Dialkylphosphine hybrid salts, their preparation methods, and applications

Abstract

This application discloses a dialkylphosphine hybrid salt, its preparation method, and its application. The dialkylphosphine hybrid salt is selected from at least one compound having the chemical formula shown in formula (I). The dialkylphosphine hybrid salt with the composition of formula (I) provided in this application requires a small amount to add, has high flame retardant efficiency for various polymer materials, and is economical. It not only overcomes the disadvantage of low flame retardant efficiency of diethylphosphine salt for polymer materials, but also overcomes the disadvantage of excessive volatility and low flame retardant efficiency of diisobutylphosphine salt for polyesters. It can be widely used in the flame retardant application of various polymer materials that require high-temperature processing.

Description

Technical Field

[0001] This application relates to a dialkylphosphine hybrid salt, its preparation method, and its application, belonging to the field of flame-retardant polymer material preparation. Background Technology

[0002] Dialkyl phosphines, especially aluminum diethyl phosphines, have been widely used as halogen-free flame retardants for polymer materials. Dialkyl phosphines offer low density, require smaller amounts of flame retardant, and exhibit good mechanical properties. However, the flame retardant efficiency of existing dialkyl phosphines is limited. For example, polydialkyl phosphines, while used as flame retardants for glass fiber-reinforced nylon, exhibit low flame retardant efficiency and significantly negatively impact the physical properties of flame-retardant polymers. There are also reports of using aluminum diisobutyl phosphines for nylon flame retardancy. While aluminum diisobutyl phosphines demonstrates very high flame retardant efficiency, its low thermal stability leads to significant degradation and volatilization at 300°C, which is detrimental to engineering plastics requiring high-temperature processing. Furthermore, aluminum diisobutyl phosphines show poor flame retardant effects on polyesters. Additionally, its high plasticity negatively impacts the physical properties of flame-retardant polymers. Summary of the Invention

[0003] To solve the above-mentioned technical problems, this application provides a dialkylphosphine hybrid salt, its preparation method and application. The dialkylphosphine hybrid salt with the composition of formula (Ⅰ) has a low addition amount, high flame retardant efficiency for various polymer materials, and good economic efficiency.

[0004] According to a first aspect of this application, a dialkylphosphine hybrid salt is provided, said dialkylphosphine hybrid salt being selected from at least one compound having the chemical formula shown in formula (I):

[0005]

[0006] In this context, M is the central atom, and diethylphosphine ion, ethylisobutylphosphine ion, and diisobutylphosphine ion are all ligands.

[0007] M is selected from metallic elements; the metallic element is selected from at least one of Group IIA, IIIA, IVA, VA metallic elements, transition metallic elements, and lanthanide metallic elements;

[0008] n represents the valence state of metal M; n is selected from 2, 3, or 4.

[0009] 0≤x≤0.95; 0.05≤y≤0.8; 0≤z≤0.5, and x+y+z=1, x+z>0.

[0010] In this embodiment of the application, in formula (Ⅰ), if y is less than 0.05, the flame retardant effect is poor; if y is greater than 0.8, the preparation cost is high, the economy is poor, and the thermal stability of the dialkylphosphine hybrid salt will decrease, which is detrimental to the preparation and physical properties of the flame retardant polymer material. If x is greater than 0.95, the flame retardant performance is poor. If z is greater than 0.5, the preparation cost is high, the economy is poor, and the thermal stability decreases, which is detrimental to the preparation and physical properties of the flame retardant polymer material.

[0011] Optionally, the lower limit of x is independently selected from 0, 0.15, 0.2, 0.25, 0.3, 0.35, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, and 0.03; and the upper limit is independently selected from 0.95, 0.9, 0.85, 0.87, and 0.7.

[0012] Optionally, the lower limit of y is independently selected from 0.05, 0.1, 0.15, 0.2, 0.13, and 0.29; and the upper limit is independently selected from 0.8, 0.7, 0.6, 0.5, 0.4, 0.35, 0.3, 0.25, and 0.68.

[0013] Optionally, the lower limit of z is independently selected from 0 and 0.02; the upper limit is independently selected from 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, and 0.05.

[0014] Optionally, the Group IIA metal element is selected from at least one of Be, Mg, Ca, Sr, and Ba;

[0015] The Group IIIA metallic element is Al;

[0016] The Group IVA metal element is Sn;

[0017] The Group VA metal element is Sb;

[0018] The transition metal element is selected from at least one of Fe, Zn, Cu, Ti, Zr, and Mn;

[0019] The lanthanide metal element is Ce.

[0020] Optionally, the metallic element is selected from at least one of Al, Zn, Ca, and Fe.

[0021] Optionally, the metallic element is Al, and n = 3.

[0022] Alternatively, 0.03≤x≤0.87; 0.13≤y≤0.68; 0≤z≤0.45.

[0023] Alternatively, 0.03≤x≤0.7; 0.29≤y≤0.68; 0.01≤z≤0.45.

[0024] Alternatively, 0.5≤x≤0.7; 0.29≤y≤0.48; 0.01≤z≤0.21.

[0025] In the embodiments of this application, the larger the z value, the earlier the thermal weight loss of the dialkylphosphine hybrid salt occurs.

[0026] The dialkylphosphine hybrid salts in this application are not simple physical mixtures of different dialkylphosphineates, for example, not simply mixtures of aluminum diethylphosphine and aluminum ethyl isobutylphosphine, but hybrid salts comprising diethylphosphine ions, ethyl isobutylphosphine ions, and diisobutylphosphine ions coordinated to the same aluminum atom. The X-ray diffraction (XRD) spectra of these hybrid salts are very different from those of simple physical mixtures of dialkylphosphineates. In the XRD pattern, the dialkylphosphine hybrid salts with the composition of formula (I) exhibit a single peak or overlapping double peaks in the region of strongest absorption. Furthermore, the interplanar spacing peaks shown by the maximum peaks are also different from those of aluminum diethylphosphine and aluminum diisobutylphosphine. The maximum peak of aluminum diethylphosphinate shows an interplanar spacing of d = 9.663, while that of aluminum diisobutylphosphinate is d = 12.084. The interplanar spacing d of the dialkylphosphinate hybrid salt of formula (I) falls between these two. Even with overlapping double peaks, their d values ​​indicate that they are not simple aluminum diethylphosphinate or aluminum diisobutylphosphinate. However, the physically mixed salt obtained by simply mixing aluminum diethylphosphinate and aluminum diisobutylphosphinate exhibits two completely independent peaks in the XRD pattern, and their d values ​​are close to those of aluminum diethylphosphinate and aluminum diisobutylphosphinate, respectively.

[0027] In the embodiments of this application, after a simple physical mixing of a dialkylphosphine hybrid salt having the composition of formula (I) and aluminum diethylphosphine, two independent peaks also appeared in their XRD patterns. These results strongly indicate that the dialkylphosphine hybrid salt having the composition of formula (I) obtained by the present invention is not a simple mixture of aluminum diethylphosphine, aluminum ethyl isobutylphosphine, and aluminum diisobutylphosphine, but rather a structure containing a diethylphosphine ion, an ethyl isobutylphosphine ion, and a diisobutylphosphine ion paired with the same aluminum atom.

[0028] In the embodiments of this application, at the same dosage, the flame retardant effect of pure diethylphosphonate or diisobutylphosphonate is far inferior to that of hybrid salts containing both diethylphosphonate and ethylisobutylphosphonate. Furthermore, the flame retardant performance is also related to the content of ethylisobutylphosphonate; only compositions within a specific range possess good flame retardant properties, thermal properties, and good economic efficiency.

[0029] According to a second aspect of this application, a method for preparing the above-mentioned dialkylphosphine hybrid salt is provided, the method comprising:

[0030] The material containing mixture A and metal element M source is reacted in an aqueous phase to obtain the dialkylphosphine hybrid salt;

[0031] The mixture A contains diethylphosphonic acid and / or its alkali metal salt, ethyl isobutylphosphonic acid and / or its alkali metal salt, and diisobutylphosphonic acid and / or its alkali metal salt.

[0032] Optionally, the molar ratio of the diethylphosphonic acid and / or its alkali metal salt, ethyl isobutylphosphonic acid and / or its alkali metal salt, diisobutylphosphonic acid and / or its alkali metal salt to the metal element M source is approximately x:y:z:q;

[0033] Where q = 1 / n.

[0034] Due to the different values ​​of M, the solubility of hybrid salts in water varies. For hybrid salts with high solubility, the values ​​of x, y, z in the solution of diethylphosphonic acid and / or its alkali metal salt, ethyl isobutylphosphonic acid and / or its alkali metal salt, and diisobutylphosphonic acid and / or its alkali metal salt differ from those in the hybrid salt, thus affecting their molar ratio with the M source. Furthermore, to obtain more M-containing precipitates, the molar ratios of reactants x, y, z, and M can exceed the theoretically calculated values.

[0035] In practice, the actual values ​​of x, y, z, and q can be determined using phosphorus NMR.

[0036] Optionally, the molar ratio of diethylphosphonic acid and / or its alkali metal salt, ethyl isobutylphosphonic acid and / or its alkali metal salt to diisobutylphosphonic acid and / or its alkali metal salt in the mixture A is the same as or substantially the same as the x, y, z ratio in formula (I).

[0037] Optionally, the conditions for reaction I are: temperature 0-250℃; pressure 0.1MPa-10MPa; time 0.1-20h.

[0038] Optionally, obtaining the mixture A includes the following steps:

[0039] Ethylene and isobutylene are passed into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator, and reaction II is carried out to obtain the mixture A.

[0040] Optionally, the molar ratio of the hypophosphonic acid and / or its alkali metal salt, ethylene, and isobutylene is 1:0.05-1.95:0.5-1.5.

[0041] In actual reactions, due to the presence of some side reactions, such as the long-chain dialkylphosphinates obtained from ethylene polymerization, the consumption of olefins is higher than the theoretical ratio.

[0042] Optionally, the molar ratio of the hypophosphite and / or its alkali metal salt, ethylene, and isobutylene is the same as or close to the values ​​of x, y, and z in formula (I). Optionally, in reaction II, the reaction rate is determined by the values ​​of x, y, and z. The larger the z value, the slower the reaction rate; therefore, the z value needs to be controlled for economic efficiency. Meanwhile, it has been found that in the reaction of hypophosphite or its alkali metal salt with ethylene or isobutylene, the y value has a maximum value less than 1. After reaching this maximum value, x or z increases, so y cannot reach 1. If it is necessary to prepare y = 1, the reaction intermediate product needs to be separated and purified to remove diethylphosphite and / or diisobutylphosphite or their salts, which is unfavorable for economic efficiency.

[0043] Specifically, in reaction II, the order in which ethylene and isobutylene are added can be interchanged, or they can be added simultaneously, or some can be added first.

[0044] Optionally, in reaction II, hypophosphite and / or its alkali metal salt react with isobutylene first to obtain the corresponding y,z values, and then react with ethylene substantially or completely. "Substantially complete" means that the total phosphorus content in the reaction mixture of ethylphosphite, isobutylphosphite, and hypophosphite is less than 5% molar of the total phosphorus content in the reaction solution.

[0045] Specifically, after reaction II is completed, there is no need to separate diethylphosphonic acid, ethyl isobutylphosphonic acid, diisobutylphosphonic acid, or their alkali metal mixtures; the next reaction can proceed directly.

[0046] Optionally, in the aqueous solution, the mass of the water is 10-99% of the total mass of the free radical initiator, the phosphonic acid and / or its alkali metal salt, and the water.

[0047] Specifically, in the aqueous solution, if there is too little water, the salting-out effect leads to low solubility of olefins in water and a slower reaction rate; if there is too much water, the utilization rate of the reaction vessel decreases.

[0048] Optionally, in the aqueous solution, the mass of the water is 20-95% of the total mass of the free radical initiator, the phosphonic acid and / or its alkali metal salt, and the water.

[0049] Optionally, in the aqueous solution, the mass of the water is 45-92% of the total mass of the free radical initiator, the phosphonic acid and / or its alkali metal salt, and the water.

[0050] Optionally, in the aqueous solution, the mass of the water is 50-90% of the total mass of the free radical initiator, the phosphonic acid and / or its alkali metal salt, and the water.

[0051] Optionally, in the aqueous solution, the mass of the water is 55-90% of the total mass of the free radical initiator, the phosphonic acid and / or its alkali metal salt, and the water.

[0052] Optionally, the conditions for reaction II are: temperature 0-250℃; time 0.01-50h; pressure 0-3MPa.

[0053] Specifically, if the temperature of reaction II is too low, the reaction rate is slow; if the temperature is too high, the hypophosphite is easily decomposed.

[0054] Optionally, the temperature of reaction II is 10-200°C.

[0055] Specifically, the pressure of reaction II is higher than 3 MPa, which increases the requirements for the reaction equipment and makes operation difficult.

[0056] Optionally, the pressure of reaction II is 0.2-1.5 MPa.

[0057] Optionally, the molar ratio of the free radical initiator to the phosphonic acid and / or its alkali metal salt is 0.001-0.1:1.

[0058] Optionally, the free radical initiator is selected from at least one of azo initiators, peroxide initiators, and photoinitiators. The amount of free radical initiator added can be determined according to actual needs.

[0059] Optionally, the azo initiator is selected from cationic and / or non-cationic azo initiators, including one or more of azobisisobutyronitrile, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-amidinylpropane) dihydrochloride, and 2,2'-azobisisobutyronitrile dihydrochloride.

[0060] Optionally, the peroxide initiator is preferably an inorganic peroxide or an organic peroxide radical initiator, and particularly preferably one or more of hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, sodium percarbonate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, and peracetic acid.

[0061] Preferably, the free radical initiator is a peroxide. Particularly preferably, the free radical initiator is selected from one of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0062] Optionally, the molar ratio of the free radical initiator to the phosphonic acid and / or its alkali metal salt is 0.003-0.05:1.

[0063] Optionally, obtaining the mixture A includes the following steps:

[0064] Isobutylene is introduced into an aqueous solution containing hypophosphite and / or its alkali metal salt and a free radical initiator to carry out the reaction. After the ratio of the introduced isobutylene to the total phosphorus molar of hypophosphite and / or its alkali metal salt reaches (y+2z) / 1 in formula (Ⅰ), the introduction of isobutylene is stopped, and ethylene is introduced to continue the reaction to obtain the mixture A.

[0065] Optionally, obtaining the mixture A includes the following steps:

[0066] Isobutylene is introduced into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator. After the isobutylene has reacted completely or nearly completely, ethylene is introduced to react and obtain the mixture A.

[0067] Optionally, phosphonic acid and / or its alkali metal salt react with isobutylene to obtain monoisobutylphosphonic acid or its alkali metal salt having or substantially close to a y value, and controlling z to be less than or equal to 0.5. Then, the addition of isobutylene is stopped and ethylene is added instead. The reaction continues in the presence of an initiator, followed by reaction with the desired metal salt to obtain a flame retardant having Formula I.

[0068] Optionally, obtaining the mixture A includes the following steps:

[0069] Isobutylene and a portion of ethylene are introduced into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator to carry out the reaction. The total phosphorus molar ratio of ethylene to phosphonic acid and / or its alkali metal salt is less than (2x+y) / 1 in formula (I). After the total phosphorus molar ratio of the introduced isobutylene to phosphonic acid and / or its alkali metal salt reaches (y+2z) / 1 in formula (I), the introduction of isobutylene is stopped, and the remaining portion of ethylene is introduced to continue the reaction to obtain the mixture A.

[0070] Optionally, obtaining the mixture A includes the following steps:

[0071] Isobutylene and a portion of ethylene are introduced into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator. After the isobutylene and a portion of ethylene have reacted completely or nearly completely, the remaining portion of ethylene is introduced to react and obtain the mixture A.

[0072] The total amount of ethylene and the molar ratio of isobutylene are 0.33-39:1.

[0073] Optionally, obtaining the mixture A includes the following steps:

[0074] A portion of ethylene is introduced into an aqueous solution containing hypophosphinoic acid and / or its alkali metal salt and a free radical initiator. The molar ratio of the portion of ethylene to the total phosphorus of hypophosphinoic acid and / or its alkali metal salt is less than (2x+y) / 1 in formula (I). After the portion of ethylene has reacted completely, isobutylene is introduced to continue the reaction. When the molar ratio of the introduced isobutylene to the total phosphorus of hypophosphinoic acid and / or its alkali metal salt reaches (y+2z) / 1 in formula (I), the introduction of isobutylene is stopped, and the remaining portion of ethylene is introduced to continue the reaction to obtain the mixture A.

[0075] Optionally, obtaining the mixture A includes the following steps:

[0076] A portion of ethylene is introduced into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator. After the partial ethylene reaction is complete or nearly complete, isobutylene is introduced to continue the reaction. After the isobutylene reaction is complete or nearly complete, the remaining portion of ethylene is introduced to continue the reaction, resulting in the mixture A.

[0077] The total amount of ethylene and the molar ratio of isobutylene are 0.33-39:1.

[0078] Optionally, the metal element M source is selected from at least one of the metal element M salts.

[0079] Optionally, the metal element M salt is selected from at least one of the following: nitrate, sulfate, hydrochloride, acetate, and oxide of metal element M.

[0080] Optionally, hypophosphonic acid and / or its alkali metal salt react simultaneously with isobutylene and a portion of ethylene in the presence of a free radical initiator. The amounts of isobutylene and ethylene are controlled until the molar percentage of isobutyl hypophosphonic acid or its alkali metal salt in the reaction system is close to the value y, and the molar percentage of diisobutyl hypophosphonic acid or its alkali metal salt is close to the value z, and z is less than or equal to 0.5. Then, the addition of isobutylene is stopped, and the remaining ethylene is added. The reaction continues in the presence of the initiator until the end. Subsequently, it reacts with the desired metal salt to obtain a dialkyl hypophosphonic acid hybrid salt having formula (I).

[0081] According to a third aspect of this application, a flame retardant is also provided, the flame retardant comprising at least one of the above-mentioned dialkylphosphine hybrid salts.

[0082] Optionally, the flame retardant further contains at least one selected from phosphate ions, phosphite ions, alkylphosphonate ions, and alkylphosphine ions, wherein the molar content of these phosphorus-containing acid ions in the flame retardant is less than or equal to 10% of the molar flame retardant, and the molar number of the flame retardant is calculated based on the molar number of phosphorus elements contained therein.

[0083] According to a fourth aspect of this application, a flame-retardant material is provided, the flame-retardant material comprising a flame retardant P and a thermoplastic polymer material;

[0084] The flame retardant P is selected from the above-mentioned dialkylphosphine hybrid salts and the application of at least one of the above-mentioned flame retardants in flame retardant materials.

[0085] Optionally, the flame retardant P has a mass content of 1-35% in the flame retardant material.

[0086] Optionally, the flame retardant material includes 1-35 wt% flame retardant P and 65-99 wt% thermoplastic polymer material.

[0087] In this application, thermoplastic polymer materials refer to plastics that soften when heated and harden when cooled.

[0088] Specifically, the amount of flame retardant P used depends on the thermoplastic polymer material.

[0089] Optionally, the flame retardant P has a mass content of 3-20% in the flame retardant material.

[0090] Optionally, the flame-retardant material may also include functional additives;

[0091] The functional additive is selected from at least one of the following: reinforcing agent, anti-dripping agent, stabilizer, pigment, dye, char-forming catalyst, dispersant, nucleating agent, inorganic filler, and antioxidant.

[0092] Optionally, the reinforcing agent is selected from glass fiber.

[0093] Optionally, the anti-dripping agent is selected from Teflon.

[0094] Optionally, the inorganic filler is selected from at least one of mica, calcium carbonate, calcium oxide, and silica.

[0095] Optionally, the functional additive in the flame retardant material has a mass content of 5-40%.

[0096] Optionally, the flame-retardant material further includes a flame retardant Q;

[0097] The flame retardant Q is selected from at least one of nitrogen-based flame retardants and boron-based flame retardants.

[0098] Optionally, the nitrogen-based flame retardant is selected from at least one of melamine cyanurate, melamine polyphosphate, and ammonium polyphosphate;

[0099] The boron-based flame retardant is selected from zinc borate.

[0100] Optionally, the flame retardant Q has a mass content of 0.5-20% in the flame retardant material.

[0101] Optionally, the thermoplastic polymer material is selected from at least one of polyamide and polyester.

[0102] Optionally, the polyamide is selected from at least one of aliphatic polyamide, aromatic polyamide, semi-aromatic polyamide, and copolymers of semi-aromatic polyamide and aliphatic polyamide.

[0103] According to common knowledge in this field, polyamide, also known as nylon, is a general term for polymers whose structural units contain -NH-C(O)- amide groups. It is synthesized through condensation or ring-opening reactions of one or more dicarboxylic acids and one or more diamines, and / or one or more amino acids, and / or one or more lactams. Based on the composition of its main chain, polyamides are generally classified into aliphatic polyamides, aromatic polyamides, and semi-aromatic polyamides. Semi-aromatic polyamides refer to those whose synthetic monomers contain at least one aromatic group in their structure.

[0104] Optionally, the aliphatic polyamide may be selected from a copolymer of polyamide 6 and polyamide 66, polyamide 6, polyamide 66, or a mixture of one or more of them.

[0105] Optionally, the semi-aromatic polyamide can be prepared from any one or more aromatic dicarboxylic acids and any one or more aliphatic diamines, or from any one or more aromatic diamines and any one or more aliphatic dicarboxylic acids. One or more of dicarboxylic acids, diamines, lactams, and amino acids can also be added to the system to prepare polyamide copolymers with corresponding properties. The added dicarboxylic acid is an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid; the added diamine is an aromatic diamine and / or an aliphatic diamine; the added lactam can be an aliphatic or aromatic lactam. The added amino acid can be an aromatic or aliphatic amino acid.

[0106] Optionally, the semi-aromatic polyamide is prepared from one or more aromatic dicarboxylic acids selected from terephthalic acid, isophthalic acid and naphthalic acid, and one or more aliphatic diamines selected from butanediamine, hexamethylenediamine, octanediamine, decanediamine and 2-methylpentanediamine.

[0107] Optionally, the semi-aromatic polyamide is prepared from aliphatic diamines, aromatic dicarboxylic acids, and aliphatic dicarboxylic acids.

[0108] Optionally, the semi-aromatic polyamide is prepared from an aliphatic diamine and an aromatic dicarboxylic acid; alternatively, an aliphatic dicarboxylic acid may also be added, wherein the molar fraction of the aliphatic dicarboxylic acid accounts for 0-45% of the total amount of dicarboxylic acid, i.e., the molar number of aliphatic dicarboxylic acid / (the molar number of aliphatic dicarboxylic acid + the molar number of aromatic dicarboxylic acid) = 0-45%.

[0109] Optionally, the aromatic dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, and naphthalic acid; the aliphatic diamine is selected from one or more of butanediamine, hexamethylenediamine, octanediamine, decanediamine, and 2-methylpentanediamine; and the aliphatic dicarboxylic acid is selected from one or more of succinic acid, succinic acid, sebacic acid, and octanoic acid.

[0110] Optionally, the polyamide may be selected from poly(hexamethylene terephthalamide) (abbreviated as PA6T), poly(hexamethylene isophthalamide) (abbreviated as PA6I), terephthalic acid / hexamethylenediamine / caprolactam copolymer (abbreviated as PA6T / 6), terephthalic acid / hexamethylenediamine / adipic acid copolymer (abbreviated as PA6T / 66), terephthalic acid / hexamethylenediamine / adipic acid / isophthalic acid copolymer (abbreviated as PA6T / 6I / 66), poly(nonadiamine terephthalamide) (abbreviated as PA9T), poly(hexamethylene terephthalamide ... One or more of the following: terephthaloyl decanediamine (abbreviated as PA10T), polyterephthaloyl dodecyl diamine (abbreviated as PA12T), terephthalic acid / hexamethylenediamine / dodecyl lactam copolymer (abbreviated as PA6T / 12), polyadipoxymethylenediamine (abbreviated as MXD6), terephthalic acid / hexamethylenediamine / 2-methylpentanediamine copolymer (abbreviated as PA6T / 2-MPMDT), and terephthalic acid / 2,2,4-trimethylhexamethylenediamine / 2,4,4-trimethylhexamethylenediamine copolymer.

[0111] Optionally, the aliphatic polyamide is selected from at least one of polyamide 6, polyamide 66, and copolymers of polyamide 6 and polyamide 66.

[0112] Optionally, the semi-aromatic polyamide is selected from polyphthalamide (PPA).

[0113] Optionally, the polyester is selected from polybutylene terephthalate (PBT).

[0114] In this embodiment of the invention, the values ​​of x, y, and z in Formula I do not consider the amount of other phosphorus-containing impurities, x + y + z = 1, and x + z > 0. Flame retardants with Formula (I) may contain trace amounts of other phosphorus-containing ions. Due to impurities in raw materials or impurities generated during the synthesis process, trace amounts of phosphate ions, phosphite ions, alkylphosphonate ions, and alkylphosphine ions may exist in the flame retardant. Some oligomer products derived from ethylene polymerization, such as ethyl n-butylphosphine ions, ethylhexylphosphine ions, butylbutylphosphine ions, and butylhexylphosphine ions, may also exist as impurities in flame retardants with Formula (I). However, as long as the total amount of these other phosphorus-containing acid ions does not exceed 10% molar of total phosphorus, it does not affect the normal operation of the flame retardant with Formula (I).

[0115] In this embodiment of the application, the ratio of x, y, z in formula (Ⅰ) can be obtained by alkaline or acid hydrolysis of the flame retardant, using... 31 P-NMR (nuclear magnetic resonance) is used to determine this. Diethylphosphine, ethylisobutylphosphine, and diisobutylphosphine have different... 31 The chemical shift of P, in 31 The P-NMR spectrum shows three independent peaks, and the peak areas of these three peaks correspond to the molar concentrations of the three phosphonates, respectively. Therefore, the values ​​of x, y, and z can be easily calculated by the ratio of the peak areas.

[0116] The beneficial effects that this application can produce include:

[0117] (1) The dialkylphosphine hybrid salt with the composition of formula (Ⅰ) provided by the present invention requires a small amount of addition, has high flame retardant efficiency for various polymer materials, and is economical. It not only overcomes the disadvantage of low flame retardant efficiency of diethylphosphine for polymer materials, but also overcomes the disadvantage of excessive volatility and low flame retardant efficiency of diisobutylphosphine for polyesters, and can be widely used in flame retardant applications for various polymer materials that require high-temperature processing;

[0118] (2) This application provides a method for preparing dialkylphosphine hybrid salts, which avoids the disadvantage of needing to prepare dialkylphosphine separately, uses water as the reaction solvent, and is environmentally friendly. The raw materials are readily available and economical. Attached Figure Description

[0119] Figure 1 Thermogravimetric curves of dialkylphosphine hybrid salts with different x, y, z values, as well as aluminum diethylphosphine and aluminum diisobutylphosphine (for ease of display, the values ​​shown in the table header are 100 times x, y, z).

[0120] Figure 2 XRD curves of dialkylphosphine hybrid salts, aluminum diethylphosphine and aluminum diisobutylphosphine with different x, y, z values ​​(for ease of display, the values ​​shown in the table header are 100 times x, y, z; physical mixing refers to the mixing of aluminum diethylphosphine and aluminum diisobutylphosphine).

[0121] Figure 3 The dialkylphosphine hybrid salt after alkaline hydrolysis in Example 3 31 P-NMR image. Detailed Implementation

[0122] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0123] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0124] The raw materials used in the implementation are as follows:

[0125] PA66 (also known as polyamide 66 or nylon 66): DuPont Zytel 70G35 HSL NC010, with a glass fiber content of 35% by weight.

[0126] PA6 (also known as polyamide 6 or nylon 6): DuPont Zytel 73G30L NC010, with a glass fiber content of 30% by weight.

[0127] PPA (High Temperature Nylon): DuPont HTN 51G35 HSL NC010, with a glass fiber content of 35% by weight;

[0128] PBT (polybutylene terephthalate): DuPont Crastin SK605 NC010, with a glass fiber content of 30% by weight;

[0129] ADP: Aluminum diethylphosphinic acid, Exolit OP1230 from Clariant GmbH, Germany;

[0130] ABP: aluminum diisobutylphosphinic acid, prepared according to US Patent 7807737;

[0131] MPP: Melamine polyphosphate, Suzhou Kaima Chemical Technology Co., Ltd.

[0132] Antioxidant 1010: Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid], Shanghai Maclean Biochemical Technology Co., Ltd.

[0133] Antioxidant 168: Tris[2,4-di-tert-butylphenyl]phosphite, Strem, Inc., USA.

[0134] Compound antioxidants: Antioxidant 1010 (tetra-[β-(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid] pentaerythritol ester) and antioxidant 168 (tris[2,4-di-tert-butylphenyl] phosphite) are mixed in a 1:1 weight ratio.

[0135] Combustion test standard: GB / T 2408-2008 standard;

[0136] Nuclear magnetic resonance (NMR) test: The instrument used was an AVANCE III 400MHz, manufactured by Bruker GmbH, Germany.

[0137] Phosphorus nuclear magnetic resonance spectroscopy (NMR) 31P-NMR test method: with the chemical shift of 85% phosphoric acid as 0, the pre-delay D1 = 10 seconds, 32 scans, and the ratio of peak areas is used as the ratio of the molar number of diethylphosphine, ethylisobutylphosphine, and diisobutylphosphine ions.

[0138] The instrument used for X-ray diffraction (XRD) testing was a D8 ADVANCE DAVINCI, manufactured by Bruker GmbH, Germany.

[0139] The instrument used for TGA thermogravimetric analysis is model Q500, manufactured by TA Instruments, Inc., USA.

[0140] Example 1

[0141] Preparation of hybrid salts with the composition of formula (Ⅰ), where x=0.87, y=0.13, z=0, M=Al, n=3

[0142] Dissolve 100g of sodium hypophosphite monohydrate in 500g of water and add it to a 1L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90℃, at which point the pressure gauge reads 0.3MPa. Then, inject a 4% sodium persulfate aqueous solution at a uniform rate of 10ml / h, while continuously feeding isobutylene into the vessel. Measure the amount of olefin introduced using a gas flow meter. After 0.3 hours, stop feeding isobutylene and begin feeding ethylene, increasing the pressure to 0.8MPa. After 9.0 hours, stop feeding ethylene but continue injecting the initiator. After half an hour, the pressure in the vessel no longer decreases, indicating the reaction is complete. Cool, depressurize, purge with N2, and discharge to obtain a colorless, transparent reaction solution.

[0143] Samples were taken during the intermediate stages of the reaction and subjected to NMR. 31 The p-NMR results are shown in Table 1:

[0144] Table 1

[0145]

[0146] *Long-chain alkyl phosphine ions: including ethyl n-butyl phosphine ions, ethyl hexyl phosphine ions, and butyl butyl phosphine ions.

[0147] 690 g of the above solution was slowly added to a 20% aqueous solution containing 89.97 g of aluminum sulfate octadecylhydrate. The reaction temperature was controlled at 70°C, and the pH was adjusted to less than or equal to 3.0, resulting in a large amount of precipitate. The addition was completed after 1 hour. The solution was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.5. The filter cake was then dried at 120°C, yielding 106.75 g, a yield of 92.9%. The sample was dissolved in an aqueous solution of sodium hydroxide, and phosphorus NMR was performed. The results showed 85.79% diethylphosphonate, 12.36% ethylisobutylphosphonate, 0.45% diisobutylphosphonate, and the remainder being long-chain alkylphosphonates, ethylphosphonates, and phosphite impurities. After normalization, x = 0.87, y = 0.13, and z = 0.

[0148] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively... (100%) (66.1%), the results are shown in Table 2.

[0149] Table 2

[0150]

[0151]

[0152] Example 2a Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.83, y = 0.16, z = 0.01, M = Al, n = 3

[0153] Dissolve 100g of sodium hypophosphite monohydrate in 500g of water and add it to a 1L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90℃, at which point the pressure gauge reads 0.3MPa. Then, inject a 4% sodium persulfate aqueous solution at a uniform rate of 10ml / h, while continuously feeding isobutylene into the vessel. Measure the amount of olefin introduced using a gas flow meter. After 1.0 hour, stop feeding isobutylene and start feeding ethylene, increasing the pressure to 0.8MPa. After 9.0 hours, stop feeding ethylene but continue injecting the initiator. After half an hour, the pressure in the vessel no longer decreases, indicating the reaction is complete. Cool, depressurize, purge with N2, and discharge to obtain a colorless, transparent reaction solution.

[0154] The reaction solution was sampled and subjected to NMR analysis. 31 The p-NMR results are shown in Table 3:

[0155] Table 3

[0156]

[0157] 766 g of the above partial solution was slowly added to a 20% (w / w) aqueous solution containing 89.97 g of aluminum sulfate octadechydrate. The reaction temperature was controlled at 70°C, and the pH was adjusted to less than or equal to 3.0, resulting in a large amount of precipitate. The addition was completed dropwise after 1 hour. The mixture was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.5. The filter cake was then dried at 120°C to obtain 95.2 g of a white powdery product, with a yield of 90.7%.

[0158] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results showed that 80.35% of diethylphosphonate, 16.05% of ethylisobutylphosphonate, and 0.70% of diisobutylphosphonate were obtained. The remainder consisted of long-chain alkylphosphonates, ethylphosphonates, and phosphite impurities. After normalization, x = 0.83, y = 0.16, and z = 0.01.

[0159] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively... (100%) (86.7%), the results are shown in Table 4.

[0160] Table 4

[0161]

[0162] Example 2b Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.83, y = 0.16, z = 0.01, M = Cu, n = 2

[0163] Following the method of Example 2a, copper sulfate was used instead of aluminum sulfate to obtain a copper hybrid salt with x = 0.83, y = 0.16, and z = 0.01. XRD analysis was performed on the sample, and the XRD results are shown in Table 5.

[0164] Table 5

[0165]

[0166] Example 3: Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.70, y = 0.29, z = 0.01, M = Al, and n = 3.

[0167] 100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water and added to a 1 L stainless steel pressure vessel. The vessel was purged twice with nitrogen and evacuated. Isobutylene was then introduced until the pressure stopped rising. The reaction solution was heated to approximately 90 °C, at which point the pressure gauge read 0.3 MPa. A 3.0% sodium persulfate aqueous solution was then injected at a uniform rate of 10 ml / h, while isobutylene was continuously introduced into the vessel. The amount of olefin introduced was measured using a gas flow meter. After 1.5 hours, the isobutylene injection was stopped, and ethylene was introduced, increasing the pressure to 0.8 MPa. After 10.5 hours, the ethylene injection was stopped, but the initiator was continued. After half an hour, the pressure in the vessel stopped decreasing, indicating that the reaction was complete. The mixture was cooled, depressurized, purged with N2, and discharged to obtain a colorless and transparent reaction solution.

[0168] The results of NMR spectroscopy performed on samples taken during the intermediate reaction process are shown in Table 6.

[0169] Table 6

[0170]

[0171] Take 724 g of the above solution and slowly add it to a 20% (w / w) aqueous solution containing 104.79 g of aluminum sulfate octahydrate. Control the reaction temperature at 70°C and adjust the pH to less than or equal to 3.0, resulting in a large amount of precipitate. The addition was complete after 1 hour. Filter while hot, and wash the filter cake with water until the pH is greater than 4.5. Then dry the filter cake at 120°C to obtain 117.5 g, a yield of 90.2%.

[0172] The sample was dissolved in an aqueous solution of sodium hydroxide and subjected to phosphorus NMR. The results showed that 69.15% of diethylphosphonate, 28.57% of ethylisobutylphosphonate, 1.12% of diisobutylphosphonate, and the remainder were long-chain alkylphosphonate impurities. After normalization, x = 0.70, y = 0.29, and z = 0.01.

[0173] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively... (100%) (47.4%), the results are shown in Table 7.

[0174] Table 7

[0175]

[0176] The hybrid salt obtained in this embodiment was subjected to alkaline hydrolysis. 31 p-NMR (nuclear magnetic resonance) spectrum as follows Figure 3 As shown, the peak areas of these three peaks correspond to the molar concentrations of the three phosphonates, respectively. Therefore, the values ​​of x, y, and z can be easily calculated by the ratio of their peak areas.

[0177] Example 4a Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.60, y = 0.38, z = 0.02, M = Al, n = 3

[0178] 100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water and added to a 1 L stainless steel pressure vessel. The vessel was purged twice with nitrogen and evacuated. Isobutylene was then introduced until the pressure stopped rising. The reaction solution was heated to approximately 90 °C, at which point the pressure gauge read 0.3 MPa. A 3.0% sodium persulfate aqueous solution was then injected at a uniform rate of 10 ml / h, while isobutylene was continuously introduced into the vessel. The amount of olefin introduced was measured using a gas flow meter. After 2.0 hours, the isobutylene injection was stopped, and ethylene was introduced, increasing the pressure to 0.8 MPa. After 15.5 hours, the ethylene injection was stopped, but the initiator was continued. After half an hour, the pressure in the vessel stopped decreasing, indicating that the reaction was complete. The mixture was cooled, depressurized, purged with N2, and discharged to obtain a colorless and transparent reaction solution.

[0179] The results of NMR spectroscopy performed on samples taken during the intermediate reaction process are shown in Table 8.

[0180] Table 8

[0181]

[0182] 847 g of the above solution was slowly added to a 20% (w / w) aqueous solution containing 104.79 g of aluminum sulfate octadechydrate. The reaction temperature was controlled at 70°C, and the pH was adjusted to be less than or equal to 3.0, resulting in a large amount of precipitate. The addition was completed dropwise after 1 hour. The solution was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.5. The filter cake was then dried at 120°C, yielding 126.1 g, a yield of 94.9%.

[0183] The sample was dissolved in an aqueous solution of sodium hydroxide and subjected to phosphorus NMR. The results showed that the diethylphosphonate content was 60.29%, the ethylisobutylphosphonate content was 38.24%, and the diisobutylphosphonate content was 1.47%, i.e., x = 0.60, y = 0.38, z = 0.02.

[0184] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0185] (100%) (14.2%), the results are shown in Table 9.

[0186] Table 9

[0187]

[0188] Example 4b Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.63, y = 0.36, z = 0.01, M = Fe, n = 3

[0189] Following Example 4a, 49.46 g of the reaction solution was slowly added to a 15% aqueous solution containing 5.41 g of ferric chloride hexahydrate. The reaction temperature was controlled at 70°C, and the pH was adjusted to be less than or equal to 2.0, resulting in a large amount of precipitate. The addition was completed after 1 hour. The mixture was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.0. The filter cake was then dried at 120°C to obtain 8.40 g of the precipitate, with a yield of 93.7%.

[0190] The sample was dissolved in an aqueous solution of sodium hydroxide and subjected to phosphorus NMR. The results showed that the diethylphosphonate content was 63.26%, the ethylisobutylphosphonate content was 35.82%, and the diisobutylphosphonate content was 0.92%, i.e., x = 0.63, y = 0.36, z = 0.01.

[0191] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0192] (100%) (8.0%), the results are shown in Table 10.

[0193] Table 10

[0194]

[0195] Example 4c Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.62, y = 0.37, z = 0.01, M = Zn, n = 2

[0196] According to Example 4a, 197.85 g of the reaction solution was slowly added to a 15% aqueous solution containing 34.51 g of zinc sulfate heptahydrate. The reaction temperature was controlled at 70°C. After the addition was complete, the solution was cooled and dried to obtain a white solid. The sample was dissolved in an aqueous solution of sodium hydroxide and subjected to phosphorus NMR. The results showed 62.0% diethylphosphonate, 36.7% ethylisobutylphosphonate, and 1.3% diisobutylphosphonate, i.e., x = 0.62, y = 0.37, z = 0.01.

[0197] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively... (100%) (57.6%), the results are shown in Table 11.

[0198] Table 11

[0199]

[0200] Example 5a Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.45, y = 0.52, z = 0.03, M = Al, n = 3

[0201] Dissolve 100g of sodium hypophosphite monohydrate in 500g of water and add the solution to a 1L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge the vessel with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90℃, at which point the pressure gauge reads 0.3MPa. Then, inject a 3.0% sodium persulfate aqueous solution at a uniform rate of 10ml / h, while continuously feeding isobutylene into the vessel. After 5.5 hours, stop feeding isobutylene and begin feeding ethylene, increasing the pressure to 0.8MPa. After 17 hours, the reaction is complete. Stop feeding ethylene, cool the vessel, release the pressure, purge with N2, and discharge the solution to obtain a colorless and transparent reaction liquid.

[0202] The results of NMR spectroscopy performed on samples taken during the intermediate reaction process are shown in Table 12.

[0203] Table 12

[0204]

[0205] *Long-chain alkyl groups: including ethyl n-butylphosphine and butyl butylphosphine.

[0206] Take 445 g of the above solution and slowly add it to a 10% aqueous solution containing 59.98 g of aluminum sulfate octadechydrate. Control the reaction temperature at 70°C and adjust the pH to less than or equal to 2.9, resulting in a large amount of precipitate. The addition was complete after 1 hour. Filter while hot, and wash the filter cake with water until the pH is greater than 4.5. Then dry the filter cake at 120°C to obtain 69.3 g, a yield of 89%.

[0207] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results are as follows: diethylphosphonate 44.18%, ethyl isobutylphosphonate 50.45%, diisobutylphosphonate 3.24%, and the remainder were long-chain alkylphosphonates and ethylphosphonates as impurities. After normalization, x = 0.45, y = 0.52, z = 0.03.

[0208] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0209] (100%) (12.7%), the results are shown in Table 13.

[0210] Table 13

[0211]

[0212] Example 5b Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.48, y = 0.49, z = 0.03, M = Fe, n = 3

[0213] Following Example 5a, 51.3 g of the reaction solution was slowly added to a 15% aqueous solution containing 5.41 g of ferric chloride hexahydrate. The reaction temperature was controlled at 70°C, and the pH was adjusted to be less than or equal to 2.0, resulting in a large amount of precipitate. The addition was completed after 1 hour. The mixture was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.0. The filter cake was then dried at 120°C to obtain 8.70 g of the precipitate, with a yield of 94.7%.

[0214] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results are as follows: diethylphosphonate 47.22%, ethyl isobutylphosphonate 48.25%, diisobutylphosphonate 2.13%, and the remainder were long-chain alkylphosphonates and ethylphosphonates as impurities. After normalization, x = 0.48, y = 0.49, z = 0.03.

[0215] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0216] (100%) (11.2%), the results are shown in Table 14.

[0217] Table 14

[0218]

[0219] Example 6: Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.31, y = 0.64, z = 0.05, M = Al, and n = 3.

[0220] Dissolve 100 g of sodium hypophosphite monohydrate in 500 g of water and add the solution to a 1 L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge the vessel with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90 °C, at which point the pressure gauge reads 0.3 MPa. Then, inject a 4.0% aqueous solution of 2,2'-azobis(2-amidinepropane) dihydrochloride at a constant rate of 10 ml / h, while continuously feeding isobutylene into the vessel. After 9.5 hours, stop feeding isobutylene and begin feeding ethylene, increasing the pressure to 0.8 MPa. After 20 hours, the reaction is complete. Stop feeding ethylene, cool the vessel, release the pressure, purge with N2, and discharge the solution to obtain a colorless and transparent reaction liquid.

[0221] The results of NMR spectroscopy performed on samples taken during the intermediate reaction process are shown in Table 15.

[0222] Table 15

[0223]

[0224] Take 512 g of the above solution and slowly add it to a 10% aqueous solution containing 59.98 g of aluminum sulfate octadechydrate. Control the reaction temperature at 70°C and adjust the pH to less than or equal to 2.9, resulting in a large amount of precipitate. The addition was complete after 1 hour. Filter while hot, and wash the filter cake with water until the pH is greater than 4.5. Then dry the filter cake at 120°C to obtain 74.46 g, a yield of 93.7%.

[0225] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results are as follows: diethylphosphonate 30.76%, ethyl isobutylphosphonate 63.27%, diisobutylphosphonate 4.60%, and the remainder were long-chain alkylphosphonates and ethylphosphonates as impurities. After normalization, x = 0.31, y = 0.64, z = 0.05.

[0226] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0227] (100%) (9.9%), the results are shown in Table 16.

[0228] Table 16

[0229]

[0230] Example 7: Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.28, y = 0.68, z = 0.04, M = Al, and n = 3.

[0231] Dissolve 100g of sodium hypophosphite monohydrate in 500g of water and add the solution to a 1L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge the vessel with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90℃, at which point the pressure gauge reads 0.3MPa. Then, inject a 3.0% sodium persulfate aqueous solution at a uniform rate of 10ml / h, while continuously feeding isobutylene into the vessel. After 10.5 hours, stop feeding isobutylene and begin feeding ethylene, increasing the pressure to 0.8MPa. After 21 hours, the reaction is essentially complete. Stop feeding ethylene, cool the vessel, depressurize, purge with N2, and discharge the solution to obtain a colorless and transparent reaction liquid.

[0232] The results of NMR spectroscopy performed on samples taken during the intermediate reaction process are shown in Table 17.

[0233] Table 17

[0234]

[0235] The monoaddition product was first oxidized with sufficient 30% hydrogen peroxide, and then slowly added to a 10% aqueous solution containing 104.79 g of aluminum sulfate octadechydrate. The reaction temperature was controlled at 70°C, and the pH was adjusted to less than or equal to 2.9, resulting in a large amount of precipitate. The addition was completed dropwise after 1 hour. The mixture was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.5. The filter cake was then dried at 120°C, yielding 124.99 g, a yield of 91.7%.

[0236] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results are as follows: diethylphosphonate 27.78%, ethyl isobutylphosphonate 66.83%, diisobutylphosphonate 4.00%, and the remainder were other phosphorus-containing impurities. After normalization, x = 0.28, y = 0.68, z = 0.04.

[0237] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0238] (100%) (12.6%), the results are shown in Table 18.

[0239] Table 18

[0240]

[0241] Example 8: Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.03, y = 0.58, z = 0.39, M = Al, and n = 3.

[0242] Dissolve 100g of sodium hypophosphite monohydrate in 500g of water and add the solution to a 1L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge the vessel with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90℃, at which point the pressure gauge reads 0.3MPa. Then, inject a 3.0% sodium persulfate aqueous solution at a uniform rate of 10ml / h, while continuously feeding isobutylene into the vessel. After 13 hours, stop feeding isobutylene and begin feeding ethylene, increasing the pressure to 0.8MPa. After 25 hours, stop feeding ethylene, cool and depressurize, purge with N2, and discharge the solution to obtain a colorless and transparent reaction liquid.

[0243] The monoaddition product was first oxidized with sufficient 30% hydrogen peroxide. Then, 500g of the solution was slowly added to a 10% aqueous solution containing 13.33g of aluminum sulfate octadecahydrate. The reaction temperature was controlled at 70℃, and the pH was adjusted to less than or equal to 2.9, resulting in a large amount of precipitate. The addition was completed after 1 hour. The solution was filtered while hot, and the filter cake was washed with water until the pH was greater than 4.5. The filter cake was then dried at 120℃, yielding 19.05g, a yield of 94%.

[0244] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results are as follows: diethylphosphonate 2.69%, ethylisobutylphosphonate 52.89%, and diisobutylphosphonate 35.84%. After normalization, x = 0.03, y = 0.58, and z = 0.39.

[0245] XRD tests were performed on the sample, and the interlayer spacings corresponding to the highest and second highest relative intensities of the characteristic peaks obtained from the XRD measurements were respectively...

[0246] (100%) (11.7%), the results are shown in Table 19.

[0247] Table 19

[0248]

[0249] Example 9: Preparation of a hybrid salt having the composition of formula (Ⅰ), wherein x = 0.03, y = 0.52, z = 0.45, M = Al, and n = 3.

[0250] Dissolve 100g of sodium hypophosphite monohydrate in 500g of water and add the solution to a 1L stainless steel pressure vessel. Purge the vessel twice with nitrogen, then evacuate it. Purge the vessel with isobutylene until the pressure stops rising. Heat the reaction solution to approximately 90℃, at which point the pressure gauge reads 0.3MPa. Then, inject a 3.0% sodium persulfate aqueous solution at a uniform rate of 10ml / h, while continuously feeding isobutylene into the vessel. After 15 hours, stop feeding isobutylene and begin feeding ethylene, increasing the pressure to 0.8MPa. After 27 hours, the reaction is complete. Stop feeding ethylene, cool the vessel, depressurize, purge with N2, and discharge the solution to obtain a colorless, transparent reaction liquid.

[0251] The results of NMR spectroscopy performed on samples taken during the intermediate reaction process are shown in Table 20.

[0252] Table 20

[0253]

[0254] Take 280 g of the above solution and slowly add it to a 10% aqueous solution containing 7.46 g of aluminum sulfate octadechydrate. Control the reaction temperature at 70°C and adjust the pH to less than or equal to 2.9, resulting in a large amount of precipitate. The addition was complete after 1 hour. Filter while hot, and wash the filter cake with water until the pH is greater than 4.5. Then dry the filter cake at 120°C to obtain 10.7 g, a yield of 94.3%.

[0255] The sample was dissolved in an aqueous sodium hydroxide solution, and phosphorus NMR was performed. The results are as follows: diethylphosphonate 2.9%, ethylisobutylphosphonate 51.0%, and diisobutylphosphonate 43.5%. After normalization, x = 0.03, y = 0.52, and z = 0.45.

[0256] XRD tests were performed on the dried samples, and the X-ray diffraction (XRD) results are shown in Table 1 below. From the characteristic peaks with the highest relative intensities in Table 1, it can be seen that the interlayer spacing is mainly [missing information]. The results are shown in Table 21.

[0257] Table 21

[0258]

[0259] The dialkylphosphonic acid hybrid salts obtained in Examples 1, 2a, 4a, 7, 8, and 9 were subjected to TGA testing, and the results are as follows: Figure 1 As shown, Figure 1 The graphs show the thermogravimetric analysis (TGA) curves of hybrid salts with different x, y, and z values, as well as aluminum diethylphosphinate (ADP) and aluminum diisobutylphosphinate (ABP). As can be seen from the graph, aluminum diisobutylphosphinate exhibits the earliest thermal weight loss and the lowest thermal stability. The larger the z value, the earlier the hybrid salt experiences thermal weight loss.

[0260] Example 10 (Comparative Example) Ferric Diethylphosphinate

[0261] 93.82 g of an 18.4% (w / w) aqueous solution of sodium diethylphosphonate (containing 2.1 mol% ethylbutylphosphonate and 0.5 mol% ethylphosphonate) was slowly added to a 15% (w / w) aqueous solution containing 10.81 g of ferric chloride hexahydrate. The reaction temperature was maintained at 70°C and pH = 2. The addition was completed over half an hour, and the mixture was kept at this temperature for another half hour. The mixture was filtered while hot, and the filter cake was washed with water until the pH was greater than 4. The filter cake was then dried at 120°C to obtain 15.5 g of the product, with a yield of 92.5%.

[0262] The samples were subjected to XRD tests, and the results are shown in Table 22:

[0263] Table 22

[0264]

[0265] Example 11

[0266] Polyamide PA66, the hybrid salt prepared in Example 1, and the compounded antioxidant were mixed in a weight ratio of 79.6:20:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 280°C. The mixture was then filled into a mold, preheated at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 V-1.

[0267] Example 12

[0268] Polyamide PA6, the hybrid salt prepared in Example 1, and the compounded antioxidant were mixed in a weight ratio of 79.6:20:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 260°C. The mixture was then filled into a mold, preheated in a flat vulcanizing press at 260°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 V-1.

[0269] Example 13

[0270] Polyester PBT, the hybrid salt prepared in Example 1, and the compounded antioxidant were mixed in a weight ratio of 84.6:15:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 260°C. The mixture was then filled into a mold, preheated at 260°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 V-0.

[0271] Examples 14-40

[0272] The flame retardants of Examples 2-9 were prepared and tested in polyamides PA66, PA6, PPA, and PBT according to the methods of Examples 11-13. The results are shown in Tables 23 and 24.

[0273] Example 41

[0274] Polyamide PA66, the hybrid salt prepared in Example 8, MPP, and the compounded antioxidant were mixed in a weight ratio of 82.6:12:5:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 280°C. The mixture was then filled into a mold, preheated at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 V-0.

[0275] Comparative Example 1

[0276] Polyamide PA66, iron diethylphosphinate prepared in Example 10, and compounded antioxidants were mixed in a weight ratio of 79.6:20:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 280°C. The mixture was then filled into a mold, preheated at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 unrated.

[0277] Comparative Example 2

[0278] Polyamide PA66, ADP, and a compound antioxidant were mixed in a weight ratio of 79.6:20:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 280°C. The mixture was then filled into a mold and preheated in a flat vulcanizing press at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 unrated.

[0279] Comparative Example 3

[0280] Polyamide PA6, ADP, and a compound antioxidant were mixed in a weight ratio of 79.6:20:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 260°C. The mixture was then filled into a mold and preheated in a flat vulcanizing press at 260°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6mm sample was UL-94 unrated.

[0281] Comparative Example 4

[0282] Polyester PBT, ADP, and compounded antioxidants were mixed in a weight ratio of 84.6:15:0.4 in an internal mixer at 50 rpm. The mixture was then set to 260℃ and allowed to cool and dry after 5 minutes. The mixture was then filled into a mold and preheated in a flat vulcanizing press at 260℃ for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6mm sample was UL94V-2.

[0283] Comparative Example 5

[0284] Polyester PBT, aluminum diisobutylphosphinate (ABP), and a compound antioxidant were mixed in a weight ratio of 84.6:15:0.4 in an internal mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 260°C. The mixture was then filled into a mold and preheated in a flat vulcanizing press at 260°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 V-2.

[0285] Comparative Example 6

[0286] Polyamide PA66, aluminum diisobutylphosphinate (ABP), and a compound antioxidant were mixed in a weight ratio of 87.1:12.5:0.4 in a Banbury mixer at 50 rpm. The mixture was then cooled and dried after 5 minutes at 280°C. The mixture was then filled into a mold, preheated at 280°C for 10 minutes, held at 10 MPa for 5 minutes, and then cold-pressed. After cooling, samples were cut and tested. The flame retardancy rating of the 1.6 mm sample was UL94 V-1.

[0287] The comparative results are shown in Table 25.

[0288]

[0289]

[0290] Table 25 Formulations and test results of Comparative Examples 1-6

[0291] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PA66 79.6 79.6 87.1 PA6 79.6 PBT 84.6 84.6 Flame retardant preparation Example 10 Equation (I) 1.00 / 0 / 0 / Fe Flame retardant parts 20 ADP 20 20 15 ABP 15 12.5 Compound antioxidants 0.4 0.4 0.4 0.4 0.4 0.4 UL-94 NG NG NG V-2 V-2 V-1

[0292] *: NG has no grade

[0293] Examples 11-41 illustrate that the flame retardants containing the dialkylphosphinic acid hybrid salts of this invention exhibit outstanding flame retardant efficiency against both polyamides and polyesters. Comparative Example 1 shows that pure iron diethylphosphinic acid has low flame retardant efficiency against both polyamides and polyesters. Comparative Examples 2-4 show that pure aluminum diethylphosphinic acid has low flame retardant efficiency against both polyamides and polyesters. Comparative Example 5 shows that pure aluminum diisobutylphosphinic acid has low flame retardant efficiency against polyesters. Comparative Example 6 shows that, at the same addition amount, pure aluminum diisobutylphosphinic acid is less effective at flame retardant polyamides than the hybrid salts containing ethyl isobutylphosphinic acid (see Examples 20, 26, 32, and 37). Furthermore, it was found in the examples that for the hybrid salts containing diisobutylphosphinic acid, the higher the content, the darker the color of the flame-retardant sample, indicating greater degradation. The polymer sample obtained by flame retardant treatment with pure aluminum diisobutylphosphinic acid had the darkest color.

[0294] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A dialkylphosphine hybrid salt, characterized in that, The dialkylphosphine hybrid salt is selected from at least one of compounds having the chemical formula shown in formula (I): Equation (I) In this context, M is the central atom, and diethylphosphine ion, ethylisobutylphosphine ion, and diisobutylphosphine ion are all ligands. M is selected from a metallic element; the metallic element is selected from at least one of Group IIIA metallic elements and transition metal elements; n represents the valence state of metal M; n is selected from 2, 3, or 4. 0.03≤x≤0.87; 0.13≤y≤0.7; 0≤z≤0.45, and x+y+z=1, x+z>0.

2. The dialkylphosphine hybrid salt according to claim 1, characterized in that, The Group IIIA metallic element is Al; The transition metal element is selected from at least one of Fe, Zn, Cu, Ti, Zr, and Mn.

3. The dialkylphosphine hybrid salt according to claim 1, characterized in that, 0.03≤x≤0.7;0.29≤y≤0.68;0.01≤z≤0.45; 4. The method for preparing the dialkylphosphine hybrid salt according to any one of claims 1 to 3, characterized in that, The preparation method includes: The material containing mixture A and metal element M source is reacted in an aqueous phase to obtain the dialkylphosphine hybrid salt; The mixture A contains diethylphosphonic acid and / or its alkali metal salt, ethyl isobutylphosphonic acid and / or its alkali metal salt, and diisobutylphosphonic acid and / or its alkali metal salt.

5. The preparation method according to claim 4, characterized in that, The conditions for reaction I are: temperature 0-250℃; pressure 0.1MPa-10MPa; time 0.1-20h.

6. The preparation method according to claim 4, characterized in that, The mixture A is obtained by the following steps: Ethylene and isobutylene are passed into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator, and reaction II is carried out to obtain the mixture A.

7. The preparation method according to claim 6, characterized in that, In the aqueous solution, the mass of the water is 10-99% of the total mass of the free radical initiator, the phosphonic acid and / or its alkali metal salt and water.

8. The preparation method according to claim 6, characterized in that, The conditions for reaction II are: temperature 0-250℃; time 0.01-50h; pressure 0-3MPa.

9. The preparation method according to claim 6, characterized in that, The molar ratio of the free radical initiator to the total amount of the phosphonic acid and / or its alkali metal salt is 0.001-0.1:

1.

10. The preparation method according to claim 6, characterized in that, The mixture A is obtained by the following steps: Isobutylene is introduced into an aqueous solution containing hypophosphite and / or its alkali metal salt and a free radical initiator to carry out the reaction. After the ratio of the introduced isobutylene to the total phosphorus molar of hypophosphite and / or its alkali metal salt reaches (y+2z) / 1 in formula (Ⅰ), the introduction of isobutylene is stopped, and ethylene is introduced to continue the reaction to obtain the mixture A.

11. The preparation method according to claim 6, characterized in that, The mixture A is obtained by the following steps: Isobutylene and a portion of ethylene are introduced into an aqueous solution containing phosphonic acid and / or its alkali metal salt and a free radical initiator to carry out the reaction. The ratio of the total phosphorus molar of ethylene to phosphonic acid and / or its alkali metal salt is less than (2x+y) / 1 in formula (I). After the ratio of the total phosphorus molar of isobutylene to phosphonic acid and / or its alkali metal salt reaches (y+2z) / 1 in formula (I), the introduction of isobutylene is stopped, and the remaining portion of ethylene is introduced to continue the reaction to obtain the mixture A.

12. The preparation method according to claim 6, characterized in that, The mixture A is obtained by the following steps: A portion of ethylene is introduced into an aqueous solution containing hypophosphinoic acid and / or its alkali metal salt and a free radical initiator. The molar ratio of the portion of ethylene to the total phosphorus of hypophosphinoic acid and / or its alkali metal salt is less than (2x+y) / 1 in formula (I). After the portion of ethylene has reacted completely, isobutylene is introduced to continue the reaction. After the molar ratio of the introduced isobutylene to the total phosphorus of hypophosphinoic acid and / or its alkali metal salt reaches (y+2z) / 1 in formula (I), the introduction of isobutylene is stopped, and the remaining portion of ethylene is introduced to continue the reaction to obtain the mixture A.

13. The preparation method according to claim 4, characterized in that, The metal element M source is selected from at least one of the metal element M salts.

14. A flame retardant, characterized in that, The flame retardant is selected from the dialkylphosphonic acid hybrid salts according to any one of claims 1 to 3.

15. A flame-retardant material, characterized in that, The flame-retardant material includes flame retardant P and thermoplastic polymer material; The flame retardant P is selected from at least one of the flame retardants described in claim 14.

16. The flame-retardant material according to claim 15, characterized in that, The flame retardant P has a mass content of 1-35% in the flame retardant material.

17. The flame-retardant material according to claim 15, characterized in that, The flame-retardant material also includes functional additives; The functional additive is selected from at least one of the following: reinforcing agent, anti-dripping agent, stabilizer, pigment, dye, char-forming catalyst, dispersant, nucleating agent, inorganic filler, and antioxidant.

18. The flame-retardant material according to claim 17, characterized in that, The functional additives in the flame-retardant material have a mass content of 5-40%.

19. The flame-retardant material according to claim 17, characterized in that, The flame-retardant material also includes flame retardant Q; The flame retardant Q is selected from at least one of nitrogen-based flame retardants and boron-based flame retardants.

20. The flame-retardant material according to claim 19, characterized in that, The flame retardant Q has a mass content of 0.5-20% in the flame retardant material.

21. The flame-retardant material according to claim 15, characterized in that, The thermoplastic polymer material is selected from at least one of polyamide and polyester.

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