' is ethyl, the other is not butyl.

[0044] The substituents in R1' and R2' are each independently selected from at least one of C1-C8 (e.g., C2, C3, C4, C5, C6, C7, etc.) straight or branched alkyl groups and C6-C18 (e.g., C6, C9, C10, C12, C14, C15, C16, C17, C18, etc.) aryl groups.

[0045] Preferably, the polymer additive includes 5-60 parts by mass of dialkyl phosphinate A, and the mass parts of the dialkyl phosphinate A can be 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 58 parts, as well as specific point values ​​between the above point values, or, for example, can be in the range of 5-10 parts, 10.1-20 parts, 20.1-30 parts, 30.1-40 parts, 40.1-50 parts, 50.1-60 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0046] Preferably, the polymer additive includes 0.05-7 parts of ethyl butyl phosphinate by mass, and the mass parts of the ethyl butyl phosphinate can be 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts or 6.5 parts, as well as specific point values ​​between the above point values, or for example, it can be in the range of 0.05-0.1 parts, 0.11-0.5 parts, 0.51-1 parts, 1.1-3 parts, 3.1-5 parts, 5.1-7 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0047] Preferably, in Formula IA, R1' and R2' are each independently selected from any one of a substituted or unsubstituted C2-C8 straight chain or branched alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, and a substituted or unsubstituted phenyl group.

[0048] Preferably, the substituents in R1' and R2' are each independently selected from at least one of a C1-C6 straight-chain or branched alkyl group and a phenyl group.

[0049] Preferably, R1' and R2' are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl, and more preferably any one of n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, cyclohexyl, methylcyclohexyl, and phenyl.

[0050] Preferably, in Formula IA, the total number of carbon atoms in R1' and R2' is ≥6, for example, it can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc. More preferably, the total number of carbon atoms in R1' and R2' is 6-14, more preferably 8-12.

[0051] Preferably, the dialkyl phosphinate A comprises ethylpentylphosphinate, ethylhexylphosphinate, hexyloctylphosphinate, ethylcyclohexylphosphinate, ethylphenylphosphinate, ethylphenylethylphosphinate, ethylheptylphosphinate, dipropylphosphinate, propylbutylphosphinate, propylpentylphosphinate, propylhexylphosphinate, hexyloctylphosphinate, propylcyclohexylphosphinate, propylphenylphosphinate, propylphenylpropylphosphinate, propylheptylphosphinate, dibutylphosphinate, butylpentylphosphinate, butylhexylphosphinate, hexyloctylphosphinate, butylcyclohexylphosphinate, butylphenylphosphinate The salt is preferably any one of butylbenzenebutylphosphinate, butylheptylphosphinate, dicyclohexylphosphinate, dihexylphosphinate, and diphenylphosphinate, or a combination of at least two thereof; further preferably di-n-propylphosphinate, n-propylisopropylphosphinate, diisopropylphosphinate, di-n-butylphosphinate, diisobutylphosphinate, n-butylisobutylphosphinate, di-sec-butylphosphinate, n-butylsec-butylphosphinate, isobutylsec-butylphosphinate, n-butylcyclohexylphosphinate, isobutylcyclohexylphosphinate, dicyclohexylphosphinate, di-n-hexylphosphinate, and a combination of at least two thereof.

[0052] Preferably, R3 is selected from any one of C2-C8 straight chain or branched alkyl, C3-C8 cycloalkyl, and C6-C18 aryl, further preferably any one of C2-C6 straight chain or branched alkyl, C3-C6 cycloalkyl, and phenyl, more preferably any one of n-butyl, isobutyl, hexyl, cyclohexyl, and phenyl.

[0053] Preferably, the hydrocarbyl phosphinate includes any one of n-butyl phosphinate, isobutyl phosphinate, n-hexyl phosphinate, cyclohexyl phosphinate, and phenyl phosphinate, or a combination of at least two thereof.

[0054] In the present invention, M1 represents the cation portion of the dialkyl phosphinate of the structure shown in Formula I, the dialkyl phosphinate A of the structure shown in Formula IA, and the ethylbutyl phosphinate of the structure shown in Formula IB, which can be a metal or a non-metal (such as an amine cation, a cation corresponding to melamine and its derivatives), preferably a metal.

[0055] Preferably, the M1 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, more preferably Al.

[0056] In the present invention, M2 represents the cation portion of the hydrocarbyl phosphinate of the structure shown in Formula II, which can be a metal or a non-metal (such as an amine cation, a cation corresponding to melamine and its derivatives), preferably a metal.

[0057] Preferably, M2 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, and Al is more preferred.

[0058] In the present invention, the diethylphosphinate includes any one of a metal diethylphosphinate and a non-metal diethylphosphinate, or a combination of at least two thereof. For example, the non-metal cation in the non-metal diethylphosphinate may be an amine cation, such as a cation corresponding to melamine and its derivatives. Preferably, the diethylphosphinate is a metal diethylphosphinate.

[0059] Preferably, the diethylphosphinate includes any one or a combination of at least two of diethylphosphinate aluminum, diethylphosphinate calcium, diethylphosphinate magnesium, diethylphosphinate copper, diethylphosphinate zinc, diethylphosphinate iron, and diethylphosphinate titanium, and further preferably diethylphosphinate aluminum.

[0060] In the present invention, the ethylphosphonate includes any one of a metal ethylphosphonate and a non-metal ethylphosphonate, or a combination of at least two thereof. For example, the non-metal cation in the non-metal ethylphosphonate may be an amine cation, such as a cation corresponding to melamine and its derivatives. Preferably, the ethylphosphonate is a metal ethylphosphonate.

[0061] Preferably, the ethylphosphonate includes any one or a combination of at least two of aluminum ethylphosphonate, calcium ethylphosphonate, magnesium ethylphosphonate, copper ethylphosphonate, zinc ethylphosphonate, iron ethylphosphonate, and titanium ethylphosphonate, and aluminum ethylphosphonate is further preferred.

[0062] Preferably, the polymer additive further includes 0.01-25 parts by mass of phosphite, and the mass of the phosphite can be 0.05 parts, 0.1 parts, 0.5 parts, 1 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts or 24 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0063] In the present invention, the phosphite can be expressed as (Mc z+ )2(HPO3)z,Mc z+ represents an ion with a valence of +z, where z is an integer selected from 2 to 4, for example, 2, 3, or 4. Mc is the cationic portion of the phosphite, which can be a metal or a non-metal (for example, an amine cation, a cation corresponding to melamine and its derivatives), preferably a metal; Mc is further preferably any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, more preferably Al.

[0064] The phosphite includes any one of a metal phosphite and a non-metal phosphite, or a combination of at least two thereof. For example, the non-metal cation in the non-metal phosphite may be an amine cation, such as a cation corresponding to melamine and its derivatives. Preferably, the phosphite is a metal phosphite.

[0065] Preferably, 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, and aluminum phosphite is more preferred.

[0066] As a preferred technical solution of the present invention, the polymer additive comprises the following components in parts by mass:

[0067] 30-90 parts of diethylphosphinate

[0068] 0.01-3 parts of ethylphosphonate

[0069] 0.05-7 parts of ethylbutylphosphinate

[0070] 5-60 parts of dialkyl phosphinate A

[0071] 0.01-5.5 parts of hydrocarbyl phosphinate

[0072] Phosphite 0-25 parts.

[0073] Preferably, the mass percentage of diethylphosphinate in the polymer additive is 30%-90%, for example, it can be 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, as well as specific values ​​between the above points, or for example, it can be in the range of 30-40%, 41-50%, 51-60%, 61-70%, 71-80%, 81-90%. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific values ​​included in the range.

[0074] Preferably, the mass percentage of ethyl phosphonate in the polymer additive is 0.01%-3%, for example, it can be 0.05%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5% or 2.8%, as well as specific values ​​between the above points, or for example, it can be in the range of 0.01-0.1%, 0.11-0.5%, 0.51-1%, 1.1-1.5%, 1.51-2%, 2.1-2.5%, 2.51-3%. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific points included in the said range.

[0075] Preferably, the mass percentage of ethylbutylphosphinate in the polymer additive is 0.05%-7%, for example, it can be 0.08%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% or 6.5%, and specific point values ​​between the above point values, or for example, it can be in the range of 0.05-0.1%, 0.11-0.5%, 0.51-1%, 1.1-2%, 2.1-3%, 3.1-4%, 4.1-5%, 5.1-6%, 6.1-7%. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0076] Preferably, the mass percentage of the dialkylphosphinate A in the polymer additive is 5%-60%, for example, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or 55%, as well as specific values ​​between the above points, or, for example, in the range of 5-10%, 11-20%, 21-30%, 31-40%, 41-50%, 51-60%. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific values ​​included in the range.

[0077] Preferably, the mass percentage of the hydrocarbyl phosphinate in the polymer additive is 0.01%-5.5%, for example, 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5% or 4.8%, and specific values ​​between the above points, or for example, in the range of 0.01-0.1%, 0.11-0.5%, 0.51-1%, 1.1-2%, 2.1-3%, 3.1-4%, 4.1-5%. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific values ​​included in the range.

[0078] Preferably, the mass percentage of phosphite in the polymer additive is 0-25%, for example, it can be 0, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22% or 24%, as well as specific point values ​​between the above point values, or for example, it can be in the range of 0-5%, 5.1-10%, 10.1-15%, 15.1-20%, 20.1-25%. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0079] In the present invention, the preparation method of the polymer additive comprises: mixing diethyl phosphinate, ethyl phosphonate, dialkyl phosphinate, alkyl phosphinate, and optionally phosphite to obtain the polymer additive.

[0080] In the present invention, the diethyl phosphinate, ethyl phosphonate, dialkyl phosphinate, alkyl phosphinate, and phosphite can be purchased from the market or prepared by synthetic methods known in the art.

[0081] The following examples illustrate the preparation methods of several organic phosphinates (diethyl phosphinate, dialkyl phosphinate, and alkyl phosphinate) and ethyl phosphonate. However, the preparation methods of diethyl phosphinate, dialkyl phosphinate, alkyl phosphinate, and ethyl phosphonate in the present invention are not limited to the following preparation methods.

[0082] In a preferred technical solution, the preparation method of the alkyl phosphinate having the structure shown in Formula III comprises: performing an addition reaction between a phosphinate and a first olefin in the presence of an initiator to obtain a water-soluble alkyl phosphinate; performing a metathesis reaction between the water-soluble alkyl phosphinate and an M salt to obtain the alkyl phosphinate;

[0083] Formula III.

[0084] In formula III, R A1 Any one selected from substituted or unsubstituted C2-C8 straight or branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, R A2 H, or R A2 is with R A1 The same group, or R A2 It is R A1 isomeric groups.

[0085] The first olefin has R A1 The same number of carbon atoms, its molecular structure contains a C = C group, the group in the presence of an initiator undergoes a free radical addition reaction to obtain a water-soluble alkyl phosphinate.

[0086] In formula III, M is the cationic portion of the alkylphosphinate, having the same definition as M1 and M2; and a is an integer selected from 2-4.

[0087] In the preparation method, the molar amount of the hypophosphite is n1, the molar amount of the first olefin is n2, when n2 / n1 ≥ 2, for example, n2 / n1 is 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, etc., the product thus obtained is a dialkyl phosphinate (i.e., R A2 With R A1Same, or R A2 It is R A1 isomeric groups) are mainly dialkyl phosphinates. When n2 / n1≤1, for example, n2 / n1 is 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, the product is monoalkyl phosphinate ( ) (all of which may be monoalkyl phosphinates). When 1 < n2 / n1 < 2, for example, n2 / n1 is 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9, the resulting product is a combination of dialkyl phosphinates and monoalkyl phosphinates.

[0088] In another preferred technical solution, the preparation method of the dialkyl phosphinate having the structure shown in Formula IV comprises: performing an addition reaction between a phosphite and a second olefin in the presence of an initiator to obtain a water-soluble dialkyl phosphinate; performing a metathesis reaction between the water-soluble dialkyl phosphinate and an M salt to obtain the dialkyl phosphinate;

[0089] Formula IV.

[0090] In Formula IV, R B1 Any one selected from substituted or unsubstituted C2-C8 straight or branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, R B2 is selected from any one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, and R B2 The number of carbon atoms is R B1 b times the number of carbon atoms, b is an integer ≥ 1, such as 1, 2, 3, 4, etc., preferably 1-2; when R B2 With R B1 When the number of carbon atoms in the two groups is the same (i.e., b=1), the two groups can be the same group or isomeric groups.

[0091] The second olefin has B1 The same number of carbon atoms, its molecular structure contains a C = C group, which can react with hypophosphite in the presence of an initiator to form PR B1 Groups and PR B21 Group (R B21 With R B1 Same, or R B21 With R B1 At the same time, multiple second olefins react with each other and with hypophosphite to form PR B22 Group (R B22 The number of carbon atoms is R B1 at least 2 times the number of carbon atoms of the alkyl group), thereby obtaining a water-soluble dialkyl phosphinate.

[0092] M and a in formula IV have the same definitions as in formula III.

[0093] Preferably, the molar amount of the hypophosphite is n1, the molar amount of the second olefin is n3, and n3 / n1>2, for example, it can be 2.01, 2.05, 2.08, 2.1, 2.12, 2.15, 2.18, 2.2, 2.22, 2.25, 2.28 or 2.3, and more preferably 2.01-2.2.

[0094] In another preferred technical solution, the preparation method of a dialkyl phosphinate having a structure shown in Formula V comprises: a first addition reaction of a phosphinate with a third olefin in the presence of an initiator to obtain a water-soluble monoalkyl phosphinate; a second addition reaction of the water-soluble monoalkyl phosphinate with a fourth olefin in the presence of an initiator to obtain a water-soluble dialkyl phosphinate; and a double decomposition reaction of the water-soluble dialkyl phosphinate with an M salt to obtain the dialkyl phosphinate.

[0095] Formula V.

[0096] In formula V, R C1 、R C2 Each is independently selected from any one of a substituted or unsubstituted C2-C8 straight or branched alkyl group, and a substituted or unsubstituted C3-C8 cycloalkyl group.

[0097] The third olefin has C1 The same number of carbon atoms, its molecular structure contains a C = C group, which undergoes a free radical addition reaction in the presence of an initiator to obtain PR C1 Group; the fourth olefin has C2 The same number of carbon atoms, its molecular structure contains a C = C group, which undergoes a free radical addition reaction in the presence of an initiator to obtain PR C2 group.

[0098] Preferably, the molar weight of the hypophosphite is n1, the molar weight of the third olefin is n4, the molar weight of the fourth olefin is n5, n4 / n1 is less than 2, for example, it can be 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 1.9, etc.; n5 / n1 is less than 2, for example, it can be 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 1.9, etc.

[0099] In another preferred technical solution, the preparation method of the organic phosphinate having the structure shown in Formula VI comprises: neutralizing an organic phosphinate with a strong base to obtain a water-soluble organic phosphinate; and performing a double decomposition reaction between the water-soluble organic phosphinate and an M salt to obtain the organic phosphinate, and the reaction formula is as follows:

[0100] .

[0101] In Formula VI, R D1 Any one selected from substituted or unsubstituted C2-C8 straight or branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C18 aryl; R D2 Any one selected from hydrogen, substituted or unsubstituted C2-C8 linear or branched alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C18 aryl.

[0102] M3OH represents a strong base, and M3 is preferably Na or K, and more preferably Na.

[0103] In a preferred technical solution, the preparation method of the ethyl phosphonate comprises: performing an addition reaction of phosphorous acid and ethylene in the presence of an initiator, followed by neutralization to obtain a water-soluble ethyl phosphonate; and performing a double decomposition reaction of the water-soluble ethyl phosphonate with an M salt to obtain the ethyl phosphonate.

[0104] In each of the above preparation methods, the hypophosphite is preferably a water-soluble hypophosphite, each independently comprising sodium hypophosphite and / or potassium hypophosphite, more preferably sodium hypophosphite; the sodium hypophosphite may be anhydrous sodium hypophosphite and / or sodium hypophosphite hydrate (e.g., sodium hypophosphite monohydrate).

[0105] In each of the aforementioned preparation methods, the initiator independently includes any one of persulfate, organic peroxide, azo initiator, photoinitiator, or a combination of at least two thereof, with persulfate being more preferred.

[0106] Preferably, the persulfate includes any one of sodium persulfate, potassium persulfate, and ammonium persulfate, or a combination of at least two of them.

[0107] Preferably, the organic peroxide includes diisobutyryl peroxide, benzoyl peroxide, bis(2-ethylhexyl peroxydicarbonate), diisopropyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, dilauroyl peroxide, di(3,3,5-trimethylacetyl) peroxide, 2,5-dimethyl-2,5-di(2-ethylacetyl peroxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, 2-methyl-2-methyl-3-hydroxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2-propoxy-4-propoxy-2 Any one or a combination of at least two of tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butyl peroxide, di-tert-pentyl peroxide, diisopropylbenzene peroxide, 2,5-di-tert-butylperoxy-2,5-dimethylhexane, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxymaleate, and tert-butyl peroxy-2-ethylhexyl carbonate

[0108] Preferably, the azo initiator includes any one of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutyramidine hydrochloride, azobisisobutylimidazoline hydrochloride, and azoisobutylcyanamide, or a combination of at least two thereof.

[0109] In each of the aforementioned preparation methods, the initiator can be added all at once, in batches, or continuously during the reaction.

[0110] In each of the aforementioned preparation methods, the addition reaction is carried out in the presence of a solvent, and the solvent includes water.

[0111] Preferably, the mass ratio of the hypophosphite to the solvent (preferably water) is 1:(0.5-10), for example, it can be 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, etc., and more preferably 1:(1-5).

[0112] Preferably, in each of the aforementioned preparation methods, the temperature of the addition reaction is independently 50-120°C, for example, it can be 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C or 115°C, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range. It is further preferred to be 70-110°C, and more preferably 95-105°C.

[0113] Preferably, in each of the aforementioned preparation methods, the pressure of the addition reaction is independently 0.2-3.5 MPa, for example, 0.3 MPa, 0.5 MPa, 0.8 MPa, 1 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa, 2 MPa, 2.2 MPa, 2.5 MPa, 2.8 MPa, 3 MPa, or 3.2 MPa, as well as specific values ​​between the aforementioned values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively enumerate the specific values ​​included in the aforementioned ranges. The pressure can be provided by the gaseous olefin, by an inert gas (e.g., nitrogen), or by both the olefin and the inert gas.

[0114] Preferably, in each of the aforementioned preparation methods, the time of the addition reaction is independently 1-20 h, for example, it can be 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h or 18 h, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0115] Preferably, in each of the aforementioned preparation methods, the M salt is a water-soluble M salt, including but not limited to M chloride and / or M sulfate, and the M comprises any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti. The M salt is an anhydrous M salt and / or an M salt hydrate.

[0116] Preferably, in each of the aforementioned preparation methods, the temperature of the metathesis reaction is independently 20-120°C, for example, it can be 25°C, 30°C, 40°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 90°C, 95°C, 100°C, 105°C, 110°C or 115°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 45-95°C is further preferred.

[0117] Preferably, in each of the aforementioned preparation methods, the time of the metathesis reaction is independently 1-10 h, for example, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h or 9 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0118] In a second aspect, the present invention provides a use of the polymer additive as described in the first aspect in a polymer material.

[0119] Preferably, the polymer additive is applied to the polymer material as a flame retardant.

[0120] Preferably, the polymer includes any one of thermoplastic resin, thermoplastic elastomer, thermosetting resin, or a combination of at least two thereof.

[0121] Preferably, the polymer includes any one of polyester, polyamide, polyurethane, styrene-based polymer, polyketone, polyolefin, polyacrylate, or a combination of at least two thereof.

[0122] Preferably, the polyurethane includes polyurethane resin and / or polyurethane elastomer.

[0123] Preferably, the polyester comprises polyester resin and / or polyester elastomer.

[0124] In a third aspect, the present invention provides a polymer composition comprising a thermoplastic polymer and a combination of the polymer additives described in the first aspect.

[0125] Preferably, the polymer composition comprises the following components in parts by mass:

[0126] 40-99.5 parts of thermoplastic polymer

[0127] 5-35 parts of the polymer additive;

[0128] Specifically, the mass fraction of the thermoplastic polymer is 40-99.5 parts, for example, it can be 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 98 parts, as well as specific point values ​​between the above point values, or for example, it can be in the range of 40-50 parts, 51-60 parts, 61-70 parts, 71-80 parts, 81-90 parts, 91-99 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0129] The mass parts of the polymer additive are 5-35 parts, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts or 34 parts, as well as specific point values ​​between the above point values, or for example, can be in the range of 5-10 parts, 11-15 parts, 16-20 parts, 21-25 parts, 26-30 parts, 31-35 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0130] Preferably, the thermoplastic polymer includes any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyketone, polyolefin, and polyacrylate.

[0131] Preferably, the polyamide includes any one of polyamide resin and polyamide elastomer, or a combination of at least two of them.

[0132] As a polyamide, it includes any one or a combination of at least two of the condensation products of dicarboxylic acids and diamines, condensation products of ω-amino acids, and ring-opening polymerization products of cyclic lactams. The dicarboxylic acids illustratively include but are not limited to: any one or a combination of at least two of adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, and isophthalic acid. The diamines illustratively include but are not limited to: any one or a combination of at least two of hexamethylenediamine, decanediamine, dodecanediamine, butanediamine, p-phenylenediamine, and m-phenylenediamine. The cyclic lactams illustratively include but are not limited to: any one or a combination of at least two of caprolactam, capryllactam, undecane lactam, and laurolactam. The ω-amino acids illustratively include but are not limited to: any one or a combination of at least two of the ω-amino acids formed by the ring opening of the aforementioned cyclic lactams and aminobenzoic acid.

[0133] Illustratively, the polyamide includes any one of polyamide 6 (polycaprolactam), polyamide 11, polyamide 12, polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1212, polyamide 6T (polyhexamethylene terephthalamide), and polyamide 10T (polydecane terephthalamide), or a combination of at least two thereof.

[0134] Illustratively, the polyamide elastomer comprises a hard segment derived from polyamide and a soft segment derived from a polyol, wherein the polyol comprises a polyether polyol and / or a polyester polyol, preferably a polyether polyol.

[0135] Preferably, the polyester comprises polyester resin and / or polyester elastomer.

[0136] Preferably, the polyester comprises a condensation product of a dicarboxylic acid and / or its derivatives with a diol, wherein the dicarboxylic acid illustratively 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, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, and hydrogenated phthalic acid, and the derivatives include acyl halides (chlorides), esters, and anhydrides formed from the dicarboxylic acids. The diol illustratively includes, but is not limited to, any one or a combination of at least two of ethylene glycol, butanediol, and hexanediol.

[0137] Exemplarily, the polyester includes polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

[0138] Preferably, the polyurethane includes polyurethane resin and / or polyurethane elastomer.

[0139] Preferably, the polyurethane comprises a reaction product of a polyol and an isocyanate, wherein the polyol illustratively includes but is not limited to: any one of polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol, or a combination of at least two thereof.

[0140] Preferably, the styrene-based polymer includes any one or a combination of at least two of a styrene homopolymer (PS), a styrene-acrylate copolymer, a styrene-olefin copolymer, and a styrene-olefin-acrylonitrile copolymer; the styrene-olefin copolymer illustratively includes but is not limited to: any one or a combination of at least two of a styrene-(ethylene-propylene) diblock copolymer, a styrene-(ethylene-butylene)-ethylene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, and a styrene-ethylene-isoprene terpolymer.

[0141] Preferably, the polyolefin includes any one or a combination of at least two of polyethylene, α-olefin homopolymer, α-olefin copolymer, ethylene-α-olefin copolymer, and ethylene-α-olefin-diene copolymer; wherein the α-olefin exemplarily includes but is not limited to: any one or a combination of at least two of propylene, butene, pentene, hexene, heptene, and octene; the diene exemplarily includes but is not limited to: any one or a combination of at least two of isoprene, butadiene, and hexadiene.

[0142] It should be noted that the polymer composition of the present invention may further include any other additives that are added with motivation in the art.

[0143] Preferably, the polymer composition further comprises 0-45 parts of filler in parts by mass, and the mass proportion of the filler may be 0.1 parts, 0.5 parts, 1 parts, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 42 parts, as well as specific values ​​between the above points, or, for example, may be in the range of 0-10 parts, 11-20 parts, 21-30 parts, 31-40 parts, 41-45 parts. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively enumerates the specific values ​​included in the range.

[0144] Preferably, the filler comprises reinforcing material and / or filler.

[0145] Preferably, the reinforcement material comprises glass fiber and / or carbon fiber.

[0146] Preferably, the filler includes any one or a combination of at least two of silicon dioxide, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass microspheres.

[0147] Preferably, the polymer composition further includes 0-15 parts by mass of other additives, and the mass of the other additives can be 0.1 parts, 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts or 14 parts, as well as specific point values ​​between the above point values, or, for example, can be in the range of 0.1-1 parts, 1.5-5 parts, 5.5-10 parts, 10.5-15 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0148] Preferably, the other additives include any one or a combination of at least two of antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, and colorants, and more preferably include antioxidants and / or lubricants.

[0149] Preferably, the mass fractions of the antioxidant, ultraviolet absorber, lubricant and nucleating agent in the polymer composition are each independently 0.01-1.5 parts, for example, 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.1 parts, 1.2 parts or 1.4 parts, as well as specific point values ​​between the above point values, or for example, the range of 0.01-0.1 parts, 0.2-0.5 parts, 0.6-1 parts, 1.1-1.5 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0150] Preferably, the antioxidant includes any one of a hindered amine antioxidant, a hindered phenol antioxidant, and a phosphite antioxidant, or a combination of at least two thereof.

[0151] Preferably, the lubricant includes any one of ester lubricants, alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, and metal soap lubricants, or a combination of at least two thereof.

[0152] Preferably, the polymer composition further comprises 0-15 parts by mass of a synergistic flame retardant, and the mass percentage of the synergistic flame retardant can be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14 parts, as well as specific point values ​​between the above point values, or, for example, can be in the range of 0-2, 3-5, 6-8, 9-12, or 13-15 parts. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0153] Preferably, the synergistic flame retardant includes any one of melamine polyphosphate, melamine polyphosphate salt, zinc borate, zinc stannate, zinc sulfide, and boehmite, or a combination of at least two thereof.

[0154] In a preferred technical solution, the polymer composition comprises the following components in parts by mass:

[0155] 40-99.5 parts of thermoplastic polymer

[0156] 5-35 parts of the polymer additive

[0157] Reinforcement material and / or filler 0-45 parts

[0158] Synergistic flame retardant 0-15 parts

[0159] 0-1.5 parts antioxidant

[0160] Lubricant 0-1.5 parts.

[0161] The thermoplastic polymer is a matrix material. Preferably, the mass percentage of the thermoplastic polymer in the polymer composition is 40%-99.5%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, and specific values ​​between the above points, or for example, it can be in the range of 40-50%, 51-60%, 61-70%, 71-80%, 81-90%, 91-99%. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific points included in the range.

[0162] The polymer additive has a flame retardant effect. Preferably, the mass percentage of the polymer additive in the polymer composition is 5%-35%, for example, it can be 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32% or 34%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range. It is further preferred to be 6%-20%, and more preferably 8%-18%.

[0163] Illustratively, the method for preparing the polymer composition includes: melt-blending the components of the polymer composition and then extruding to obtain the polymer composition.

[0164] Preferably, the thermoplastic polymer, polymer additive, optional filler, optional antioxidant and optional lubricant are first premixed to obtain a premix; and then the premix is ​​melt-blended with the reinforcing material and then extruded to obtain the polymer composition.

[0165] Preferably, the melt blending is carried out in a screw extruder.

[0166] Preferably, the screw extruder is a twin-screw extruder.

[0167] Preferably, the temperature of the screw extruder is 180-330°C, for example, it can be 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C or 320°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0168] Preferably, the extrusion further includes granulation and drying steps.

[0169] Compared with the prior art, the present invention has the following beneficial effects:

[0170] The polymer additive provided by the present invention significantly enhances flame retardancy through the design and synergistic combination of various phosphonates, resulting in the polymer additive having excellent and efficient flame retardancy while also being less susceptible to migration and precipitation under wet and hot conditions. When used in polymer materials, the polymer additive can impart excellent flame retardancy to polymer compositions containing the polymer additive even at a relatively low addition amount. Furthermore, the polymer additive exhibits good toughness, high impact strength, excellent mechanical properties, and wet and hot resistance, maintaining excellent flame retardancy and high impact strength even after wet and hot aging. DETAILED DESCRIPTION

[0171] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0172] As used herein, the terms "comprises," "including," "having," "containing" or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a listed element is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0173] In the present invention, features specified as "first," "second," "third," etc. may explicitly or implicitly include one or more of such features and are used to distinguish and describe features, without regard to order or importance. In the description of the present invention, unless otherwise specified, "plurality" means two or more.

[0174] In the following specific embodiments of the present invention, unless otherwise specified, reagents without a specific preparation method are all commercially available chemicals. The target product obtained in the following preparation example was dissolved in a deuterated sodium hydroxide aqueous solution and then subjected to nuclear magnetic resonance (NMR) P spectrum analysis to characterize the product composition and structure. The specific method includes: using a 50% deuterated sodium hydroxide aqueous solution as a solvent, preparing a 5% solution of the sample to be tested, and using a Bruker NMR spectrometer (AVANCE NEO 400 MHz) for analysis. 31 P spectrum test, by integrating the P displacement peak, obtains qualitative and quantitative analysis results based on the integrated area.

[0175] Preparation Example 1

[0176] 2000 g of sodium hypophosphite monohydrate and 3000 g of water were added to an autoclave, followed by 5 g of sodium persulfate. The atmosphere was replaced with 0.6 MPa nitrogen three times before venting. The autoclave was sealed and filled with ethylene to 0.7 MPa. The mixture was stirred and heated to 100°C. The reaction was maintained at 100°C for 3 hours. Over the same 3 hours, an aqueous solution prepared by adding 5 g of sodium persulfate and 20 g of water was continuously fed at a constant rate. During the reaction, ethylene was added using a pressure regulator to maintain the reactor pressure at 0.7 MPa. The reaction was then held at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution containing sodium diethylphosphinate and sodium ethyl-n-butylphosphinate.

[0177] The aqueous solution was diluted with water to a sodium salt content of 25% by weight. The mixture was heated to 60°C and an aqueous aluminum sulfate solution (prepared from 2094 g of aluminum sulfate 18-hydrate and 6300 g of water) was added dropwise over 1.5 hours with stirring. The mixture was then incubated for 20 minutes. After the addition was complete, the mixture was filtered and washed three times with water equal to three times the weight of the filter cake to yield 2350 g of aluminum diethylphosphinate, containing 0.36 mol% aluminum ethyl-n-butylphosphinate.

[0178] Preparation Example 2

[0179] 2000 g of sodium hypophosphite monohydrate and 3000 g of water were added to an autoclave, followed by 5 g of sodium persulfate. The atmosphere was then purged with 0.6 MPa nitrogen three times and vented. The autoclave was sealed and filled with ethylene to 4.0 MPa. The mixture was stirred and heated to 100°C. The reaction was maintained at 100°C for 3 hours. An aqueous solution prepared by adding 5 g of sodium persulfate and 20 g of water was continuously added at a constant rate over 2.5 hours. Ethylene was added via a pressure regulator to maintain the reactor pressure at 4.0 MPa. The reaction was then held at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution containing sodium diethylphosphinate and sodium ethyl-n-butylphosphinate.

[0180] The aqueous solution was diluted with water to a sodium salt content of 25% by weight. The mixture was heated to 60°C and, with stirring, an aqueous solution of aluminum sulfate (prepared from 2094 g of aluminum sulfate 18-hydrate and 6300 g of water) was continuously added dropwise over 1.5 hours. The mixture was then incubated for 20 minutes. After the addition was complete, the mixture was filtered and washed three times with water equal to three times the weight of the filter cake to yield 2355 g of aluminum diethylphosphinate, containing 13.8 mol% aluminum ethyl-n-butylphosphinate.

[0181] Preparation Example 3

[0182] 2000 g of sodium hypophosphite monohydrate and 5000 g of water were added to a high-pressure reactor, followed by 5 g of sodium persulfate. The atmosphere was replaced with 0.6 MPa nitrogen three times, then filled with nitrogen to 0.5 MPa. The high-pressure reactor was sealed, stirred, and heated to 110°C. At 110°C, 2222 g of n-butene was continuously fed using a cryogenic pump over 3 hours. Furthermore, an aqueous solution prepared by adding 5 g of sodium persulfate and 20 g of water was continuously fed over 4 hours. The temperature was then maintained at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution of sodium di-n-butylphosphinate.

[0183] Dilute the sodium dibutylphosphinate aqueous solution with water to a sodium salt content of 20% by weight. Heat to 70°C and continuously add an aluminum sulfate aqueous solution (prepared from 2094 g of aluminum sulfate 18-hydrate and 6300 g of water) dropwise over 1.5 hours with stirring. Incubate the mixture for 20 minutes. After the addition is complete, filter and wash the filter cake five times with water equal to three times its weight to yield 3333.9 g of di-n-butylaluminum phosphinate.

[0184] Preparation Example 4

[0185] 2000 g of sodium hypophosphite monohydrate and 5000 g of water were added to a high-pressure reactor, followed by 5 g of sodium persulfate. The atmosphere was replaced with 0.6 MPa nitrogen three times, then filled with nitrogen to 0.5 MPa. The reactor was sealed and heated to 110°C with stirring. The temperature was maintained at 110°C for 3 hours. During this time, 1700 g of n-butene was continuously fed using a cryogenic pump. An aqueous solution prepared by adding 5 g of sodium persulfate and 20 g of water was then continuously fed at a constant rate over 4 hours. The mixture was then kept at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution containing sodium n-butylphosphinate and sodium di-n-butylphosphinate.

[0186] The aqueous solution was acidified with 2003 g of 30% sulfuric acid aqueous solution at room temperature, 1000 mL of toluene was added and shaken evenly, and the upper and lower layers were separated using a separatory funnel.

[0187] The lower aqueous solution was removed and heated to 70°C. An aqueous aluminum sulfate solution (prepared from 840 g of aluminum sulfate 18-hydrate and 2520 g of water) was continuously added dropwise under stirring within 1.5 h. After the addition was complete, the mixture was kept warm for 20 min. After the reaction was completed, the mixture was filtered and washed five times with water 3 times the weight of the filter cake to obtain 941.6 g of n-butyl aluminum phosphinate product.

[0188] The solvent in the upper toluene phase was evaporated using a rotary evaporator, and the mixture was neutralized to pH 7 by adding a 20% aqueous sodium hydroxide solution. The mixture was diluted with water to a solid content of 20%, and the mixture was heated to 70°C. An aqueous aluminum sulfate solution (prepared from 1257 g of aluminum sulfate 18-hydrate and 3780 g of water) was continuously added dropwise under stirring over 1.5 h. After the addition was complete, the mixture was kept warm for 20 min. After the reaction was completed, the mixture was filtered and washed five times with water three times the weight of the filter cake to obtain 2008.7 g of di-n-butylaluminum phosphinate product.

[0189] Preparation Example 5

[0190] Aluminum diisobutylphosphinate was prepared. The preparation method was the same as that in Preparation Example 3 except that n-butene was replaced with an equal amount of isobutylene. Other materials, amounts, and processes were the same as those in Preparation Example 3.

[0191] Preparation Example 6

[0192] Aluminum diisobutylphosphinate and aluminum isobutylphosphinate were prepared. The preparation method differed from that in Preparation Example 4 only in that n-butene was replaced with an equal amount of isobutylene. Other materials, amounts, and processes were the same as in Preparation Example 4, yielding 1997.3 g of aluminum diisobutylphosphinate and 951.2 g of aluminum isobutylphosphinate.

[0193] Preparation Example 7

[0194] 2000 g of sodium hypophosphite monohydrate, 3200 g of cyclohexene, and 6000 g of water were added to an autoclave. 5 g of sodium persulfate was added, and the atmosphere was replaced with 0.6 MPa nitrogen three times before being filled with nitrogen to 0.5 MPa. The autoclave was sealed and heated to 110°C with stirring. The reaction was maintained at 110°C for 6 hours. An aqueous solution prepared by adding 18 g of sodium persulfate and 162 g of water was continuously added at a constant rate over the same 6 hours. The mixture was then kept at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution of sodium dicyclohexylphosphinate.

[0195] Dilute the sodium dicyclohexylphosphinate aqueous solution with water to a sodium salt content of 10% by weight. Heat to 70°C and continuously add an aluminum sulfate aqueous solution (prepared from 2094 g of aluminum sulfate 18-hydrate and 6300 g of water) dropwise over 3 hours with stirring. Incubate for 60 minutes after the addition is complete. After the reaction is complete, filter and wash the filter cake five times with water (three times the weight of the filter cake) to yield 4176.3 g of aluminum dicyclohexylphosphinate.

[0196] Preparation Example 8

[0197] 2000 g of sodium hypophosphite monohydrate, 2600 g of cyclohexene, and 6000 g of water were added to an autoclave, followed by 5 g of sodium persulfate. The atmosphere was replaced with 0.6 MPa nitrogen three times, then filled with nitrogen to 0.5 MPa. The autoclave was sealed and heated to 110°C with stirring. The reaction was maintained at 110°C for 5 hours. An aqueous solution prepared by adding 18 g of sodium persulfate and 162 g of water was continuously added at a constant rate over the same 5 hours. The mixture was then kept at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution containing sodium cyclohexylphosphinate and sodium dicyclohexylphosphinate.

[0198] The aqueous solution was acidified with 2000 g of 30% sulfuric acid aqueous solution at room temperature, 1000 mL of cyclohexane was added and shaken evenly, and the upper and lower layers were separated using a separatory funnel.

[0199] The lower aqueous solution was removed and heated to 70°C. An aluminum sulfate aqueous solution (prepared from 840 g of aluminum sulfate 18-hydrate and 2520 g of water) was continuously added dropwise under stirring within 1.5 h. After the addition was complete, the mixture was kept warm for 20 min. After the reaction was completed, the mixture was filtered and washed five times with water 3 times the weight of the filter cake to obtain 1109.3 g of cyclohexyl phosphinate aluminum product.

[0200] The solvent in the upper cyclohexane phase was evaporated using a rotary evaporator, and the mixture was neutralized to pH 7 by adding 20% ​​aqueous sodium hydroxide solution. The mixture was diluted with water to a solid content of 20%, and the mixture was heated to 70°C. An aqueous aluminum sulfate solution (prepared from 1257 g of aluminum sulfate 18-hydrate and 3780 g of water) was continuously added dropwise under stirring over 1.5 h. After the addition was complete, the mixture was kept warm for 20 min. After the reaction was completed, the mixture was filtered and washed five times with water three times the weight of the filter cake to obtain 2507.0 g of dicyclohexyl aluminum phosphinate product.

[0201] Preparation Example 9

[0202] 2000 g of diphenylphosphinic acid, 267 g of sodium hydroxide, and 8000 g of water were mixed, stirred, and heated to 80°C for 1 hour to produce an aqueous solution of sodium diphenylphosphinic acid. An aqueous solution of aluminum sulfate prepared by adding 1017 g of aluminum sulfate 18-hydrate and 4070 g of water was added dropwise over 3 hours. After the addition was complete, the mixture was heated and reacted for 60 minutes. After the reaction was complete, the mixture was filtered and washed five times with water three times the weight of the filter cake to produce the aluminum diphenylphosphinic acid product.

[0203] Preparation Example 10

[0204] Mix 1292 g of phenylphosphinic acid, 267 g of sodium hydroxide, and 8000 g of water, stir, and heat to 80°C. Reaction is continued for 1 hour to prepare an aqueous solution of sodium phenylphosphinic acid. Add an aqueous solution of aluminum sulfate prepared by adding 1017 g of aluminum sulfate octahydrate and 4070 g of water continuously over 3 hours. After addition is complete, heat and react for 60 minutes. Filter and wash the filter cake five times with water three times its weight to obtain the aluminum phenylphosphinic acid product.

[0205] Preparation Example 11

[0206] 1000 g of phosphorous acid and 3000 g of water were added to a high-pressure reactor, followed by 5 g of sodium persulfate. The atmosphere was replaced with 0.6 MPa nitrogen three times and then vented. The reactor was sealed and filled with ethylene to 0.7 MPa. The mixture was stirred and heated to 85°C. The temperature was maintained at 85°C for 3 hours. Over the same 3 hours, an aqueous solution prepared by adding 5 g of sodium persulfate and 20 g of water was continuously fed at a constant rate. During the reaction, ethylene was added using a pressure regulator to maintain the reactor pressure at 0.7 MPa. The reaction was then held at 95°C for 1 hour, cooled, and discharged. The mixture was then neutralized with 20% sodium hydroxide solution to a pH of 7 to obtain an aqueous solution of sodium ethylphosphonate.

[0207] Dilute the sodium ethylphosphonate aqueous solution with water to a sodium salt content of 25% by weight. Heat to 60°C and continuously add an aluminum sulfate aqueous solution (prepared from 2707 g of aluminum sulfate 18-hydrate and 10,830 g of water) dropwise over 2.5 hours while stirring. Incubate for 20 minutes after addition. After the reaction is complete, filter and wash three times with water equal to three times the weight of the filter cake to obtain the aluminum ethylphosphonate product.

[0208] Preparation Example 12

[0209] 2000 g of sodium hypophosphite monohydrate and 3000 g of water were added to an autoclave, followed by 5 g of sodium persulfate. The atmosphere was replaced with 0.6 MPa nitrogen three times before venting. The autoclave was sealed and filled with propylene to 0.6 MPa. The reactor was stirred and heated to 105°C. The temperature was maintained at 105°C for 5 hours. Over the same 5 hours, an aqueous solution prepared by adding 10 g of sodium persulfate and 40 g of water was continuously added at a constant rate. During the reaction, propylene was added using a pressure regulator to maintain the reactor pressure at 0.6 MPa. The reactor was then kept at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution containing sodium di-n-propylphosphinate and sodium n-propylisopropylphosphinate.

[0210] The aqueous solution was diluted with water to a sodium salt content of 25% by weight. The mixture was heated to 55°C and an aqueous aluminum sulfate solution (prepared from 2094 g of aluminum sulfate 18-hydrate and 6300 g of water) was added dropwise over 1.5 hours with stirring. After the addition was complete, the mixture was incubated for 40 minutes. After the reaction was complete, the mixture was filtered and washed three times with water equal to three times the weight of the filter cake. A total of 2899 g of aluminum di-n-propylphosphinate was obtained, containing 4.3 mol% aluminum n-propylisopropylphosphinate.

[0211] Preparation Example 13

[0212] 2000 g of sodium hypophosphite monohydrate and 3000 g of water were added to an autoclave, followed by 5 g of sodium persulfate. The atmosphere was then purged with 0.6 MPa nitrogen three times and vented. 160 g of n-hexene was added, and the autoclave was sealed. The temperature was raised to 105°C with stirring and maintained at 105°C for 5 hours. Over the same 5 hours, an aqueous solution of 10 g of sodium persulfate in 40 g of water and 1950 g of n-hexene were continuously added. The reaction was then maintained at 110°C for 1 hour, cooled, and discharged to obtain an aqueous solution containing sodium di-n-hexylphosphinate and sodium n-hexylphosphinate.

[0213] The aqueous solution was acidified with 2000 g of 30% sulfuric acid aqueous solution at room temperature, 1000 mL of cyclohexane was added and shaken evenly, and the upper and lower layers were separated using a separatory funnel.

[0214] The lower aqueous solution was removed and heated to 70°C. An aqueous aluminum sulfate solution (prepared from 840 g of aluminum sulfate 18-hydrate and 2520 g of water) was continuously added dropwise under stirring within 1.5 h. After the addition was complete, the mixture was kept warm for 20 min. After the reaction was completed, the mixture was filtered and washed five times with water 3 times the weight of the filter cake to obtain 1086.4 g of n-hexyl aluminum phosphinate product.

[0215] The solvent in the upper cyclohexane phase was evaporated using a rotary evaporator, and the mixture was neutralized to pH 7 by adding 20% ​​aqueous sodium hydroxide solution. The mixture was diluted with water to a solid content of 20%, and the mixture was heated to 70°C. An aqueous aluminum sulfate solution (prepared by 1257 g of aluminum sulfate 18-hydrate and 3780 g of water) was continuously added dropwise under stirring over 1.5 h. After the addition was complete, the mixture was kept warm for 20 min. After the reaction was completed, the mixture was filtered and washed five times with water three times the weight of the filter cake to obtain 2477.5 g of di-n-hexyl aluminum phosphinate product.

[0216] Preparation Example 14

[0217] Ethyl n-butyl aluminum phosphinate was prepared according to the method of Example 4 of CN103172670A.

[0218] Several examples of the polymer additives of the present invention are exemplified below. In the following examples, the materials used are from Preparation Examples 1-14 and / or commercially available.

[0219] Examples 1-26, Comparative Examples 1-6

[0220] A polymer additive, the types and amounts of each component are shown in Table 1, Table 2 and Table 3, and the unit of the amount of each component is "parts by mass".

[0221] Table 1

[0222]

[0223] Table 2

[0224]

[0225] In Table 2, "aluminum dipropylphosphinate" includes aluminum di-n-propylphosphinate and aluminum n-propylisopropylphosphinate, and the molar ratio of the two is 94.8:4.3.

[0226] Table 3

[0227]

[0228] The following are several examples of applications of the polymer additive of the present invention in polymer compositions. In the following application examples, the specific information of the materials used is as follows:

[0229]

[0230] Application Examples 1-52, Comparative Examples 1-12

[0231] A polymer composition, specifically a polyamide composition, the types and amounts of the components are shown in Tables 4 to 8, and the units of the amounts of the components are all "parts"; the polymer additives are from Examples 1-26 and Comparative Examples 1-6.

[0232] The preparation method of the polyamide composition comprises: placing all components except glass fiber in a mixer according to the formula amount, and mixing at a speed of 60 rpm for 20 minutes to obtain a premix; adding the premix into a twin-screw extruder from a main feeding port, adding the glass fiber into the twin-screw extruder from a side feeding port, melt-blending, and then extruding, granulating, drying and cooling to obtain the polyamide composition; wherein the screw speed of the twin-screw extruder is 500 rpm, and the temperature from the feeding section to the die head is 90°C, 275°C, 270°C, 260°C, 260°C, 230°C, 230°C, 220°C, 220°C, and 260°C.

[0233] The following performance tests were performed on the polyamide composition:

[0234] (1) Flame retardancy: 125 mm × 13 mm × 1.6 mm and 125 mm × 13 mm × 0.8 mm square plates were made by injection molding and tested according to the method in standard ANSI / UL-94-1985. The test results were recorded as "pre-aging performance test";

[0235] After aging the square plate at 85°C and 85% humidity for 500 h, the flame retardancy was tested using the same method. The test results were recorded as "performance test after damp heat aging";

[0236] (2) Notched impact strength: The notched cantilever beam impact strength was tested according to the method in ISO 180-2019. The specimens were injection molded into 80 mm × 10 mm × 4 mm strips with an impact energy of 2.75 J and an A-notch. The test results were recorded as “performance test before aging”.

[0237] After aging the specimens at 85°C and 85% humidity for 500 h, the notched impact strength was tested using the same method. The test results were recorded as "performance test after damp heat aging";

[0238] The test data are shown in Tables 4 to 8.

[0239] Table 4

[0240]

[0241] Table 5

[0242]

[0243] Table 6

[0244]

[0245] Table 7

[0246]

[0247] Table 8

[0248]

[0249] Combined with the aforementioned performance test data, it can be seen that the polymer additive provided by the present invention has an excellent flame retardant effect through the design and synergistic compounding of each component, and can impart excellent flame retardancy to the polyamide composition containing it with a small addition amount, achieving a V0-V1 flame retardant effect for 1.6 mm and 0.8 mm plates. At the same time, the notched impact strength of the glass fiber reinforced polyamide composition is ≥8.9 J / m, and it has excellent toughness and impact resistance; moreover, the flame retardancy of the polyamide composition does not decay after 500 h of wet heat aging under double 85 (85°C, 85% humidity) conditions, and the retention rate of the notched impact strength is >90%, showing excellent resistance to wet heat aging.

[0250] Comparing the data in Tables 4-7 and 8, it can be seen that the polymer additives D1-D6 provided in Comparative Examples 1-6, which do not contain the combination of the four types of phosphonates specified in this invention, or whose dosage ratios exceed the range of this invention, fail to achieve a synergistic flame retardant effect, resulting in reduced flame retardancy in the polyamide compositions containing them and significant degradation of both flame retardancy and impact strength after wet-heat aging. Increasing the dosage of polymer additives D1-D6 in Comparative Examples 7-12 improves the flame retardancy of the materials, but reduces the notched impact strength of the polyamide compositions, decreases flame retardancy after wet-heat aging, and significantly deteriorates mechanical properties.

[0251] The applicant states that while the above-described embodiments illustrate the polymer additive and its application, the present invention is not limited to these embodiments. This does not necessarily mean that the present invention must rely on these embodiments in order to be implemented. Those skilled in the art will understand that any improvements to the present invention, equivalent substitutions for raw materials in the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A polymer additive, characterized in that The polymer additive comprises the following components in parts by mass: 30-90 parts of diethylphosphinate 0.01-3 parts of ethylphosphonate 5-67 parts of dialkyl phosphinate 0.01-5.5 parts of hydrocarbyl phosphinate; The dialkyl phosphinate comprises a combination of a dialkyl phosphinate A having a structure shown in formula IA and an ethyl butyl phosphinate having a structure shown in formula IB; Formula IA; Formula IB; Among them, M1 m+ Indicates ions with +m valence; R1' and R2' are each independently selected from any one of a substituted or unsubstituted C2-C8 straight or branched alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, and a substituted or unsubstituted C6-C18 aryl group; The total number of carbon atoms in R1' and R2' is ≥6, and when one of R1' and R2' is ethyl, the other is not butyl; The substituents in R1' and R2' are each independently selected from at least one of a C1-C8 straight or branched alkyl group and a C6-C18 aryl group; The polymer additive comprises 5-60 parts by mass of dialkyl phosphinate A; The polymer additive includes 0.05-7 parts by mass of ethyl butyl phosphinate; The hydrocarbyl phosphinate has a structure as shown in Formula II: Formula II; wherein R3 is selected from any one of a substituted or unsubstituted C2-C8 straight or branched alkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, and a substituted or unsubstituted C6-C18 aryl group; The substituent in R3 is selected from at least one of a C1-C8 straight or branched alkyl group and a C6-C18 aryl group; M2 n+ Indicates +n valence ions; m and n are each independently selected from integers of 2-4.

2. The polymer additive according to claim 1, characterized in that The R1 and R2 are each independently selected from any one of a substituted or unsubstituted C2-C8 straight chain or branched alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, and a substituted or unsubstituted phenyl group; the substituents in R1 and R2 are each independently selected from at least one of a C1-C6 straight chain or branched alkyl group and a phenyl group.

3. The polymer additive according to claim 2, characterized in that R1 and R2 are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenylethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl; The total number of carbon atoms in R1 and R2 is 6-14.

4. The polymer additive according to claim 1, characterized in that R1' and R2' are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenylethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl; The dialkyl phosphinate A includes ethylpentylphosphinate, ethylhexylphosphinate, hexyloctylphosphinate, ethylcyclohexylphosphinate, ethylphenylphosphinate, ethylphenylethylphosphinate, ethylheptylphosphinate, dipropylphosphinate, propylbutylphosphinate, propylpentylphosphinate, propylhexylphosphinate, hexyloctylphosphinate, propylcyclohexylphosphinate, propylphenylphosphinate, propylphenylpropylphosphinate, propylheptylphosphinate, dibutylphosphinate, butylpentylphosphinate, butylhexylphosphinate, hexyloctylphosphinate, butylcyclohexylphosphinate, butylphenylphosphinate, butylphenylbutylphosphinate, butylheptylphosphinate, dicyclohexylphosphinate, dihexylphosphinate, and any one of diphenylphosphinate or a combination of at least two thereof.

5. The polymer additive according to claim 1, characterized in that R3 is selected from any one of C2-C6 straight or branched alkyl, C3-C6 cycloalkyl, and phenyl; The hydrocarbyl phosphinate includes any one or a combination of at least two of n-butyl phosphinate, isobutyl phosphinate, n-hexyl phosphinate, cyclohexyl phosphinate, and phenyl phosphinate; The M1 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti; The M2 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

6. The polymer additive according to claim 1, characterized in that The diethylphosphinate includes any one or a combination of at least two of diethylphosphinate aluminum, diethylphosphinate calcium, diethylphosphinate magnesium, diethylphosphinate copper, diethylphosphinate zinc, diethylphosphinate iron, and diethylphosphinate titanium; The ethylphosphonate includes any one of aluminum ethylphosphonate, calcium ethylphosphonate, magnesium ethylphosphonate, copper ethylphosphonate, zinc ethylphosphonate, iron ethylphosphonate, and titanium ethylphosphonate, or a combination of at least two thereof.

7. The polymer additive according to claim 1, characterized in that The polymer additive further comprises 0.01-25 parts by mass of phosphite; The phosphite includes any one of aluminum phosphite, calcium phosphite, magnesium phosphite, copper phosphite, zinc phosphite, iron phosphite, and titanium phosphite, or a combination of at least two of them.

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

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

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