CN117777191A - Dialkyl phosphinic acid hybrid salt and preparation method and application thereof - Google Patents

Abstract

The application discloses a dialkylphosphinic acid hybridization salt, a preparation method and application thereof, wherein the dialkylphosphinic acid hybridization salt is selected from at least one of compounds with chemical formulas shown in a formula (I). The dialkylphosphinic acid hybridization salt with the composition of the formula (I) has the advantages of small addition, high flame retardant efficiency on various high polymer materials and good thermal stability, overcomes the defect of low flame retardant efficiency on the high polymer materials due to diethylphosphinate, overcomes the defect of low thermal stability of long-chain dialkylphosphinate and large smoke during combustion, and can be widely applied to flame retardance on the high polymer materials needing high-temperature processing.

Description

Dialkyl phosphinic acid hybrid salt and preparation method and application thereof

Technical Field

The application relates to a dialkyl phosphinic acid hybrid salt, a preparation method and application thereof, and belongs to the field of preparation of flame-retardant high polymer materials.

Background

Dialkylphosphinates, in particular aluminum diethylphosphinate, have been widely used as halogen-free flame retardants for polymeric materials. However, the existing dialkylphosphinate has limited flame retardant efficiency in glass fiber reinforced polymer materials and often needs to be used together with a synergist. US patent US6207736, US6255371, US6547992 etc. report diethylphosphinate and ammonium polyphosphate, melamine polyphosphate, and/or inorganic compounds such as zinc stannate in combination with flame retardant glass fiber reinforced polyamides and polyesters. However, the amount of the flame retardant is large, the heat stability of the ammonium polyphosphate is not high, and the melamine polyphosphate is easy to migrate.

U.S. patent No. 7420007 reports aluminum diethylphosphinate containing less than or equal to 6% telogen phosphinate, i.e., long chain dialkylphosphinate. Chinese patent CN104072537B reports a method for removing long chain dialkylphosphinic salts during the preparation of diethylphosphinic salts. These patents all emphasize avoiding the formation and use of higher levels of long chain dialkylphosphinic salts with low thermal stability. In practical application, long-chain dialkylphosphinic salts such as dibutyl phosphinic acid aluminum are found to be large in smoke and unfavorable for safe escape when flame-retardant glass fiber reinforced polyamide is used. Flame retardants that are highly flame retardant and produce low smoke when burned have been a goal of industry.

It has now surprisingly been found that hybrid salts composed of relatively high amounts of long-chain dialkylphosphinate ions and diethylphosphinate ions have a high thermal stability and a very high flame retardant efficiency, flame retardance of polymeric materials can be achieved without the need for synergists, and at the same time the flame-retarded materials therefrom exhibit little smoke when burned.

Disclosure of Invention

In order to solve the technical problems, the application provides the dialkyl phosphinic acid hybrid salt, and the preparation method and application thereof, wherein the dialkyl phosphinic acid hybrid salt is the dialkyl phosphinic acid hybrid salt with the composition shown in the formula (I), and has the advantages of high thermal stability, small addition amount, high flame retardant efficiency for various high polymer materials, small smoke, capability of meeting the processing requirements of engineering plastics requiring high temperature and high economy.

According to a first aspect of the present application, there is provided a dialkylphosphinic acid hybridization salt selected from at least one of compounds having a chemical formula represented by formula (I);

wherein M is a central atom; r is R ₁ 、R ₂ Are each independently selected from C ₄ -C ₁₂ And R is an alkyl group of ₁ 、R ₂ At least one of which is not isobutyl;

diethyl phosphinate ion, ethyl R ₁ Radical phosphinate ion, R ₁ Radical R ₂ The phosphinate ions are ligands;

m is selected from metal elements; the metal element is at least one selected from group IIA, IIIA, IVA, VA metal element, transition metal element and lanthanide series metal element;

n is the valence state of the metal element M; n is selected from 2,3 or 4;

ethyl R ₁ Radical phosphinate ion, diethyl phosphinate ion, R ₁ Radical R ₂ At least two acid radical ions in the phosphinate radical ions are paired with the same central atom M; and one of the ligands paired with the central atom M must be ethyl R ₁ A phosphinate ion;

x is more than or equal to 0 and less than or equal to 0.76; y is more than or equal to 0.05 and less than or equal to 0.76; 0.ltoreq.z.ltoreq.0.76, and x+y+z=1.

In the embodiment of the application, R ₁ 、R ₂ Are each independently selected from C ₄ -C ₁₂ Alkyl groups of (2), which may be the same or different, and R ₁ 、R ₂ At least one is not isobutyl. C (C) ₄ -C ₁₂ The alkyl group may be a straight or branched alkyl group including, but not limited to, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, zhong Kuiji, tert-decyl, n-undecyl, isoundecyl, sec-undecyl Alkyl, tertiary undecyl, n-dodecyl, iso-dodecyl, secondary dodecyl, tertiary dodecyl.

In the present application, when R ₁ Or R is ₂ When the mixture having isomers is included, the calculation is performed as a substance when calculating the y value, the substances which are isomers to each other. For example, R ₁ Is butyl, which includes n-butyl, isobutyl, sec-butyl and tert-butyl. In calculating y in formula (I), ethylbutylphosphinate ion (R in formula (1) ₁ =butyl) includes ethyl n-butylphosphinate ion, ethyl isobutyl phosphinate ion, ethyl sec-butylphosphinate ion, and ethyl tert-butylphosphinate ion. y is the total number of moles of the four ethylbutylphosphinate ions to the total number of moles of all dialkylphosphinate ions (i.e., moles of diethylphosphinate ions, moles of ethylbutylphosphinate ions, and R) ₁ Radical R ₂ Sum of moles of phosphinate ions). In calculating z in formula (I), R ₁ And R is ₂ If all of the isomers are present, the calculation is performed by similarly calculating the substances which are isomers to each other as one substance according to the above-mentioned method. In the examples herein, in the formula (I), if x is greater than 0.76, the flame retardant property is poor. If z is greater than 0.76, the thermal stability is lowered, which is disadvantageous for the preparation and physical properties of the flame-retardant polymer material. y is larger than 0.76, the preparation cost is high, and the economy is poor.

Alternatively, the lower limit of x is independently selected from 0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30; the upper limit is independently selected from 0.76, 0.70, 0.67, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35.

Alternatively, the lower limit of y is independently selected from 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40; the upper limit is independently selected from 0.76, 0.70, 0.67, 0.65, 0.60, 0.55, 0.50, 0.45.

Alternatively, the lower limit of z is independently selected from 0, 0.001, 0.005, 0.01, 0.02, 0.03, 0.05, 0.08; the upper limit is independently selected from 0.76, 0.70, 0.67, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35, 0.30, 0.25, 0.20, 0.15, 0.10.

Optionally, the group iia metal element is selected from at least one of Be, mg, ca, sr, ba;

the III A metal element is Al;

the group IVA metal element is Sn;

the group VA metal element is Sb;

the transition metal element is selected from at least one of Fe, zn, cu, ti, zr, mn;

the lanthanide metal element is Ce.

Optionally, the metal element is selected from at least one of Al, zn, ca, fe.

Optionally, the metal element is Al, n=3.

Optionally, 0.ltoreq.x.ltoreq.0.76; y is more than or equal to 0.05 and less than or equal to 0.67; z is more than or equal to 0.005 and less than or equal to 0.76.

Optionally, 0.ltoreq.x.ltoreq.0.70; y is more than or equal to 0.05 and less than or equal to 0.67; z is more than or equal to 0.005 and less than or equal to 0.70.

Optionally, 0.1.ltoreq.x.ltoreq.0.65; y is more than or equal to 0.30 and less than or equal to 0.67; z is more than or equal to 0.01 and less than or equal to 0.50.

Optionally, x is more than or equal to 0.30 and less than or equal to 0.65; y is more than or equal to 0.30 and less than or equal to 0.65; z is more than or equal to 0.02 and less than or equal to 0.40.

In the examples herein, the greater the z value, the earlier the thermal weight loss of the dialkylphosphinic acid hybrid salt.

The dialkylphosphinic acid hybrid salts herein are not simple physical mixtures of different dialkylphosphinic salts. For example, when R ₁ And R is ₂ In the case of butyl, a hybrid salt composed of at least two acid radical ions of diethyl phosphinate ion, ethyl butyl phosphinate ion and dibutyl phosphinate ion coordinated with the same aluminum atom is contained instead of a mixture simply mixed by diethyl phosphinate aluminum, ethyl butyl phosphinate aluminum and dibutyl phosphinate aluminum, and one ligand in the hybrid salt is ethyl butyl phosphinate ion. The X-ray diffraction spectra (XRD) of these hybrid salts are very different from those of the simple physically mixed salts of dialkylphosphinic salts. The dialkylphosphinic acid hybrid salt having the composition of formula (I) exhibits a single peak in the XRD spectrum at the strongest absorption peak region. But from aluminium diethylphosphinate and dibutylphosphinate The physically mixed salts of aluminum acid obtained by simple mixing exhibit 2 completely independent peaks in the XRD pattern, and their d values are close to the d values of each of aluminum diethylphosphinate and aluminum dibutylphosphinate, respectively.

In the examples herein, after simple physical mixing of a dialkylphosphinic acid hybrid salt having the composition of formula (I) and either aluminum diethylphosphinate or aluminum dibutylphosphinate, two separate peaks also appear in the strongest absorption peak regions of their XRD patterns. These results strongly suggest that the dialkylphosphinic acid hybrid salt of the formula (I) obtained according to the present invention is not simply an aluminum diethylphosphinate, ethyl R ₁ Aluminum phosphinate, R ₁ Radical R ₂ Mixtures of aluminum phosphinates, but containing diethylphosphinate ions, ethyl R ₁ Radical phosphinate ion, R ₁ Radical R ₂ Structure in which at least two acid radical ions in the phosphinate radical ions are paired with the same aluminum atom, and one of the ligands is ethyl R ₁ And (3) phosphinate ions.

In the examples herein, pure long chain dialkylphosphinic aluminum (R) ₁ ，R ₂ Is C ₄ -C ₁₂ Alkyl) has low thermal stability, and is difficult to meet the requirements of high-molecular materials requiring high-temperature processing. The flame retardant efficiency is not high, and in practical application, the flame retardant polymer of the long-chain dialkyl phosphinate aluminum is found to have large smoke compared with the flame retardant system of diethyl phosphinate aluminum when being burnt. However, the pure diethyl phosphinic acid aluminum has low flame retardant efficiency when being used alone, and the polymer material is difficult to obtain good flame retardant effect when being used alone. In contrast, the dialkylphosphinic acid hybrid salts having the composition of formula (I) are highly thermally stable with longer chain dialkylphosphinic acids aluminum, have less smoke, and have better flame retardant effects than pure aluminum diethylphosphinate and pure aluminum long chain dialkylphosphinate.

According to a second aspect of the present application, there is provided a method for preparing the above dialkylphosphinic acid hybridization salt, the method comprising:

carrying out reaction I on a material containing the mixture A and a metal element M source in a water phase to obtain the dialkylphosphinic acid hybrid salt;

the mixture A contains diethyl phosphinic acid and/or alkali metal salt thereof, and ethyl R ₁ The phosphinic acid and/or alkali metal salt thereof and R ₁ Radical R ₂ The phosphinic acid and/or alkali metal salts thereof.

Alternatively, the conditions of reaction I are: the temperature is 0-250 ℃; the pressure is 0.1MPa-10MPa; the time is 0.01-20h.

Alternatively, the reaction I is carried out at a pH of 0 to 4.

Optionally, the metal element is Al, and the pH value of the reaction I is 0-4; preferably 1 to 3.5; more preferably 2.3 to 3.3.

Specifically, reaction I above has a pH that is too low to precipitate. Too high a pH will produce metal ion hydroxides, introducing impurities.

Optionally, the diethyl phosphinic acid and/or alkali metal salt thereof, ethyl R ₁ Phosphinic acid and/or alkali metal salts thereof, R ₁ Radical R ₂ The molar ratio of the phosphinic acid and/or alkali metal salt thereof to the source of the metal element M is at or near x:y:z:q, wherein q=1/n.

Optionally, diethyl phosphinic acid and/or alkali metal salts thereof, ethyl R in the mixture A ₁ The phosphinic acid and/or alkali metal salt thereof and R ₁ Radical R ₂ The molar ratio of the phosphinic acid and/or alkali metal salt thereof is the same or substantially the same as the x, y, z ratio in formula (I).

Due to the difference in M, the solubility of the hybrid salt in water is not the same. For the high-solubility hybrid salts, the diethylphosphinic acid and/or alkali metal salts thereof, ethyl R in the mixture A ₁ Phosphinic acid and/or alkali metal salts thereof, R ₁ Radical R ₂ The molar ratio of the molar amount of the phosphinic acid and/or alkali metal salt thereof to the M source varies as a result of the difference between the calculated values of x, y and z in the hybrid salt. In addition, in order to obtain more M-containing precipitate, the molar ratio of x, y, z and M corresponding to the reactants at the time of feeding can also exceed the theoretical calculation value.

In the actual operation process, the actual values of x, y, z and q can be judged through phosphorus nuclear magnetism.

Optionally, the obtaining of the mixture a comprises the steps of:

introducing ethylene and C into an aqueous solution containing phosphinic acid and/or alkali metal salt thereof and a free radical initiator ₄ -C ₁₂ Reaction II) to give said mixture a.

Optionally, the phosphinic acid and/or alkali metal salt thereof, ethylene, C ₄ -C ₁₂ The molar ratio of olefins is 1:0.24-1.76:1.76-0.24.

In actual reaction, due to the presence of some side reactions, such as ethylene and/or C ₄ -C ₁₂ Longer chain dialkylphosphinic salts obtained by olefin polymerization, and thus ethylene and/or C ₄ -C ₁₂ The consumption of olefins is higher than theoretical.

Optionally, the phosphinic acid and/or alkali metal salt thereof, ethylene, C ₄ -C ₁₂ The molar ratio of the olefins is the same as or close to the theoretical value calculated from the values x, y, z in formula (I). During the reaction of hypophosphorous acid or its alkali metal salt with ethylene or other olefin, the value of y has a maximum value of less than 1. Depending on the type of olefin, this maximum is 0.76 or less, typically around 0.66. After this maximum value is reached, either x or z increases, so y cannot reach 1. If y=1 is desired, the reaction intermediate product is isolated and purified to remove diethylphosphinic acid and/or its alkali metal salts and R ₁ Radical R ₂ The phosphinic acid and/or its alkali metal salts are disadvantageous for economical reasons.

Specifically, in reaction II, ethylene and C ₄ -C ₁₂ The order of addition of the olefins may be interchanged, may be added simultaneously, or may be partially added first.

Alternatively, in reaction II, hypophosphorous acid and/or its alkali metal salt is first reacted with C ₄ -C ₁₂ The olefins are reacted to give the corresponding y, z values and then reacted substantially completely or completely with ethylene. Substantially completely refers to the ethyl phosphinate, R in the reaction mixture ₁ Radical phosphinate radical, R ₂ The sum of phosphorus contained in the phosphinate and the hypophosphite is less than 5 mol% of the sum of all phosphorus in the reaction solution.

Optionally, in the reaction II system, the mass of the water is 10-99% of the total mass of the aqueous solution.

Specifically, in the reaction II system, too little water is generated, the salting-out effect causes low solubility of olefin in water, the reaction speed is slow, too much water is generated, and the utilization rate of the reaction kettle is reduced.

Optionally, in the reaction II system, the mass of the water is 20-95% of the total mass of the aqueous solution.

Optionally, in the reaction II system, the mass of the water is 45-92% of the total mass of the aqueous solution.

Optionally, in the reaction II system, the mass of the water is 50-90% of the total mass of the aqueous solution.

Optionally, in the reaction II system, the mass of the water is 55-90% of the total mass of the aqueous solution.

Alternatively, the conditions of reaction II are: the temperature is 0-250 ℃; the time is 0.01-50h; the pressure is 0-3MPa.

Specifically, the reaction II has low temperature, low reaction speed and high temperature, and hypophosphite is easy to decompose.

Alternatively, the temperature of reaction II is 10-200 ℃.

Specifically, the pressure of the reaction II is higher than 3MPa, the requirement on reaction equipment is increased, and the operation is difficult.

Alternatively, the pressure of reaction II is 0.2-1.5MPa.

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

Optionally, the molar ratio of the free radical initiator to the phosphinic acid and/or alkali metal salt thereof is from 0.003 to 0.05:1.

Optionally, the free radical initiator is at least one selected from azo initiator, peroxide initiator and photoinitiator. Wherein the addition amount of the free radical initiator can be determined according to actual needs.

Optionally, the azo initiator is selected from cationic and/or non-cationic azo initiators, including one or more of azobisisobutyronitrile, 4 '-azobis (4-cyanovaleric acid), 2' -azobis (2-methylbutyronitrile), 2 '-azobis (2-amidinopropane) dihydrochloride, 2' -azobispropylamidine dihydrochloride.

Alternatively, the peroxide-based initiator is preferably one or more of an inorganic peroxide and an organic peroxide, particularly preferably hydrogen peroxide, ammonia persulfate, potassium persulfate, sodium percarbonate, benzoyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, peracetic acid.

Preferably, the free radical initiator is a peroxide-based initiator. Particularly preferably, the free radical initiator is selected from one of ammonium persulfate, potassium persulfate, sodium persulfate.

Optionally, the obtaining of the mixture a comprises the steps of:

introducing C into an aqueous solution containing hypophosphorous acid and/or alkali metal salt and free radical initiator ₄ -C ₁₂ To be fed C ₄ -C ₁₂ After the ratio of the olefin to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I), the introduction of C is stopped ₄ -C ₁₂ And continuing to feed ethylene for reaction to obtain the mixture A. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Optionally, the obtaining of the mixture a comprises the steps of:

introducing C into an aqueous solution containing hypophosphorous acid and/or alkali metal salt and free radical initiator ₄ -C ₁₂ To the olefins of C ₄ -C ₁₂ After complete or near complete olefin reaction, ethylene reaction is continued to give the mixture a. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Alternatively, hypophosphorous acid and/or its alkali metal saltAnd C ₄ -C ₁₂ To obtain a single R having or substantially near the y value ₁ The phosphinic acid or alkali metal salt thereof, and z is controlled to 0.76 or less, and then the addition of C is stopped ₄ -C ₁₂ Instead, ethylene is added and the reaction is continued in the presence of an initiator and then with the desired metal salt to give the flame retardant of formula (I). Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Optionally, the obtaining of the mixture a comprises the steps of:

introducing C into an aqueous solution containing hypophosphorous acid and/or alkali metal salt and free radical initiator ₄ -C ₁₂ To said C ₄ -C ₁₂ After complete or near complete reaction of the olefin with a portion of the ethylene, the remainder of the ethylene is fed to the reactor to obtain said mixture A. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Optionally, the obtaining of the mixture a comprises the steps of:

introducing C into an aqueous solution containing hypophosphorous acid and/or alkali metal salt and free radical initiator ₄ -C ₁₂ Wherein the ratio of ethylene to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt is less than (2x+y)/1 in formula (I), C to be introduced ₄ -C ₁₂ After the ratio of the olefin to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I), the introduction of C is stopped ₄ -C ₁₂ And continuing to feed the remaining part of ethylene for reaction to obtain the mixture A. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Optionally, the obtaining of the mixture a comprises the steps of:

to a composition containing hypophosphorous acid and/or alkali metal salt thereof, and free radicalsIntroducing a part of ethylene into the aqueous solution of the initiator, wherein the mole ratio of the part of ethylene to the hypophosphorous acid and/or the alkali metal salt total phosphorus thereof is (2x+y)/1 in the formula (I) or less, and continuing introducing C after the part of ethylene is reacted completely ₄ -C ₁₂ To be fed C ₄ -C ₁₂ After the ratio of the olefin to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I), the introduction of C is stopped ₄ -C ₁₂ Continuing to feed the rest of ethylene for reaction to obtain the mixture A. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Optionally, the obtaining of the mixture a comprises the steps of:

charging a portion of ethylene into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt, and a free radical initiator, and continuing charging C after the portion of ethylene has reacted completely or nearly completely ₄ -C ₁₂ To be reacted with the olefins of said C ₄ -C ₁₂ After complete or near complete reaction of the olefins, the remainder of the ethylene is fed to react to give said mixture a. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Alternatively, the total amount of ethylene and the C ₄ -C ₁₂ The molar ratio of olefins is from 0.14 to 7.33:1.

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

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

Optionally hypophosphorous acid and/or its alkali metal salt is/are simultaneously with C ₄ -C ₁₂ Wherein (2) the olefin and part of the ethylene are reacted in the presence of a free radical initiator to control C ₄ -C ₁₂ The amount of olefins and ethylene to be reacted, ethyl R ₁ Phosphinic acid or alkali metal thereofSalts of genus R ₁ The mole percent of the sum of the phosphinic acids or their alkali metal salts is close to the value y, and R ₁ Radical R ₂ The mole percent of the phosphinic acid or the alkali metal salt thereof approaches the value of z, and z is less than or equal to 0.76, and the addition of C is stopped ₄ -C ₁₂ Continuing the addition of the remaining ethylene, continuing the reaction in the presence of an initiator to completion, and subsequently reacting with the desired metal salt to obtain the dialkylphosphinic acid hybrid salt of formula (I). Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Optionally, the obtaining of the mixture a comprises the steps of:

introducing ethylene into aqueous solution containing hypophosphorous acid and/or its alkali metal salt and free radical initiator, controlling ethylene amount, stopping introducing ethylene after the molar ratio of ethylene to hypophosphorous acid and/or its alkali metal salt reaches (y+2x)/1 in the formula (I), and continuing adding C ₄ -C ₁₂ Continuing the reaction to the end in the presence of an initiator to give said mixture A. Here, C ₄ -C ₁₂ The olefins of (2) may be pure C ₄ -C ₁₂ Or C ₄ -C ₁₂ Is a mixed olefin of (a) and (b).

Specifically, after reaction II is completed, diethyl phosphinic acid and ethyl R do not need to be separated ₁ Phosphinic acid, R ₁ Radical R ₂ The phosphinic acid and/or alkali metal salt thereof can be directly subjected to the next reaction.

According to a third aspect of the present application, there is provided a flame retardant selected from at least one of the above dialkylphosphinic acid hybrid salts, dialkylphosphinic acid hybrid salts prepared according to the above method.

Optionally, the flame retardant further comprises at least one selected from phosphates, phosphites, alkylphosphonates and alkylphosphinates, and the mole content of these phosphorus-containing impurities in the flame retardant is 10% or less, the mole number of the flame retardant being based on the mole number of phosphorus element contained therein.

According to a fourth aspect of the present application, there is provided a flame retardant material, including a flame retardant P and a thermoplastic polymer material;

the flame retardant P is at least one selected from the flame retardants.

Optionally, the mass content of the flame retardant P in the flame retardant material is 1-35%.

Optionally, the flame retardant material comprises 1-35wt% of flame retardant P and 65-99wt% of thermoplastic polymer material.

Thermoplastic polymer materials in this application refer to plastics that have heat softening, cooling hardening properties.

Specifically, the amount of the flame retardant P depends on the thermoplastic polymer material.

Optionally, the mass content of the flame retardant P in the flame retardant material is 3-20%.

Optionally, in the flame retardant material, functional additives are further included;

the functional additive is at least one selected from reinforcing agents, anti-dripping agents, stabilizing agents, pigments, dyes, char-forming catalysts, dispersing agents, nucleating agents, inorganic fillers and antioxidants;

preferably, the functional additive is present in the flame retardant material in an amount of 5 to 40% by mass.

Optionally, the reinforcing agent is selected from glass fibers.

Optionally, the anti-drip agent is selected from Teflon.

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

Optionally, in the flame retardant material, a flame retardant Q is further included;

the flame retardant Q is at least one selected from nitrogen flame retardants and boron flame retardants.

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

the boron-based flame retardant is selected from zinc borate.

Optionally, the mass content of the flame retardant Q in the flame retardant material is 0.5-20%.

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

Optionally, the polyamide is selected from at least one of aliphatic polyamide, aromatic polyamide, semi-aromatic polyamide, and copolymer of semi-aromatic polyamide and aliphatic polyamide.

Polyamides, also known as chinlon or nylon, are a generic term for polymers containing-NH-C (O) -amide groups in their structural units, and are synthesized by 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, in accordance with common general knowledge in the art. Polyamides are generally classified into aliphatic polyamides, aromatic polyamides and semiaromatic polyamides according to the composition of the main chain thereof. Semi-aromatic polyamide means that at least one of its synthetic monomers contains aromatic groups in its structure.

Optionally, the aliphatic polyamide is selected from one or a mixture of more than one of a copolymer of polyamide 6 and polyamide 66, polyamide 6 and polyamide 66.

Alternatively, the semi-aromatic polyamide can be prepared from any one or more aromatic dicarboxylic acids and any one or more aliphatic diamines, and also can be prepared from any one or more aromatic diamines and any one or more aliphatic dicarboxylic acids. One or more of dicarboxylic acid, diamine, lactam and amino acid can be optionally added into the system to prepare the polyamide copolymer with corresponding properties. The added dicarboxylic acid is aromatic dicarboxylic acid and/or aliphatic dicarboxylic acid; the diamine added is aromatic diamine and/or aliphatic diamine; the added lactam may be an aliphatic or aromatic lactam. The amino acid added may be an aromatic or aliphatic amino acid.

Alternatively, the semiaromatic polyamide is made from one or more aromatic dicarboxylic acids, optionally selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and one or more aliphatic diamines, selected from Ren Xuanzi butanediamine, hexamethylenediamine, octanediamine, decanediamine and 2-methylpentanediamine.

Alternatively, the semiaromatic polyamide is made from aliphatic diamines, aromatic dicarboxylic acids and aliphatic dicarboxylic acids.

Optionally, the semi-aromatic polyamide is prepared from aliphatic diamine and aromatic dicarboxylic acid; optionally, an aliphatic dicarboxylic acid may be added thereto, wherein the mole fraction of the aliphatic dicarboxylic acid is 0-45% of the total amount of dicarboxylic acids, i.e., the mole number of aliphatic dicarboxylic acid/(mole number of aliphatic dicarboxylic acid+mole number of aromatic dicarboxylic acid) =0-45%.

Optionally, the aromatic dicarboxylic acid is any one or more selected from terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; the aliphatic diamine is selected from one or more of butanediamine, hexanediamine, octanediamine, decanediamine and 2-methylpentanediamine; the aliphatic dicarboxylic acid is one or more selected from adipic acid, succinic acid, sebacic acid and suberic acid.

Optionally, the polyamide is selected from one or more of poly (hexamethylene terephthalamide) (abbreviated as PA 6T), poly (hexamethylene isophthalamide) (abbreviated as PA 6I), a terephthalic acid/hexamethylene diamine/caprolactam copolymer (abbreviated as PA 6T/6), a terephthalic acid/hexamethylene diamine/adipic acid copolymer (abbreviated as PA 6T/66), a terephthalic acid/hexamethylene diamine/adipic acid/isophthalic acid copolymer (abbreviated as PA 6T/6I/66), poly (hexamethylene terephthalamide) (abbreviated as PA 9T), poly (hexamethylene terephthalamide) (abbreviated as PA 10T), poly (hexamethylene terephthalamide) (abbreviated as PA 12T), poly (m-xylylene adipamide) (abbreviated as MXD 6), a terephthalic acid/hexamethylene diamine/2-methylpentanediamine copolymer (abbreviated as PA 6T/2-MPMDT), terephthalic acid/2, 4 trimethylhexamethylene diamine/2, 4-trimethylhexamethylene diamine or a copolymer.

Optionally, the aliphatic polyamide is selected from at least one of polyamide 6, polyamide 66, and a copolymer of polyamide 6 and polyamide 66.

Optionally, the semiaromatic polyamide is selected from polyphthalamides (PPA).

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

In embodiments of the present invention, the values of x, y, z in formula (i) are independent of the amount of other phosphorus-containing impurities, x+y+z=1, and x+z > 0. The flame retardant having the composition of formula (i) may contain minor amounts of other phosphorus-containing impurities. Some trace amounts of phosphates, phosphites, alkylphosphonates, alkylphosphinates may be present in the flame retardant due to impurities in the raw materials or impurities generated by the synthesis process. Some of which are composed of ethylene and/or C ₄ -C ₁₂ Telomer products such as ethyl n-tetradecylphosphinate, ethyl hexadecylphosphinate, polymerized or copolymerized olefins, may also be present as impurities in flame retardants having the composition of formula (I). But as long as the total molar amount of these other phosphate-containing acid ions does not exceed 5% of the total molar amount of phosphorus, the proper functioning of the flame retardant having the composition of formula (i) is not affected.

In the examples herein, the ratio of x, y, z in formula (I) may be determined by either alkaline hydrolysis or acidolysis of the flame retardant ³¹ P-NMR (nuclear magnetic resonance). Diethyl phosphinate, ethyl R ₁ Radical phosphinate radical, R ₁ Radical R ₂ The phosphinate ions have different properties ³¹ Chemical shift of P in ³¹ In most cases, the P-NMR spectrum shows an independent peak.

The peak areas of these peaks correspond to the molar concentrations of the respective dialkylphosphinate ions, respectively, wherein some dialkylphosphinates of the same chemical formula have isomers, and thus can exhibit different peaks in the nuclear magnetic resonance spectrum, which isomers are classified into one class when the x, y, z values are calculated. For example, when R ₁ ，R ₂ In the case of butyl, the resulting dialkylphosphinic acid hybrid salt ³¹ Five sets of peaks occur in the P-NMR spectrum, which correspond to ethyl sec-butylphosphinate ion, n-butyl sec-butylphosphinate ion, diethyl phosphinate ion, ethyl n-butylphosphinate ion, di-n-butylphosphinate ion, respectively. Wherein the molar concentration of the diethyl phosphinate ion corresponds to x, ethyl sec-butylThe sum of the molar concentrations of phosphinate ions and ethyl-n-butylphosphinate ions (collectively referred to as the molar concentration of ethylbutylphosphinate ions) corresponds to y, the sum of the molar concentrations of di-n-butylphosphinate ions and n-butylsec-butylphosphinate ions (collectively referred to as the molar concentration of dibutylphosphinate ions) corresponds to z, and the ratio of the three is the value of x, y and z. In some cases, telomer dialkylphosphinate ions are present, in small amounts, and chemical shifts close to the corresponding dialkylphosphinate ions, thus incorporating them into the corresponding dialkylphosphinate ions upon integration.

The beneficial effects that this application can produce include:

(1) The dialkylphosphinic acid hybridization salt with the composition shown in the formula (I) has the advantages of small addition amount, high thermal stability, high flame retardant efficiency on high polymer materials and good economy. The flame retardant coating overcomes the defect of low flame retardant efficiency on a high polymer material when diethyl phosphinate and long-chain dialkyl phosphinate are used independently, overcomes the defects of low heat stability and large flame retardant smoke of long-chain dialkyl phosphinate, and can be widely applied to flame retardance of the high polymer material which needs high-temperature processing;

(2) The application provides a preparation method of dialkyl phosphinic acid hybrid salt, which avoids the defect that different dialkyl phosphinic acids are required to be prepared independently, uses water as a reaction solvent and has good environmental protection. The raw materials are easy to obtain, and the economy is high.

Drawings

FIG. 1 is a dialkylphosphinic acid hybrid aluminum salt having different values of x, y, z (corresponding to R in formula (I) ₁ And R is ₂ Is butyl, and in the reaction II, C used ₄ -C ₁₂ Butene) and aluminum diethylphosphinate and aluminum dibutylphosphinate;

FIGS. 2a, 2b are dialkylphosphinic acid hybrid aluminum salts having different values of x, y, z (corresponding to R in formula (I) ₁ And R is ₂ Is butyl, and in the reaction II, C used ₄ -C ₁₂ Is butene), aluminum diethylphosphinate, aluminum dibutylphosphinate, and physical mixture of aluminum dibutylphosphinate and aluminum diethylphosphinateXRD patterns of the salt-closed, wherein figure 2b is a partial enlargement of the strongest absorption peak of figure 2 a;

FIGS. 3 and 4 are, respectively, the dialkylphosphinic acid hybrid salts prepared in example 3 and example 4 (corresponding to R in formula (I) ₁ And R is ₂ Is butyl, and in the reaction II, C used ₄ -C ₁₂ The olefin of (1) is butylene) after alkaline hydrolysis ³¹ P-NMR spectrum.

Detailed Description

The present application is described in detail below with reference to examples, but the present application is not limited to these examples.

Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.

The raw materials used in the examples are as follows:

PA66 (also known as polyamide 66 or nylon 66): dupont Zytel 70g35 HSL NC010, 35% glass fiber by weight;

PA6 (also known as polyamide 6 or nylon 6) dupont Zytel 73G30L nc010, 30% glass fiber content by weight;

ADP: aluminum diethylphosphinate, exolit OP1230, clariant germany;

MPP: melamine polyphosphate, kama chemical technologies, inc;

Zinc borate: national pharmaceutical group chemical agents, inc;

antioxidant 1010: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], shanghai microphone Biochemical technology Co., ltd;

antioxidant 168: tris [2, 4-di-t-butylphenyl ] phosphite, strem corporation, usa;

and (3) compounding an antioxidant: antioxidant 1010 (tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl propionate ] pentaerythritol ester) and antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite) were mixed in a 1:1 weight ratio;

combustion test standard: GB/T2408-2008 standard;

nuclear Magnetic Resonance (NMR) test: the instrument used was of the type AVANCE III MHz and AVANCE III MHz, bruker, germany;

nuclear magnetic resonance phosphorus spectrum [ ] ³¹ P-NMR) test method: pre-delay d1=10 seconds, scanning for 32 times, and taking the ratio of peak areas as the ratio of the mole numbers of various phosphonate ions;

the instrument model used for X-ray diffraction (XRD) testing: d8 ADVANCE DAVINCI Bruker, germany;

the type of the instrument used for TGA thermal weightlessness treatment: q500, america TA, nitrogen atmosphere, heating rate 10 ℃/min.

Example 1

Preparation of a hybrid salt having the composition of formula (i), wherein x=0.40, y=0.56, z=0.04, m=al, n=3.

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water, and the solution was put into a 1L stainless steel autoclave, the autoclave was replaced twice with nitrogen, and after vacuum pumping, butene was charged until the pressure did not rise any more. The reaction solution was heated to about 90℃and the pressure gauge was set at 0.25MPa, and then a 4% strength by mass aqueous sodium persulfate solution was fed at a constant speed of 10ml/h, and butene was continuously fed into the reaction vessel, whereby the feed amount of olefin was measured by the gas flow meter. After 4 hours, the passage of butene was stopped and the passage of ethylene was started. After 12 hours, the pressure of the reaction kettle is not reduced any more, the temperature is reduced, the pressure is relieved, and N is reduced ₂ Purging and discharging to obtain colorless transparent reaction liquid. During the reaction, the final reaction liquid is sampled to measure the nuclear magnetism, ³¹ the P-NMR results are shown in Table 1:

TABLE 1

Note that: in the table, the ethylbutylphosphinate ion includes ethyl sec-butylphosphinate ion and ethyl n-butylphosphinate ion; the dibutyl phosphinate ion includes n-butyl sec-butyl phosphinate ion (R ₁ ≠R ₂ N-butyl and sec-butyl) and di-n-butylphosphinate, respectivelyIon (R) ₁ ＝R ₂ N-butyl); other bis-addition products: comprising di-sec-butylphosphinate ions and telomer dialkylphosphinate ions derived from the polymerization of ethylene and/or butene. The butyl phosphinate ion is the sum of the sec-butyl phosphinate ion and the n-butyl phosphinate ion; the butylphosphonate ion is the sum of the sec-butylphosphonate ion and n-butylphosphonate ion, as follows.

307.59 g (phosphorus content: 0.36 mol) of the above-mentioned partial solution was mixed with a 10% by mass aqueous solution containing 39.99 g of aluminum sulfate octadecabydrate at normal pressure, the reaction temperature was controlled to 70℃and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120 ℃ to give 48.15 g of a white solid. Dissolving the sample in aqueous solution of sodium hydroxide to obtain phosphorus nuclear magnetism, and preparing the phosphorus nuclear magnetism from ³¹ The P-NMR spectrum revealed that the molar content of diethylphosphinate ion was 40.23%, the molar content of ethyl-n-butylphosphinate ion was 51.98%, the molar content of ethyl-sec-butylphosphinate ion was 4.10% and the molar content of di-n-butylphosphinate ion was 3.69%. The mole fractions of phosphinate ions of the same formula were added (i.e., the sum of ethyl n-butylphosphinate ions and ethyl sec-butylphosphinate ions corresponds to the calculation of the y value) to give x=0.40, y=0.56, and z=0.04.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Example 2

Preparation of a hybrid salt having the composition of formula (i), wherein x=0, y=0.24, z=0.76, m=al, n=3.

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water, and the solution was put into a 1L stainless steel autoclave, the autoclave was replaced twice with nitrogen, and after vacuum pumping, butene was charged until the pressure did not rise any more. Heating the reaction solution to about 90deg.C, displaying pressure gauge of 0.25MPa, andthe reaction kettle is continuously filled with sodium persulfate aqueous solution with the mass concentration of 4% at a constant speed of 10ml/h, and the butene is continuously introduced, so that the olefin introduction amount is measured by a gas flow meter. After 8.5 hours, the passage of butene was stopped and ethylene was started. After 15 hours, the pressure of the reaction kettle is not reduced, the temperature is reduced, the pressure is relieved, and N is added ₂ Purging and discharging to obtain colorless transparent reaction liquid. The reaction liquid is sampled to measure the nuclear magnetism, ³¹ the P-NMR results are shown in Table 2:

TABLE 2

353.74 g (phosphorus content: 0.36 mol) of the above-mentioned partial solution was mixed with a 10% by mass aqueous solution containing 39.99 g of aluminum sulfate octadecabydrate at normal pressure, the reaction temperature was controlled to 70℃and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120 ℃ to give 66.54 g of a white solid. Dissolving the sample in aqueous solution of sodium hydroxide to obtain phosphorus nuclear magnetism, and preparing the phosphorus nuclear magnetism from ³¹ The P-NMR spectrum revealed that the molar content of ethyl sec-butylphosphinate ion was 2.42%, the molar content of ethyl n-butylphosphinate ion was 21.13%, the molar content of n-butyl sec-butylphosphinate ion was 7.25%, the molar content of di-n-butylphosphinate ion was 68.63%, and the sum of the molar contents of other phosphorus-containing impurities such as butylphosphinate ion and butylphosphinate ion was 0.57%. The mole fractions of phosphinate ions of the same formula were added (i.e. ethyl n-butylphosphinate ion and ethyl sec-butylphosphinate ion mole fraction were added for calculating the y value; n-butyl sec-butylphosphinate ion and di-n-butylphosphinate ion and dialkylphosphinate telomer mole fraction were added for calculating the z value) and normalized to give x=0, y=0.24, z=0.76.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Example 3

Preparation of a hybrid salt having the composition of formula (i), wherein x=0, y=0.32, z=0.68, m=al, n=3.

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water, and the solution was put into a 1L stainless steel autoclave, the autoclave was replaced twice with nitrogen, and after vacuum pumping, butene was charged until the pressure did not rise any more. The reaction solution was heated to about 90℃and the pressure gauge was set at 0.25MPa, and then a 4% strength by mass aqueous sodium persulfate solution was fed at a constant speed of 10ml/h, and butene was continuously fed into the reaction vessel, whereby the feed amount of olefin was measured by the gas flow meter. After 7 hours, the passage of butene was stopped and the passage of ethylene was started. After 15.5 hours, the pressure of the reaction kettle is not reduced any more, and the temperature and the pressure are reduced, and N is removed ₂ Purging and discharging to obtain colorless transparent reaction liquid. The reaction liquid is sampled to measure the nuclear magnetism, ³¹ the P-NMR results are shown in Table 3:

TABLE 3 Table 3

334.45 g (phosphorus content: 0.36 mol) of the above-mentioned partial solution was mixed with a 10% by mass aqueous solution containing 39.99 g of aluminum sulfate octadecabydrate at normal pressure, the reaction temperature was controlled to 70℃and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120℃to give 64.81 g of a white solid. Dissolving the sample in aqueous solution of sodium hydroxide to prepare phosphorus nuclear magnetism, ³¹ the P-NMR spectrum is shown in FIG. 3. From the following components ³¹ The P-NMR spectrum revealed that the molar content of ethyl sec-butylphosphinate ion was 2.45%, the molar content of ethyl n-butylphosphinate ion was 29.44%, the molar content of n-butyl sec-butylphosphinate ion was 6.83% and the molar content of di-n-butylphosphinate ion was 61.28%. Adding the mole fractions of phosphinate ions of the same formula (i.e., ethyl n-butylphosphinate ion to ethyl sec-butylphosphinate ion mole fraction)The addition of the numbers is used for calculating y value; the mole fractions of n-butyl sec-butylphosphinate ion and di-n-butylphosphinate ion are added to calculate the z value) and normalized to give x=0, y=0.32, and z=0.68.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Example 4

Preparation of a hybrid salt having the composition of formula (i), wherein x=0.02, y=0.63, z=0.35, m=al, n=3.

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water, and the solution was put into a 1L stainless steel autoclave, the autoclave was replaced twice with nitrogen, and after vacuum pumping, butene was charged until the pressure did not rise any more. The reaction solution was heated to about 90℃and the pressure gauge was set at 0.25MPa, and then a 4% strength by mass aqueous sodium persulfate solution was fed at a constant speed of 10ml/h, and butene was continuously fed into the reaction vessel, whereby the feed amount of olefin was measured by the gas flow meter. After 5.5 hours, the passage of butene was stopped and ethylene was started. After 13 hours, the pressure of the reaction kettle is not reduced any more, the temperature is reduced, the pressure is relieved, and N is reduced ₂ Purging and discharging to obtain colorless transparent reaction liquid. The reaction liquid is sampled to measure the nuclear magnetism, ³¹ the P-NMR results are shown in Table 4:

TABLE 4 Table 4

329.57 g (phosphorus content: 0.36 mol) of the above-mentioned partial solution was mixed with a 10% by mass aqueous solution containing 39.99 g of aluminum sulfate octadecabydrate at normal pressure, the reaction temperature was controlled to 70℃and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120 ℃ to give 59.60 g of a white solid. Dissolving the sample in aqueous solution of sodium hydroxide to prepare phosphorus nuclear magnetism, ³¹ The P-NMR spectrum is shown in FIG. 4. From the following components ³¹ The P-NMR spectrum revealed that the molar content of diethylphosphinate ion was 1.99%, the molar content of ethyl sec-butylphosphinate ion was 4.30%, the molar content of ethyl n-butylphosphinate ion was 58.22%, the molar content of n-butyl sec-butylphosphinate ion was 3.44%, the molar content of di-n-butylphosphinate ion was 30.67%, and the sum of the molar contents of other phosphorus-containing impurities such as ethyl phosphinate ion, butyl phosphinate ion, ethyl phosphonate ion, butyl phosphonate ion was 1.38%. The mole fractions of phosphinate ions of the same formula are added (i.e., ethyl n-butylphosphinate ion and ethyl sec-butylphosphinate ion are added to calculate the y value; n-butyl sec-butylphosphinate ion and di-n-butylphosphinate ion and dialkylphosphinate telomer mole fractions are added to calculate the z value; dialkylphosphinate telomers are also incorporated into adjacent di-n-butylphosphinate ions here) and normalized to give x=0.02, y=0.63, z=0.35.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is (100％)。

Example 5

Preparation of a hybrid salt having the composition of formula (i), wherein x=0.22, y=0.67, z=0.11, m=al, n=3.

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water, and the solution was put into a 1L stainless steel autoclave, which was replaced twice with nitrogen, and after vacuum pumping, butene was filled. The reaction solution was heated to about 90℃and the pressure gauge was set at 0.15MPa, and then a 4% strength by mass aqueous sodium persulfate solution was fed at a constant speed of 10ml/h, and butene was continuously fed into the reaction vessel, whereby the feed amount of olefin was measured by the gas flow meter. After 7.5 hours, the passage of butene was stopped and ethylene was started. After 21 hours, the pressure of the reaction kettle is basically not reduced, and the temperature and the pressure are reduced, and N is reduced ₂ Purging and discharging to obtain colorless transparent reaction liquid. The reaction liquid is sampled to measure the nuclear magnetism, ³¹ the P-NMR results are shown in Table 5:

TABLE 5

374.84 g (phosphorus content: 0.36 mol) of the above-mentioned partial solution was mixed with a 10% by mass aqueous solution containing 39.99 g of aluminum sulfate octadecabydrate at normal pressure, the reaction temperature was controlled to 70℃and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120℃to give 52.13 g of a white solid. Dissolving the sample in aqueous solution of sodium hydroxide to obtain phosphorus nuclear magnetism, and preparing the phosphorus nuclear magnetism from ³¹ The P-NMR spectrum revealed that the molar content of diethylphosphinate ion was 21.32%, the molar content of ethyl sec-butylphosphinate ion was 4.52%, the molar content of ethyl n-butylphosphinate ion was 62.02%, the molar content of n-butyl sec-butylphosphinate ion was 1.11%, the molar content of di-n-butylphosphinate ion was 9.66%, and the sum of the molar contents of other phosphorus-containing impurities such as ethyl phosphinate ion, butyl phosphinate ion, ethyl phosphonate ion, butyl phosphonate ion, and phosphite ion was 1.37%. The mole fractions of phosphinate ions of the same formula were added (i.e., ethyl n-butylphosphinate ion and ethyl sec-butylphosphinate ion were added to calculate the y value; n-butyl sec-butylphosphinate ion and di-n-butylphosphinate ion were added to calculate the z value.) and normalized to give x=0.22, y=0.67, and z=0.11. XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Example 6

Preparation of a hybrid salt having the composition of formula (i), wherein x=0.59, y=0.39, z=0.02, m=al, n=3.

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water and added to 1L of stainless steel together with 39.7 g of hexene And (3) a steel pressure kettle, wherein the reaction kettle is replaced by nitrogen twice, and part of ethylene is filled after vacuumizing. The reaction mixture was heated to about 90℃and then fed into a 4% strength by mass aqueous sodium persulfate solution at a constant speed of 10ml/h, followed by reaction for 8.5 hours, and then the remainder of ethylene was fed. After 14.5 hours, the pressure of the reaction kettle is not reduced any more, and the temperature and the pressure are reduced, and N is removed ₂ Purging and discharging to obtain colorless transparent reaction liquid. The reaction liquid is sampled to measure the nuclear magnetism, ³¹ the P-NMR results are shown in Table 6:

TABLE 6

Note that: in the table, ethylhexyl phosphinate ions include ethyl secondary hexyl phosphinate ions and ethyl n-hexyl phosphinate ions; the dihexylphosphinate ion includes n-hexyl sec-hexylphosphinate ion (R ₁ ≠R ₂ N-hexyl and sec-hexyl, respectively) and di-n-hexylphosphinate ions (R ₁ ＝R ₂ =n-hexyl); the hexyl phosphinate ions are secondary hexyl phosphinate ions and n-hexyl phosphinate ions; the hexyl phosphonate ion is the sum of a secondary hexyl phosphonate ion and a n-hexyl phosphonate ion.

367.37 g (phosphorus content: 0.36 mol) of the above-mentioned partial solution was mixed with a 10% by mass aqueous solution containing 39.99 g of aluminum sulfate octadecabydrate at normal pressure, the reaction temperature was controlled to 70℃and the pH value was adjusted to 3.0 or less to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120℃to give 50.35 g of a white solid. Dissolving the sample in aqueous solution of sodium hydroxide to obtain phosphorus nuclear magnetism, and preparing the phosphorus nuclear magnetism from ³¹ The P-NMR spectrum revealed that the molar content of diethylphosphinate ion was 57.54%, the molar content of ethylhexyl phosphinate ion was 38.19%, the molar content of dihexylphosphinate ion was 2.21%, and the sum of the molar contents of other phosphorus-containing impurities such as ethylphosphinate ion, hexylphosphinate ion, and phosphite ion was 2.06%. Gui (Chinese angelica)After the normalization, x=0.59, y=0.39, and z=0.02 are obtained.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Example 7

Preparation of a hybrid salt having the composition of formula (i), wherein x=0.01, y=0.52, z=0.47, m=cu, n=2.

137.32 g (phosphorus content: 0.15 mol) of the partial solution obtained in the first step in example 4 was mixed with a 25% strength by mass aqueous solution containing 18.73 g of copper sulfate pentahydrate at normal pressure, the reaction temperature was controlled at 70℃and the pH was adjusted to less than 4 to obtain a large amount of precipitate. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the solution is hot, and washing the filter cake with clear water until the pH value is more than 4.5. The filter cake was then dried at 120 ℃ to give 19.53 g of solid in 70% yield. Dissolving the sample in aqueous solution of sodium hydroxide to obtain phosphorus nuclear magnetism, and preparing the phosphorus nuclear magnetism from ³¹ The P-NMR spectrum revealed that the molar content of diethylphosphinate ion was 0.80%, the molar content of ethyl sec-butylphosphinate ion was 2.76%, the molar content of ethyl n-butylphosphinate ion was 49.60%, the molar content of n-butyl sec-butylphosphinate ion was 4.48% and the molar content of di-n-butylphosphinate ion was 42.36%. The mole fractions of phosphinate ions of the same formula were added (i.e., the sum of ethyl n-butylphosphinate ions and ethyl sec-butylphosphinate ions corresponds to the calculation of the y value) to give x=0.01, y=0.52, and z=0.47. The difference of solubility of different copper dialkylphosphinate salts results in lower yield of the embodiment, and the values of x, y and z in the finally obtained hybrid salt are greatly different from those of the other metal hybrid salts obtained from the same phosphorus raw material.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Fig. 1 is a graph of thermal weight loss (TGA) of hybrid salts (example 1, example 4, example 5) and aluminum diethylphosphinate and aluminum dibutylphosphinate (comparative example 1) with different x, y, z values. From the figure, the higher the z value, the lower the thermal stability of the hybrid salt, and the higher the x, the higher the thermal stability.

FIG. 2a is an XRD pattern of a hybrid salt (examples 1-5), aluminum dibutyl phosphinate (comparative example 1), aluminum Diethyl Phosphinate (ADP) and a physically mixed salt of aluminum dibutyl phosphinate and aluminum diethyl phosphinate having different x, y, z values. FIG. 2b is a close-up of the strongest absorption peak of FIG. 2 a. As can be seen from FIG. 2b, a simple physically mixed salt has 2 independent peaks in the XRD spectrum at the strongest absorption peak region and their d values are close to those of aluminum diethylphosphinate and aluminum dibutylphosphinate, respectively, and the hybrid salt having the composition of formula (I) has only one peak or overlapping peaks and d values substantially between those of aluminum diethylphosphinate and aluminum dibutylphosphinate. This illustrates that the dialkylphosphinic acid hybrid salts of the present invention having the composition of formula (I) are not simply mixtures of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, aluminum dibutylphosphinate, but rather comprise hybrid salts having a structure in which at least two of the ions diethylphosphinate, ethylbutylphosphinate, and di Ding Ci are paired with the same aluminum atom.

Example 8

Polyamide PA66, the hybrid salt prepared in example 1 and the compound antioxidant are mixed in a weight ratio of 79.6:20:0.4 in an internal mixer with a rotation speed of 50 revolutions per minute, the temperature is set to 280 ℃, and the mixture is taken out, cooled and dried after 5 minutes. Then filling the mixture into a mould, preheating the mixture for 10 minutes in a flat vulcanizing machine at 280 ℃, maintaining the pressure for 5 minutes under 10MPa, and then cold pressing the mixture. And cutting the sample after the sample is cooled, and testing. The flame retardant rating of the 1.6mm sample was UL 94V-0.

Example 9

Polyamide PA6, the hybrid salt prepared in example 1 and the compound antioxidant are mixed in an internal mixer with the rotating speed of 50 revolutions per minute according to the weight ratio of 79.6:20:0.4, the temperature is set to 260 ℃, and the mixture is taken out, cooled and dried after 5 minutes. Then filling the mixture into a mould, preheating the mixture for 10 minutes at 260 ℃ by a flat vulcanizing machine, maintaining the pressure for 5 minutes at 10MPa, and then cold pressing the mixture. And cutting the sample after the sample is cooled, and testing. The flame retardant rating of the 1.6mm sample was UL 94V-0.

Examples 10 to 22

The hybrid salts prepared in examples 1 to 7 were prepared and tested in polyamide PA66, PA6, respectively, in the manner of examples 8, 9, the results being shown in table 7.

Comparative example 1 preparation of aluminum dibutyl phosphinate

100 g of sodium hypophosphite monohydrate was dissolved in 500 g of water, and the solution was put into a 1L stainless steel autoclave, the autoclave was replaced twice with nitrogen, and after vacuum pumping, butene was charged until the pressure did not rise any more. The reaction solution was heated to about 90℃and then a sodium persulfate aqueous solution having a mass concentration of 4% was introduced at a constant rate of 10ml/h, and butene was continuously introduced into the reaction vessel, whereby the amount of butene introduced was measured by a gas flow meter. After 25.5 hours, the system pressure is not reduced any more, the reaction is stopped, the temperature is reduced, the pressure is relieved, and N is removed ₂ And (5) purging and discharging to obtain transparent reaction liquid. The reaction liquid is sampled and used as nuclear magnetism, ³¹ the P-NMR results showed that: the molar content of n-butyl sec-butyl phosphinic acid is 10.56%, the molar content of di-n-butyl phosphinic acid is 84.92%, the molar content of dibutyl phosphinic acid telomer is 3.52%, and the rest 1.00% are byproducts such as butyl phosphinic acid, butyl phosphonic acid, phosphorous acid and the like.

A large amount of precipitate was obtained by mixing 394 g (0.3996 mol) of the above solution with 10% by mass of an aqueous solution containing 44.38 g of aluminum sulfate octadecabydrate at normal pressure, controlling the reaction temperature to 70℃and adjusting the pH to 3.0 or less. After the addition and mixing are completed, the temperature is kept for 0.5 hour. Filtering while the filter cake is hot, filtering slowly, and washing the filter cake with clear water until the pH is more than 4.5. The filter cake was then dried at 120℃to give 67.28 g of a white solid.

XRD testing of the sample, wherein the layer spacing corresponding to the characteristic peak with highest relative intensity measured by the obtained XRD is(100％)。

Comparative example 2

Mixing polyamide PA66, aluminum dibutyl phosphinate prepared in comparative example 1 and a compound antioxidant according to the weight ratio of 79.6:20:0.4, in an internal mixer with the rotating speed of 50 revolutions per minute, setting the temperature to 280 ℃, taking out after 5 minutes, cooling and drying. Then filling the mixture into a mould, preheating the mixture for 10 minutes in a flat vulcanizing machine at 280 ℃, maintaining the pressure for 5 minutes under 10MPa, and then cold pressing the mixture. And cutting the sample after the sample is cooled, and testing. The flame retardant rating for the 1.6mm sample was UL94 no rating.

Comparative example 3

Mixing polyamide PA6, aluminum dibutyl phosphinate prepared in comparative example 1 and a compound antioxidant according to the weight ratio of 79.6:20:0.4 in an internal mixer with the rotating speed of 50 revolutions per minute, setting the temperature to 260 ℃, taking out after 5 minutes, cooling and drying. Then filling the mixture into a mould, preheating the mixture for 10 minutes at 260 ℃ by a flat vulcanizing machine, maintaining the pressure for 5 minutes at 10MPa, and then cold pressing the mixture. And cutting the sample after the sample is cooled, and testing. The flame retardant rating of the 1.6mm sample was UL-94V-1.

Comparative example 4

Mixing polyamide PA66, diethyl aluminum phosphinate and compound antioxidant according to the weight ratio of 79.6:20:0.4 in an internal mixer with the rotating speed of 50 revolutions per minute, setting the temperature to 280 ℃, taking out after 5 minutes, cooling and drying. Then filling the mixture into a mould, preheating the mixture for 10 minutes in a flat vulcanizing machine at 280 ℃, maintaining the pressure for 5 minutes under 10MPa, and then cold pressing the mixture. And cutting the sample after the sample is cooled, and testing. The flame retardant rating for the 1.6mm sample was UL94 no rating.

Comparative example 5

Mixing polyamide PA6, diethyl aluminum phosphinate and compound antioxidant in the weight ratio of 79.6:20:0.4 in an internal mixer with the rotating speed of 50 revolutions per minute, setting the temperature to 260 ℃, taking out after 5 minutes, cooling and drying. Then filling the mixture into a mould, preheating the mixture for 10 minutes at 260 ℃ by a flat vulcanizing machine, maintaining the pressure for 5 minutes at 10MPa, and then cold pressing the mixture. And cutting the sample after the sample is cooled, and testing. The flame retardant rating of the 1.6mm sample was UL-94 no rating.

Table 7 test results for examples 10-22

Examples 8-22 illustrate the outstanding flame retardant efficiency of polyamides with flame retardants containing the dialkylphosphinic acid hybrid salts of the present invention. The prepared flame-retardant PA66 spline has good toughness and no obvious degradation. And no obvious smoke exists in the flame-retardant polyamide combustion test. Comparative examples 2 to 3 show that dibutyl phosphinate has a lower flame retardant efficiency for polyamide than the hybrid salt having the structure of formula (I) according to the present invention, and that smoke is large when flame retardant polyamide burns, which is disadvantageous for escape. In addition, as can be seen from fig. 1, the thermal stability is too low, and the prepared flame-retardant PA66 has high brittleness, which indicates degradation. Comparative examples 4-5 demonstrate the low flame retardant efficiency of pure aluminum diethylphosphinate to polyamide.

The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (10)

1. A dialkylphosphinic acid hybrid salt, characterized in that the dialkylphosphinic acid hybrid salt is selected from at least one of the compounds having the chemical formula shown in formula (I);

wherein M is a central atom; r is R ₁ 、R ₂ Are each independently selected from C ₄ -C ₁₂ And R is an alkyl group of ₁ 、R ₂ At least one of which is not isobutyl;

diethyl phosphinate ion, ethyl R ₁ Radical phosphinate ion, R ₁ Radical R ₂ The phosphinate ions are ligands;

m is selected from metal elements; the metal element is at least one selected from group IIA, IIIA, IVA, VA metal element, transition metal element and lanthanide series metal element;

n is the valence state of the metal element M; n is selected from 2,3 or 4;

ethyl R ₁ Radical phosphinate ion, diethyl phosphinate ion, R ₁ Radical R ₂ At least two acid radical ions in the phosphinate radical ions are paired with the same central atom M; and wherein one of the ligands paired with the central atom M is ethyl R ₁ A phosphinate ion;

x is more than or equal to 0 and less than or equal to 0.76; y is more than or equal to 0.05 and less than or equal to 0.76; 0.ltoreq.z.ltoreq.0.76, and x+y+z=1.

2. The dialkylphosphinic acid hybridization salt according to claim 1, wherein the group IIA metal element is selected from at least one of Be, mg, ca, sr, ba;

the III A metal element is Al;

The group IVA metal element is Sn;

the group VA metal element is Sb;

the transition metal element is selected from at least one of Fe, zn, cu, ti, zr, mn;

the lanthanide metal element is Ce;

preferably, 0.ltoreq.x.ltoreq.0.76; y is more than or equal to 0.05 and less than or equal to 0.67; z is more than or equal to 0.005 and less than or equal to 0.76;

preferably, 0.ltoreq.x.ltoreq.0.70; y is more than or equal to 0.05 and less than or equal to 0.67; z is more than or equal to 0.005 and less than or equal to 0.70;

preferably, 0.1.ltoreq.x.ltoreq.0.65; y is more than or equal to 0.30 and less than or equal to 0.67; z is more than or equal to 0.01 and less than or equal to 0.50;

preferably, 0.30.ltoreq.x.ltoreq.0.65; y is more than or equal to 0.30 and less than or equal to 0.65; z is more than or equal to 0.02 and less than or equal to 0.40;

preferably, m=al, n=3.

3. A process for the preparation of a dialkylphosphinic acid hybrid salt according to claim 1 or 2, characterized in that said process comprises:

carrying out reaction I on a material containing the mixture A and a metal element M source in a water phase to obtain the dialkylphosphinic acid hybrid salt;

the mixture A contains diethyl phosphinic acid and/or alkali metal thereofSalts, ethyl R ₁ The phosphinic acid and/or alkali metal salt thereof and R ₁ Radical R ₂ The phosphinic acid and/or alkali metal salts thereof.

4. A process according to claim 3, wherein the conditions of reaction I are: the temperature is 0-250 ℃; the pressure is 0.1MPa-10MPa; the time is 0.01-20h;

Preferably, the reaction I is carried out at a pH of 0 to 4;

preferably, the obtaining of the mixture a comprises the following steps:

introducing ethylene and C into an aqueous solution containing phosphinic acid and/or alkali metal salt thereof and a free radical initiator ₄ -C ₁₂ Reaction II to obtain said mixture a;

preferably, the phosphinic acid and/or alkali metal salt thereof, ethylene, C ₄ -C ₁₂ The molar ratio of olefins is 1:0.24-1.76:1.76-0.24;

preferably, in the aqueous solution, the mass of the water is 10-99% of the total mass of the aqueous solution;

preferably, the conditions of reaction II are: the temperature is 0-250 ℃; the time is 0.01-50h; the pressure is 0-3MPa;

preferably, the molar ratio of the free radical initiator to the hypophosphorous acid and/or its alkali metal salt is from 0.001 to 0.1:1;

preferably, the molar ratio of the free radical initiator to the hypophosphorous acid and/or its alkali metal salt is 0.003-0.05:1;

preferably, the obtaining of the mixture a comprises the following steps:

introducing C into an aqueous solution containing hypophosphorous acid and/or alkali metal salt and free radical initiator ₄ -C ₁₂ To be fed C ₄ -C ₁₂ After the ratio of the olefin to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I), the introduction of C is stopped ₄ -C ₁₂ Continuously introducing ethylene to react to obtain a mixture A;

preferably, the obtaining of the mixture a comprises the following steps:

introducing C into an aqueous solution containing hypophosphorous acid and/or alkali metal salt and free radical initiator ₄ -C ₁₂ Wherein the ratio of ethylene to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt is less than (2x+y)/1 in formula (I), C to be introduced ₄ -C ₁₂ After the ratio of the olefin to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I), the introduction of C is stopped ₄ -C ₁₂ Continuously introducing the rest part of ethylene to react to obtain a mixture A;

preferably, the obtaining of the mixture a comprises the following steps:

charging a portion of ethylene into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator, wherein the mole ratio of the portion of ethylene to the total phosphorus of the hypophosphorous acid and/or its alkali metal salt is (2x+y)/1 or less in formula (I), and continuing charging C after the portion of ethylene has reacted completely ₄ -C ₁₂ To be fed C ₄ -C ₁₂ After the ratio of the olefin to the total phosphorus mole of hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I), the introduction of C is stopped ₄ -C ₁₂ Continuously introducing the rest part of ethylene to react to obtain the mixture A;

preferably, the total amount of ethylene and the C ₄ -C ₁₂ The molar ratio of the total amount of olefins is 0.14-7.33:1;

preferably, the source of the metal element M is selected from at least one of metal element M salts;

preferably, the metal element M salt is selected from at least one of nitrate, sulfate, hydrochloride, acetate, and oxide of the metal element M.

5. A flame retardant selected from at least one of the dialkylphosphinic acid hybrid salts according to claim 1 or 2, and the dialkylphosphinic acid hybrid salts prepared according to the process of claim 3 or 4.

6. The flame retardant material is characterized by comprising a flame retardant P and a thermoplastic polymer material;

the flame retardant P is at least one selected from the flame retardants described in claim 5.

7. The flame retardant material according to claim 6, wherein the mass content of the flame retardant P in the flame retardant material is 1 to 35%.

8. The flame retardant material of claim 6, further comprising a functional additive in the flame retardant material;

The functional additive is at least one selected from reinforcing agents, anti-dripping agents, stabilizing agents, pigments, dyes, char-forming catalysts, dispersing agents, nucleating agents, inorganic fillers and antioxidants;

preferably, the functional additive is present in the flame retardant material in an amount of 5 to 40% by mass.

9. The flame retardant material of claim 8, further comprising a flame retardant Q in the flame retardant material;

the flame retardant Q is at least one selected from nitrogen flame retardants and boron flame retardants.

10. The flame retardant material according to claim 9, wherein the mass content of the flame retardant Q in the flame retardant material is 0.5 to 20%;

preferably, the thermoplastic polymer material is at least one selected from polyamide and polyester.