WO2024060020A1 - 二烷基次膦酸杂化盐及其制备方法、应用 - Google Patents

二烷基次膦酸杂化盐及其制备方法、应用 Download PDF

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WO2024060020A1
WO2024060020A1 PCT/CN2022/119947 CN2022119947W WO2024060020A1 WO 2024060020 A1 WO2024060020 A1 WO 2024060020A1 CN 2022119947 W CN2022119947 W CN 2022119947W WO 2024060020 A1 WO2024060020 A1 WO 2024060020A1
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flame retardant
salt
acid
preparation
ethylene
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PCT/CN2022/119947
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French (fr)
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姚强
赵月英
曹微虹
唐天波
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中国科学院宁波材料技术与工程研究所
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Priority to PCT/CN2022/119947 priority Critical patent/WO2024060020A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]

Definitions

  • the present application relates to a dialkylphosphinic acid hybrid salt and its preparation method and application, and belongs to the field of flame retardant polymer material preparation.
  • Dialkylphosphinates especially aluminum diethylphosphinate, have been widely used as halogen-free flame retardants for polymer materials.
  • the flame retardant efficiency of existing dialkyl phosphinates in glass fiber reinforced polymer materials is limited, and they often need to be used together with synergists.
  • US patents US6207736, US6255371, US6547992, etc. reported that diethyl phosphinate and ammonium polyphosphate, melamine polyphosphate, and/or inorganic compounds such as zinc stannate synergistically flame retardant glass fiber reinforced polyamide and polyester.
  • the amount of flame retardant is large, and the thermal stability of ammonium polyphosphate is not high, and melamine polyphosphate is easy to migrate.
  • hybrid salts composed of a relatively high content of long-chain dialkylphosphinate ions and diethylphosphinate ions have high thermal stability and very high flame retardant efficiency without the need for Synergists, when used alone, can achieve flame retardancy of polymer materials. At the same time, the flame-retardant materials have low smoke when burning.
  • the dialkylphosphinic acid hybrid salt is a dialkyl compound having formula (I).
  • Phosphinic acid hybrid salt has high thermal stability, low addition amount, high flame retardant efficiency for various polymer materials, low smoke, can meet the processing requirements of engineering plastics that require high temperatures, and is highly economical.
  • a dialkylphosphinic acid hybrid salt is provided, the dialkylphosphinic acid hybrid salt being selected from at least one compound having a chemical formula represented by formula (I) ;
  • M is the central atom
  • R 1 and R 2 are independently selected from C 4 -C 12 alkyl groups, and at least one of R 1 and R 2 is not isobutyl;
  • Diethylphosphinate ion, ethyl R 1- based phosphinate ion, and R 1- based R 2 -based phosphinate ion are all ligands;
  • M is selected from a metal element;
  • the metal element is selected from at least one of group IIA, IIIA, IVA, VA metal elements, transition metal elements, and lanthanide metal elements;
  • n is the valence state of the metal element M; n is selected from 2, 3 or 4;
  • At least two of the ethyl R 1 -based phosphinate ions, diethyl phosphinate ions, and R 1- based R 2 -based phosphinate ions are paired with the same central atom M; and one of them is paired with the central atom M
  • the ligand must be ethyl R 1 -yl phosphinate ion;
  • R 1 and R 2 are independently selected from C 4 -C 12 alkyl groups, which may be the same or different, and at least one of R 1 and R 2 is not isobutyl.
  • the C 4 -C 12 alkyl group can be a straight chain or branched chain 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 Base, n-nony
  • R 1 or R 2 when calculating the y value, substances that are isomers of each other are counted as one substance for calculation.
  • R 1 is butyl, which includes n-butyl, isobutyl, sec-butyl and tert-butyl.
  • y is the total number of moles of these four ethylbutylphosphinate ions and the total number of moles of all dialkylphosphinate ions (i.e., the number of moles of diethylphosphinate ions, the number of moles of ethylbutylphosphinate ions, and The ratio of the sum of the moles of R 1- based R 2- based phosphinate ions).
  • the lower bound of 0.40, 0.35 is 0.40, 0.35.
  • 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.
  • 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.
  • the Group IIA metal element is selected from at least one of Be, Mg, Ca, Sr, and Ba;
  • the Group IIIA 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, and Mn;
  • the lanthanide metal element is Ce.
  • the metal element is selected from at least one of Al, Zn, Ca, and Fe.
  • the dialkylphosphinic acid hybrid salt in this application is not a simple physical mixture of different dialkylphosphinic acid salts.
  • R 1 and R 2 are butyl
  • it is not a simple mixture of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, and aluminum dibutylphosphinate, but contains A hybrid salt composed of at least two acid ions among diethylphosphinate ion, ethylbutylphosphinate ion and dibutylphosphinate ion coordinated with the same aluminum atom, and the hybridization
  • One ligand in the salt is the ethylbutylphosphinate ion.
  • the X-ray diffraction patterns (XRD) of these hybrid salts are very different from those of simple physical mixed salts of dialkylphosphinates.
  • the dialkylphosphinic acid hybrid salt having formula (I) exhibits a single peak in the strongest absorption peak region in the XRD spectrum.
  • the physical mixed salt obtained by simply mixing aluminum diethylphosphinate and aluminum dibutylphosphinate shows two completely independent peaks in the XRD pattern, and their d values are close to diethylphosphinate respectively.
  • the respective d values of aluminum phosphate and aluminum dibutylphosphinate are very different from those of simple physical mixed salts of dialkylphosphinates.
  • dialkylphosphinic acid hybrid salt having the formula (I) obtained in the present invention is not simply aluminum diethylphosphinate, ethylR 1yl aluminum phosphinate, R 1yl R A mixture of 2 -based aluminum phosphinate, but contains at least two acid ions of diethyl phosphinate ion, ethyl R 1 -based phosphinate ion, R 1- based R 2 -based phosphinate ion and the same one A structure in which aluminum atoms are paired, and one of the ligands is an ethyl R 1 -yl phosphinate ion.
  • the thermal stability of pure long-chain aluminum dialkylphosphinate (R 1 , R 2 is C 4 -C 12 alkyl) is low, and it is difficult to meet the needs of high-temperature processing. Molecular material requirements.
  • the flame retardant efficiency is not high, and in practical applications, it has been found that long-chain dialkyl aluminum phosphinate flame retardant polymers produce more smoke when burned than diethyl aluminum diethyl phosphinate flame retardant systems.
  • the flame retardant efficiency of pure aluminum diethylphosphinate is not high when used alone, and it is difficult to achieve good flame retardant effects on polymer materials when used alone.
  • dialkylphosphinic acid hybrid salt with the formula (I) has higher thermal stability and longer chain aluminum dialkylphosphinate, has less smoke, and has a flame retardant effect better than pure diethylphosphine.
  • Aluminum phosphate is better than pure long-chain aluminum dialkylphosphinate, which is very unexpected.
  • a method for preparing the above-mentioned dialkylphosphinic acid hybrid salt includes:
  • the material containing the mixture A and the source of the metal element M is reacted I in the aqueous phase to obtain the dialkylphosphinic acid hybrid salt;
  • the mixture A contains diethyl phosphinic acid and/or its alkali metal salt, ethyl R 1 phosphinic acid and/or its alkali metal salt and R 1 yl R 2 phosphinic acid and/or its base. Metal salts.
  • the conditions of the reaction I are: temperature is 0-250°C; pressure is 0.1MPa-10MPa; time is 0.01-20h.
  • reaction I is carried out at a pH of 0 to 4.
  • the metal element is Al
  • the pH of reaction I is 0 to 4; preferably 1 to 3.5; more preferably 2.3 to 3.3.
  • the solubility of hybrid salts in water is different.
  • diethylphosphinic acid and/or its alkali metal salts, ethyl R 1 -yl phosphinic acid and/or its alkali metal salts, R 1- yl R 2- yl phosphinic acid and The calculated mole number of phosphonic acid and/or its alkali metal salt is different from the x, y, z values in the hybrid salt, so the molar ratio to the M source will also change.
  • the molar ratios of x, y, z and M corresponding to the reactants during feeding can also exceed the theoretically calculated values.
  • the actual values of x, y, z and q can be determined by phosphorus NMR.
  • obtaining the mixture A includes the following steps:
  • Ethylene and C 4 -C 12 olefins are passed into an aqueous solution containing phosphinic acid and/or its alkali metal salt and a free radical initiator to react II to obtain the mixture A.
  • the molar ratio of the phosphinic acid and/or its alkali metal salt, ethylene, and C 4 -C 12 olefins is 1:0.24-1.76:1.76-0.24.
  • the molar ratio of the phosphinic acid and/or its alkali metal salt, ethylene, and C4 - C12 olefin is the same as or close to the theoretical value calculated according to the x, y, and z values in formula (I).
  • the y value has a maximum value less than 1. Depending on the type of olefin, this maximum value is 0.76 or less, and is generally around 0.66. After reaching this maximum value, x or z increases, so y cannot reach 1.
  • reaction intermediate product needs to be separated and purified to remove diethylphosphinic acid and/or its alkali metal salt and R1 - based R2 -based phosphinic acid and/or its alkali metal salt, which is not economically favorable.
  • reaction II the order of addition of ethylene and C 4 -C 12 olefins can be interchanged, they can also be added at the same time, or some of them can be added first.
  • hypophosphorous acid and/or its alkali metal salt reacts with C 4 -C 12 olefins first, and then reacts with ethylene substantially completely or completely after obtaining the corresponding y and z values.
  • Roughly complete means that in the reaction mixture, the sum of the phosphorus contained in ethyl phosphinate, R 1 -based phosphinate, R 2 -based phosphinate, and phosphinate is less than 5 mol% of the total phosphorus in the reaction solution. .
  • the mass of the water is 10-99% of the total mass of the aqueous solution.
  • the salting out effect will cause the solubility of olefins in water to be low and the reaction speed will slow down; if there is too much water, the utilization rate of the reactor will decrease.
  • the mass of the water is 20-95% of the total mass of the aqueous solution.
  • the mass of the water is 45-92% of the total mass of the aqueous solution.
  • the mass of the water is 50-90% of the total mass of the aqueous solution.
  • the mass of the water is 55-90% of the total mass of the aqueous solution.
  • the conditions of the reaction II are: temperature is 0-250°C; time is 0.01-50h; pressure is 0-3MPa.
  • the reaction speed is slow, and if the temperature is too high, the hypophosphite is easily decomposed.
  • the temperature of reaction II is 10-200°C.
  • the pressure of reaction II is higher than 3MPa, which places higher requirements on reaction equipment and makes operation difficult.
  • the pressure of reaction II is 0.2-1.5MPa.
  • the molar ratio of the free radical initiator to the hypophosphorous acid and/or its alkali metal salt is 0.001-0.1:1.
  • the molar ratio of the free radical initiator to the phosphinic acid and/or alkali metal salt thereof is 0.003-0.05:1.
  • 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.
  • the azo initiator is selected from cationic and/or non-cationic azo initiators, including azobisisobutyronitrile, 4,4'azobis(4-cyanovaleric acid) , 2,2'-Azobis(2-methylbutyronitrile), 2,2'-Azobis(2-amidinopropane)dihydrochloride, 2,2'-Azobis(2-amidinopropane)dihydrochloride, One or more hydrochlorides.
  • the peroxide initiator is preferably an inorganic peroxide or an organic peroxide, and is particularly preferably hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, sodium percarbonate, or benzene peroxide.
  • hydrogen peroxide ammonium persulfate, potassium persulfate, sodium persulfate, sodium percarbonate, or benzene peroxide.
  • Formyl, di-tert-butyl peroxide, tert-butyl perbenzoate, and peracetic acid are examples of peracetic acid.
  • the free radical initiator is a peroxide initiator.
  • the free radical initiator is selected from one of ammonium persulfate, potassium persulfate, and sodium persulfate.
  • obtaining the mixture A includes the following steps:
  • a C 4 -C 12 olefin is passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator to react, and the C 4 -C 12 olefin to be passed in reacts with hypophosphorous acid and/or its base .
  • the flow of C 4 -C 12 olefins is stopped, and then the flow of ethylene is continued to react to obtain the mixture A.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • obtaining the mixture A comprises the following steps:
  • C 4 -C 12 olefins into an aqueous solution containing hypophosphorous acid and/or its alkali metal salts and free radical initiators. After the reaction of the C 4 -C 12 olefins is complete or nearly complete, continue to pass Ethylene reacts to obtain the mixture A.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • hypophosphorous acid and/or its alkali metal salts and C 4 -C 12 alkenes are first reacted to obtain mono-R 1 -based phosphinic acid or its alkali metal salts with a y value or substantially close to it, and control z is less than Equal to 0.76, then stop adding C 4 -C 12 olefins, add ethylene instead, continue the reaction in the presence of the initiator, and then react with the required metal salt to obtain a flame retardant with formula (I).
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • obtaining the mixture A comprises the following steps:
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • obtaining the mixture A includes the following steps:
  • C 4 -C 12 olefins and part of ethylene are passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salts and a free radical initiator to react.
  • the total phosphorus moles of ethylene and hypophosphorous acid and/or its alkali metal salts are The ratio is less than (2x+y)/1 in formula (I), and the total phosphorus molar ratio of the C 4 -C 12 olefin to be introduced to hypophosphorous acid and/or its alkali metal salt reaches the ratio in formula (I)
  • the flow of C 4 -C 12 olefins is stopped, and then the remaining part of ethylene is continued to be flown for reaction to obtain the mixture A.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • obtaining the mixture A includes the following steps:
  • Part of the ethylene is passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator, and the molar ratio of the partial ethylene to the total phosphorus of hypophosphorous acid and/or its alkali metal salt is less than or equal to formula (I) (2x+y)/1 in, after the partial ethylene reaction is complete, continue to pass in the C 4 -C 12 olefins to react, the C 4 -C 12 olefins to be passed in are reacted with hypophosphorous acid and/or After the total phosphorus molar ratio of the alkali metal salt reaches (y+2z)/1 in formula (I), the flow of C 4 -C 12 olefins is stopped, and the remaining part of ethylene is continued to be fed for reaction to obtain the mixture A.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed
  • obtaining the mixture A includes the following steps:
  • Part of the ethylene is passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator.
  • C 4 -C 12 olefins are continued to be introduced for reaction.
  • the remaining part of ethylene is introduced for reaction to obtain the mixture A.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • the molar ratio of the total amount of ethylene to the C 4 -C 12 olefin is 0.14-7.33:1.
  • the source of metal element M is selected from at least one metal element M salt.
  • the metal element M salt is selected from at least one of nitrates, sulfates, hydrochlorides, acetates, and oxides of the metal element M.
  • hypophosphorous acid and/or its alkali metal salts are simultaneously reacted with C 4 -C 12 olefins and part of ethylene in the presence of a free radical initiator, controlling the amounts of C 4 -C 12 olefins and ethylene to be reacted
  • the molar percentage of the sum of ethyl R 1 -based phosphinic acid or its alkali metal salt and R 1 -based phosphinic acid or its alkali metal salt in the system is close to the y value, and R 1- based R 2 -based phosphinic acid or its alkali metal salt The molar percentage is close to the z value, and z is less than or equal to 0.76.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • obtaining the mixture A includes the following steps:
  • Ethylene is passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator, and the amount of ethylene is controlled until the molar ratio of ethylene to the total phosphorus of hypophosphorous acid and/or its alkali metal salt reaches After (y+2x)/1 in formula (I), stop feeding ethylene, continue to add C 4 -C 12 olefins, and continue the reaction to completion in the presence of the initiator to obtain the mixture A.
  • the C 4 -C 12 olefin may be a pure C 4 -C 12 olefin or a C 4 -C 12 mixed olefin.
  • reaction II there is no need to separate diethyl phosphinic acid, ethyl R 1 -based phosphinic acid, R 1- based R 2 -based phosphinic acid and/or their alkali metal salts, and directly proceed to the next step of the reaction That’s it.
  • a flame retardant is provided, the flame retardant being selected from the above-mentioned dialkylphosphinic acid hybrid salt and the dialkylphosphinic acid hybrid salt prepared according to the above method. of at least one.
  • the flame retardant also contains at least one selected from the group consisting of phosphates, phosphites, alkyl phosphonates, and alkyl phosphinates. These phosphorus-containing impurities are present in the flame retardant.
  • the molar content of the flame retardant is less than or equal to 10%, and the mole number of the flame retardant is calculated by the mole number of phosphorus element contained therein.
  • a flame retardant material which includes a flame retardant P and a thermoplastic polymer material;
  • the flame retardant P is selected from at least one of the above flame retardants.
  • the mass content of the flame retardant P in the flame retardant material is 1-35%.
  • the flame retardant material includes 1-35wt% flame retardant P and 65-99wt% thermoplastic polymer material.
  • thermoplastic polymer material refers to plastic that has the characteristics of softening when heated and hardening when cooled.
  • the amount of the flame retardant P depends on the thermoplastic polymer material.
  • the mass content of the flame retardant P in the flame retardant material is 3-20%.
  • the flame retardant material also includes functional additives
  • the functional additive is selected from at least one of a reinforcing agent, an anti-dripping agent, a stabilizer, a pigment, a dye, a carbon-forming catalyst, a dispersant, a nucleating agent, an inorganic filler, and an antioxidant;
  • the mass content of the functional additive in the flame retardant material is 5-40%.
  • the reinforcing agent is selected from glass fibers.
  • the anti-drip agent is selected from Teflon.
  • the inorganic filler is selected from at least one of mica, calcium carbonate, calcium oxide, and silica.
  • the flame retardant material further includes a flame retardant Q;
  • the flame retardant Q is selected from at least one of nitrogen-based flame retardants and boron-based flame retardants.
  • the nitrogen-based flame retardant is selected from at least one of melamine cyanurate, melamine polyphosphate, and ammonium polyphosphate;
  • the boron-based flame retardant is selected from zinc borate.
  • the mass content of the flame retardant Q in the flame retardant material is 0.5-20%.
  • thermoplastic polymer material is selected from at least one of polyamide and polyester.
  • the polyamide is selected from at least one selected from the group consisting of aliphatic polyamide, aromatic polyamide, semi-aromatic polyamide, and copolymers of semi-aromatic polyamide and aliphatic polyamide.
  • polyamide also known as nylon or nylon
  • nylon is a general name for polymers containing -NH-C(O)-amide groups in its structural units, through one or more dicarboxylic acids and a Or multiple diamines, and/or one or more amino acids, and/or one or more lactams, synthesized by condensation or ring-opening reaction.
  • polyamide is generally divided into aliphatic polyamide, aromatic polyamide and semi-aromatic polyamide.
  • Semi-aromatic polyamide means that at least one of its synthetic monomers contains an aromatic group in its monomer structure.
  • the aliphatic polyamide may be selected from one or a mixture of a copolymer of polyamide 6 and polyamide 66, polyamide 6, polyamide 66.
  • the semi-aromatic polyamide can be made from any one or several aromatic dicarboxylic acids and any one or several aliphatic diamines, or can also be made from any one or several aromatic diamines. It is prepared from amines and any one or several aliphatic dicarboxylic acids.
  • One or any several selected from 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 aromatic dicarboxylic acid and/or aliphatic dicarboxylic acid;
  • the added diamine is aromatic diamine and/or aliphatic diamine;
  • the added lactam can be aliphatic family or aromatic lactams.
  • the added amino acids can be aromatic or aliphatic amino acids.
  • the semi-aromatic polyamide is composed of one or more aromatic dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, and optionally composed of butanediamine, It is prepared from one or more aliphatic diamines among hexamethylenediamine, octanediamine, decanediamine and 2-methylpentanediamine.
  • the semi-aromatic polyamide is made from aliphatic diamine, aromatic dicarboxylic acid and aliphatic dicarboxylic acid.
  • the aromatic dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid;
  • the aliphatic diamine is selected from butanediamine, One or more of hexamethylenediamine, octanediamine, decanediamine and 2-methylpentanediamine;
  • the aliphatic dicarboxylic acid is optionally adipic acid, succinic acid, sebacic acid, octanoic acid One or more diacids.
  • the polyamide is selected from polyhexamethylene terephthalamide (abbreviated as PA6T), polyhexamethylene 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), polynonamethylene terephthalamide (abbreviated as PA9T), poly One or more of decanediamine terephthalamide (abbreviated as PA10T), polydodecanediamine terephthalamide (abbreviated as PA12T), terephthalic acid/hexamethylenediamine/laurolactam copolymer (abbreviated as PA
  • the aliphatic polyamide is selected from at least one of polyamide 6, polyamide 66, and copolymers of polyamide 6 and polyamide 66.
  • the semi-aromatic polyamide is selected from polyphthalamide (PPA).
  • the polyester is selected from polybutylene terephthalate (PBT).
  • PBT polybutylene terephthalate
  • Flame retardants having the composition of formula (I) may contain trace amounts of other phosphorus-containing impurities. Due to impurities contained in raw materials or impurities generated by the synthesis process, some trace amounts of phosphates, phosphites, alkylphosphonates, and alkylphosphinates may be present in flame retardants.
  • telomer products derived from the polymerization or copolymerization of ethylene and/or C 4 -C 12 olefins such as ethyl n-tetradecyl phosphinate and ethyl hexadecyl phosphinate may also It exists as an impurity in the flame retardant having the composition of formula (I). However, as long as the total molar amount of these other phosphorus-containing acid ions does not exceed 5% of the total phosphorus molar amount, it will not affect the normal operation of the flame retardant composed of formula (I).
  • the ratio of x, y, and z in formula (I) can be determined by 31 P-NMR (nuclear magnetic resonance) after alkali or acid hydrolysis of the flame retardant.
  • Diethyl phosphinate, ethyl R 1 -based phosphinate, and R 1- based R 2 -based phosphinate ions have different 31 P chemical shifts, and in most cases present independent peaks in the 31 P-NMR spectrum.
  • the peak areas of these peaks respectively correspond to the molar concentrations of the respective dialkylphosphinate ions.
  • Some of the dialkylphosphinate ions with the same chemical formula will have isomers, and thus can show different patterns in the NMR phosphorus spectrum. Peaks, these isomers are grouped together when calculating x, y, z values. For example, when R 1 and R 2 are butyl groups, five groups of peaks will appear in the 31 P-NMR spectrum of the resulting dialkylphosphinic acid hybrid salt, and these five groups of peaks respectively correspond to ethyl sec-butylphosphinate radicals.
  • the molar concentration of diethylphosphinate ions corresponds to ) corresponds to y
  • the sum of the molar concentrations of di-n-butylphosphinate ions and n-butyl-sec-butylphosphinate ions (collectively referred to as the molar concentration of dibutylphosphinate ions) corresponds to z
  • the ratio of the three is x, y and value of z.
  • telomer dialkylphosphinate ions are present in small amounts and with chemical shifts close to the corresponding dialkylphosphinate ions, and therefore are incorporated into the corresponding dialkyl ions during integration.
  • base phosphinate ion is present in small amounts and with chemical shifts close to the corresponding dialkylphosphinate ions, and therefore are incorporated into the corresponding dialkyl ions during integration.
  • the dialkylphosphinic acid hybrid salt having formula (I) provided by the present invention has a small addition amount, high thermal stability, high flame retardant efficiency for polymer materials, and good economy. It not only overcomes the shortcomings of low flame retardant efficiency for polymer materials when diethylphosphinate and long-chain dialkylphosphinate are used alone, but also overcomes the thermal stability of long-chain dialkylphosphinate. It has the disadvantage of low flame retardant smoke and large flame retardant smoke. It can be widely used for flame retardant of polymer materials that require high temperature processing;
  • the present application provides a method for preparing a hybrid salt of a dialkylphosphinic acid, which avoids the disadvantage of having to prepare different dialkylphosphinic acids separately and independently, uses water as a reaction solvent, and is environmentally friendly.
  • the raw materials are easily available and economical.
  • Figure 1 shows dialkylphosphinic acid hybrid aluminum salts with different x, y, z values (corresponding to formula (I) in which R 1 and R 2 are butyl groups, and in the reaction II, C 4 - is used The C 12 olefin is butene) and the thermal weight loss curves of aluminum diethylphosphinate and aluminum dibutylphosphinate;
  • Figures 2a and 2b show dialkylphosphinic acid hybrid aluminum salts with different x, y, and z values (corresponding to formula (I) in which R 1 and R 2 are butyl groups, and in the reaction II, C used 4 - XRD curves of C 12 olefins (butene), aluminum diethylphosphinate, aluminum dibutylphosphinate, and physical mixed salts of aluminum dibutylphosphinate and aluminum diethylphosphinate, where Figure 2b is a partial enlargement of the strongest absorption peak in Figure 2a;
  • Figure 3 and Figure 4 respectively show the dialkylphosphinic acid hybrid salt prepared in Example 3 and Example 4 (corresponding to formula (I) in which R 1 and R 2 are butyl groups, and in the reaction II, the 31 P-NMR spectrum after alkaline hydrolysis (C 4 -C 12 olefin is butene).
  • PA66 also known as polyamide 66 or nylon 66
  • PA6 also known as polyamide 6 or nylon 6: American DuPont Zytel 73G30L NC010, glass fiber content is 30% by weight;
  • ADP aluminum diethylphosphinate, Exolit OP1230 from Clariant, Germany;
  • MPP melamine polyphosphate, Suzhou Kaima Chemical Technology Co., Ltd.;
  • Zinc borate Sinopharm Chemical Reagent Co., Ltd.
  • Antioxidant 1010 pentaerythritol tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Shanghai MacLean Biochemical Technology Co., Ltd.;
  • Antioxidant 168 Tris[2,4-di-tert-butylphenyl]phosphite, Strem Company of the United States;
  • antioxidant 1010 tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenylpropionate]pentaerythritol ester
  • antioxidant 168 tris[2,4-di-tert-butylphenyl]phosphite
  • Combustion test standard GB/T 2408-2008 standard
  • Nuclear magnetic resonance (NMR) test The instrument models used are AVANCE III 600MHz and AVANCE III 400MHz, Bruker Company of Germany;
  • ethyl butyl phosphinate ion includes ethyl sec-butyl phosphinate ion and ethyl n-butyl phosphinate ion; dibutyl phosphinate ion includes n-butyl sec-butyl phosphinate ion.
  • R 1 ⁇ R 2 n-butyl and sec-butyl respectively
  • other double addition products including di-sec-butylphosphine Acid ions and telomer dialkylphosphinate ions obtained by polymerizing ethylene and or butene.
  • Butylphosphinate ion is the sum of sec-butylphosphinate ion and n-butylphosphinate ion
  • butylphosphonate ion is the sum of sec-butylphosphinate ion and n-butylphosphinate ion, the same below.
  • the molar content of diethylphosphinate ions is 40.23% and the molar content of ethyl-n-butylphosphinate ions is 51.98%.
  • the molar content of ethyl sec-butylphosphinate ions is 4.10%, and the molar content of di-n-butylphosphinate ions is 3.69%.
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • the molar content of ethyl sec-butylphosphinate ions is 2.42%, and the molar content of ethyl n-butylphosphinate ions is 2.42%.
  • the molar content of n-butyl sec-butylphosphinate ion is 7.25%
  • the molar content of di-n-butylphosphinate ion is 68.63%
  • the molar content of other phosphorus-containing impurities such as butylphosphinate ion and butylphosphinate ion
  • the total is 0.57%.
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • the molar content of diethylphosphinate ions is 1.99%
  • the molar content of ethyl sec-butylphosphinate ions is 4.30%
  • the molar content of ethyl n-butylphosphinate ions is 58.22%.
  • the molar content of n-butyl sec-butylphosphinate ion is 3.44%
  • the molar content of di-n-butylphosphinate ion is 30.67%
  • other phosphorus-containing impurities such as ethylphosphinate ion, butylphosphinate ion, ethyl
  • the total molar content of phosphonate ions and butylphosphonate ions is 1.38%.
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • the molar content of diethylphosphinate ions is 21.32% and the molar content of ethyl sec-butylphosphinate ions is 4.52%.
  • the molar content of ethyl n-butylphosphinate ions is 62.02%
  • the molar content of n-butyl sec-butylphosphinate ions is 1.11%
  • the molar content of di-n-butylphosphinate ions is 9.66%
  • other phosphorus-containing impurities such as ethanol
  • the total molar content of ethylphosphinate ions, butylphosphinate ions, ethylphosphonate ions, butylphosphonate ions, and phosphite ions is 1.37%.
  • the molar content of diethylphosphinate ions is 57.54%
  • the molar content of ethylhexylphosphinate ions is 38.19%
  • the molar content of diethylphosphinate ions is 38.19%.
  • the molar content of hexylphosphinate ion is 2.21%
  • the total molar content of other phosphorus-containing impurities such as ethylphosphinate ion, hexylphosphinate ion, ethylphosphonate ion, hexylphosphonate ion, and phosphite ion is 2.06%.
  • x 0.59
  • y 0.39
  • z 0.02.
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • the sample was dissolved in an aqueous solution of sodium hydroxide and subjected to phosphorus nuclear magnetic resonance. From the 31 P-NMR spectrum, it was known that the molar content of diethyl phosphinate ion was 0.80%, the molar content of ethyl sec-butyl phosphinate ion was 2.76%, the molar content of ethyl n-butyl phosphinate ion was 49.60%, the molar content of n-butyl sec-butyl phosphinate ion was 4.48%, and the molar content of di-n-butyl phosphinate ion was 42.36%.
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • Figure 1 is a graph of hybrid salts with different x, y, z values (Example 1, Example 4, Example 5) as well as aluminum diethylphosphinate and aluminum dibutylphosphinate (Comparative Example 1) Thermogravimetric graph (TGA). It can be seen from the figure that the larger the z value, the lower the thermal stability of the hybrid salt, and the larger the x value, the higher the thermal stability.
  • Figure 2a shows hybrid salts with different x, y, z values (Examples 1-5), aluminum dibutylphosphinate (Comparative Example 1), aluminum diethylphosphinate (ADP) and dibutyl XRD pattern of physical mixed salts of aluminum phosphinate and diethyl aluminum phosphinate.
  • Figure 2b is a partial enlargement of the strongest absorption peak in Figure 2a. It can be seen from Figure 2b that a simple physical mixed salt has two independent peaks in the XRD spectrum in the strongest absorption peak area, and their The d value is close to the d value of diethyl aluminum phosphinate and dibutyl aluminum phosphinate respectively.
  • the hybrid salt composed of formula (I) has only one peak or overlapping peaks, and the d value is basically between diethyl aluminum phosphinate and diethyl aluminum phosphinate. Between the d values of aluminum phosphonate and aluminum dibutylphosphinate.
  • the dialkylphosphinic acid hybrid salt having formula (I) according to the present invention is not simply aluminum diethylphosphinate, aluminum ethylbutylphosphinate, or aluminum dibutylphosphinate.
  • the mixture is a hybrid salt containing a structure in which at least two acid ions of diethylphosphinate, ethylbutylphosphinate, and dibutylphosphinate are paired with the same aluminum atom.
  • Polyamide PA6, the hybrid salt prepared in Example 1 and the compound antioxidant were mixed according to the weight ratio of 79.6:20:0.4 in an internal mixer with a rotation speed of 50 rpm, and the set temperature was 260°C. After 5 minutes, take it out to cool and dry. Then fill it into the mold, preheat it in a flat vulcanizer at 260°C for 10 minutes, maintain the pressure at 10MPa for 5 minutes, and then cold press. After cooling, cut the sample and test it.
  • the flame retardant level of the 1.6mm sample is UL94V-0.
  • the reaction solution was sampled for nuclear magnetic resonance.
  • the 31 P-NMR results showed that the molar content of n-butyl sec-butylphosphinic acid was 10.56%, the molar content of di-n-butylphosphinic acid was 84.92%, and the molar content of dibutylphosphinic acid telomer was 3.52%. , the remaining 1.00% is by-products such as butylphosphinic acid, butylphosphonic acid and phosphorous acid.
  • the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
  • Polyamide PA66, aluminum dibutylphosphinate prepared in Comparative Example 1, and compound antioxidant were mixed according to the weight ratio of 79.6:20:0.4 in an internal mixer with a rotation speed of 50 rpm, and the set temperature was 280°C, take out after 5 minutes, cool and dry. Then fill it into the mold, preheat it in a flat vulcanizer at 280°C for 10 minutes, maintain the pressure at 10MPa for 5 minutes, and then cold press. After cooling, cut the sample and test it. The flame retardant level of the 1.6mm sample is UL94 unrated.
  • Polyamide PA6, the aluminum dibutylphosphinate prepared in Comparative Example 1, and the compound antioxidant were mixed according to the weight ratio of 79.6:20:0.4 in an internal mixer with a rotation speed of 50 rpm, and the set temperature was 260°C, take out after 5 minutes, cool and dry. Then fill it into the mold, preheat it in a flat vulcanizer at 260°C for 10 minutes, maintain the pressure at 10MPa for 5 minutes, and then cold press. After cooling, cut the sample and test it.
  • the flame retardant level of the 1.6mm sample is UL-94V-1.
  • Polyamide PA6, aluminum diethylphosphinate, and compound antioxidant were mixed in a mixer at a speed of 50 rpm in a weight ratio of 79.6:20:0.4, and the temperature was set to 260°C. After 5 minutes, the mixture was taken out for cooling and drying. Then it was filled into the mold, preheated for 10 minutes in a flat vulcanizer at 260°C, and then cold pressed at 10MPa for 5 minutes. After cooling, the sample was cut and tested.
  • the flame retardant grade of the 1.6mm sample is UL-94 without grade.
  • Examples 8-22 illustrate that the flame retardant containing the dialkylphosphinic acid hybrid salt of the present invention has outstanding flame retardant efficiency for polyamide.
  • the prepared flame-retardant PA66 splines have good toughness and no obvious degradation. And during the flame-retardant polyamide burning test, there was no obvious smoke. Comparative Examples 2-3 show that the flame retardant efficiency of dibutyl phosphinate on polyamide is not as good as that of the hybrid salt with the structure of formula (I) described in the present invention, and when the flame retardant polyamide burns, the smoke is large, which is harmful to the polyamide. Unfavorable for escape.

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Abstract

本申请公开了一种二烷基次膦酸杂化盐及其制备方法、应用，所述二烷基次膦酸杂化盐选自具有式(Ⅰ)所示化学式的化合物中的至少一种。本申请提供的具有式(Ⅰ)组成的二烷基次膦酸杂化盐添加量少，对各类高分子材料阻燃效率高，热稳定性好，其不仅克服了二乙基次膦酸盐对高分子材料阻燃效率低的缺点，并且克服了长链二烷基次膦酸盐热稳定性低，燃烧时烟雾大的缺点，可以广泛应用于需要高温加工的高分子材料的阻燃。

Description

二烷基次膦酸杂化盐及其制备方法、应用 技术领域
本申请涉及一种二烷基次膦酸杂化盐及其制备方法、应用，属于阻燃高分子材料制备领域。
背景技术
二烷基次膦酸盐，特别是二乙基次膦酸铝，已经广泛作为高分子材料的无卤阻燃剂。但现有的二烷基次膦酸盐在玻纤增强高分子材料中的阻燃效率有限，常需要跟协同剂一起使用。美国专利US6207736，US6255371，US6547992等报道了二乙基次膦酸盐和聚磷酸铵，三聚氰胺聚磷酸盐，和/或无机化合物譬如锡酸锌协同阻燃玻纤增强聚酰胺和聚酯。但阻燃剂用量较大，且聚磷酸铵的热稳定性不高，三聚氰胺聚磷酸盐容易迁移。
美国专利US7420007报道了含有小于等于6％调聚次膦酸盐，即长链二烷基次膦酸盐的二乙基次膦酸铝。中国专利CN104072537B报道了在制备二乙基次膦酸盐过程中去除长链二烷基次膦酸盐的方法。这些专利都强调避免生成和使用含有较高含量的热稳定性低的长链二烷基次膦酸盐。实际应用中发现，长链二烷基次膦酸盐譬如二丁基次膦酸铝在阻燃玻纤增强聚酰胺时候，烟雾大，对安全逃生不利。具有高效阻燃并且燃烧时产生低烟雾的阻燃剂一直是业界追求的目标。
现在令人惊讶地发现，由较高含量的长链二烷基次膦酸根离子和二乙基次膦酸根离子共同组成的杂化盐具有高的热稳定性以及非常高的阻燃效率，无需协同剂，单独使用就能实现高分子材料的阻燃，同时由其阻燃的材料在燃烧时烟雾小。
发明内容
为解决上述技术问题，本申请提供了一种二烷基次膦酸杂化盐及其制备方法和应用，所述二烷基次膦酸杂化盐为具有式(Ⅰ)组成的二烷基次膦酸杂化盐，该杂化盐热稳定性高，添加量少，对各类高分子材料阻燃效率高，烟雾小，能满足需要高温的工程塑料的加工要求，经济性高。
根据本申请的第一方面，提供了一种二烷基次膦酸杂化盐，所述二烷基次膦酸杂化盐选自具有式(I)所示化学式的化合物中的至少一种；
Figure PCTCN2022119947-appb-000001
其中，M为中心原子；R 1、R 2均独立地选自C 4-C 12的烷基，且R 1、R 2中至少一个不为异丁基；
二乙基次膦酸根离子、乙基R 1基次膦酸根离子、R 1基R 2基次膦酸根离子均为配体；
M选自金属元素；所述金属元素选自第ⅡA、ⅢA、ⅣA、ⅤA族金属元素、过渡金属元素、镧系金属元素中的至少一种；
n为金属元素M的价态；n选自2，3或4；
乙基R 1基次膦酸根离子、二乙基次膦酸根离子、R 1基R 2基次膦酸根离子中至少两种酸根离子与同一个中心原子M配对；且其中一个与中心原子M配对的配体必须为乙基R 1基次膦酸根离子；
0≤x≤0.76；0.05≤y≤0.76；0≤z≤0.76,且x+y+z＝1。
本申请实施例中，R 1、R 2均独立地选自C 4-C 12的烷基，它们可以相同或不同，并且R 1、R 2至少一个不是异丁基。C 4-C 12烷基可以是直链或支链烷基，包括但不局限于正丁基，异丁基，仲丁基，叔丁基，正戊基，异戊基，新戊基，仲戊基，叔戊基，正己基，异己基，仲己基，叔己基，正庚基，异庚基，仲庚基，叔庚基，正辛基，异辛基，仲辛基，叔辛基，正壬基，仲壬基，叔壬基，正葵基，异葵基，仲葵基，叔葵基，正十一烷基，异十一烷基，仲十一烷基，叔十一烷基，正十二烷基，异十二烷基，仲十二烷基，叔十二烷基。
本申请中，当R 1或R 2中包括具有同分异构体的混合物时，在计算y值时，互为同分异构体的物质算作一种物质进行计算。譬如，R 1为丁基，它包含了正丁基，异丁基，仲丁基和叔丁基。在计算式(Ⅰ)中的y时，乙基丁基次膦酸根离子(式(1)中R 1＝丁基)包括了乙基正丁基次膦酸根离子，乙基异丁基次膦酸根离子，乙基仲丁基次膦酸根离子和乙基叔丁基次膦酸根离子。y是这四种乙基丁基次膦酸根离子的摩尔总数与所有二烷基次膦酸根离子摩尔总数(即二乙基次膦酸根离子摩尔数，乙基丁基次膦酸根离子摩尔数以及R 1基R 2基次膦酸根离子摩尔数之和)的比值。在计算式(Ⅰ)中的z时，R 1和R 2若都有同分异构体，则同样按照上述方法将互为同分异构体的物质算作一种物质进行计算。本申请实施例中，在式(Ⅰ)中，x若大于0.76，阻燃性能不佳。z若大于0.76，热稳定性下降，对阻燃高分子材料制备和物理性能不利。y大于0.76，制备成本高，经济性差。
可选地，x的下限独立地选自0、0.01、0.03、0.05、0.10、0.15、0.20、0.25、0.30；上限独立地选自0.76、0.70、0.67、0.65、0.60、0.55、0.50、0.45、0.40、0.35。
可选地，y的下限独立地选自0.05、0.10、0.15、0.20、0.25、0.30、0.35、0.40；上限独立地选自0.76、0.70、0.67、0.65、0.60、0.55、0.50、0.45。
可选地，z的下限独立地选自0、0.001、0.005、0.01、0.02、0.03、0.05、0.08；上限独立地选自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。
可选地，所述第ⅡA族金属元素选自Be、Mg、Ca、Sr、Ba中的至少一种；
所述第ⅢA族金属元素为Al；
所述第ⅣA族金属元素为Sn；
所述第ⅤA族金属元素为Sb；
所述过渡金属元素选自Fe、Zn、Cu、Ti、Zr、Mn中的至少一种；
所述镧系金属元素为Ce。
可选地，所述金属元素选自Al、Zn、Ca、Fe中的至少一种。
可选地，所述金属元素为Al，n＝3。
可选地，0≤x≤0.76；0.05≤y≤0.67；0.005≤z≤0.76。
可选地，0≤x≤0.70；0.05≤y≤0.67；0.005≤z≤0.70。
可选地，0.1≤x≤0.65；0.30≤y≤0.67；0.01≤z≤0.50。
可选地，0.30≤x≤0.65；0.30≤y≤0.65；0.02≤z≤0.40。
本申请实施例中，z值越大，二烷基次膦酸杂化盐的热失重越早。
本申请中的二烷基次膦酸杂化盐，并非是不同二烷基次膦酸盐的简单物理混合物。譬如，当R 1和R 2为丁基时，不是由二乙基次膦酸铝，乙基丁基次膦酸铝，和二丁基次膦酸铝简单混合而成的混合物，而是包含了跟同一个铝原子配位的二乙基次膦酸根离子、乙基丁基次膦酸根离子、二丁基次膦酸根离子中的至少两种酸根离子组成的杂化盐，并且该杂化盐中的一个配体是乙基丁基次膦酸根离子。这些杂化盐的X-射线衍射谱(XRD)跟简单的二烷基次膦酸盐的物理混合盐的XRD谱图非常不一样。具有式(Ⅰ)组成的二烷基次膦酸杂化盐在XRD谱图中，在最强的吸收峰区域，呈现单峰。但由二乙基次膦酸铝和二丁基次膦酸铝通过简单混合得到的物理混合盐在XRD图谱中则呈现2个完全独立的峰，且它们的d值分别接近二乙基次膦酸铝和二丁基次膦酸铝各自的d值。
本申请实施例中，将具有式(Ⅰ)组成的二烷基次膦酸杂化盐和二乙基次膦酸铝或者二丁基次膦酸铝通过简单的物理混合后，它们的XRD图谱中最强的吸收峰区域也出现两个独立的峰。这些结果强烈说明本发明所获得的具有式(Ⅰ)组成的二烷基次膦酸杂化盐不是简单的二乙基次膦酸铝、乙基R 1基次膦酸铝、R 1基R 2基次膦酸铝的混合物，而是包含了二乙基次膦酸根离子、乙基R 1基次膦酸根离子、R 1基R 2基次膦酸根离子中至少两种酸根离子跟同一个铝原子配对的结构，并且其中一个配体是乙基R 1基次膦酸根离子。
本申请实施例中，在相同的用量下，纯的长链二烷基次膦酸铝(R 1，R 2为C 4-C 12烷基)热稳定性低，难以满足需要高温加工的高分子材料的要求。阻燃效率不高，并且实际应用中发现，长链二烷基次膦酸铝阻燃的高分子燃烧时相比于二乙基次膦酸铝阻燃的体系烟雾大。但纯的二乙基次膦酸铝单独使用时阻燃效率也不高，单独使用时候难以促使高分子材料获得良好的阻燃效果。相比之下，具有式(Ⅰ)组成的二烷基次膦酸杂化盐热稳定性较长链二烷基次膦酸铝高，烟雾小，阻燃效果比纯的二乙基次膦酸铝和纯的长链二烷基次膦酸铝好，这是非常出乎预料的。
根据本申请的第二方面，提供了一种上述二烷基次膦酸杂化盐的制备方法，所述制备方法包括：
将含有混合物A和金属元素M源的物料在水相中进行反应I，得到所述二烷基次膦酸杂化盐；
所述混合物A中包含二乙基次膦酸和/或其碱金属盐、乙基R 1基次膦酸和/或其碱金属盐与R 1基R 2基次膦酸和/或其碱金属盐。
可选地，所述反应I的条件为：温度为0-250℃；压力为0.1MPa-10MPa；时间为0.01-20h。
可选地，所述反应I在pH为0～4下进行。
可选地，所述金属元素为Al，所述反应I的pH为0～4；优选1～3.5；更优选为2.3～3.3。
具体地，上述反应I pH太低，会不沉淀。pH太高，会生成金属离子的氢氧化物，引入杂质。
可选地，所述二乙基次膦酸和/或其碱金属盐、乙基R 1基次膦酸和/或其碱金属盐、R 1基R 2基次膦酸和/或其碱金属盐与金属元素M源的摩尔比为或接近为x:y:z:q，其中，q＝1/n。
可选地，所述混合物A中二乙基次膦酸和/或其碱金属盐、乙基R 1基次膦酸和/或其碱金属盐与R 1基R 2基次膦酸和/或其碱金属盐的摩尔比与式(Ⅰ)中的x,y,z比值相同或者大体相同。
由于M的不同，杂化盐在水里面的溶解度不尽相同。对于溶解度大的杂化盐，所述混合物A中二乙基次膦酸和/或其碱金属盐、乙基R 1基次膦酸和/或其碱金属盐、R 1基R 2基次膦酸和/或其碱金属盐的摩尔数计算所得值与杂化盐中的x,y,z的值有差别，因而跟M源的摩尔比也会变化。另外，为了获得更多的含M沉淀物，投料时反应物对应的x,y,z和M的摩尔比例也可以超过理论计算值。
实际操作过程中，可以通过磷核磁来判断x,y,z和q的实际值。
可选地，所述混合物A的获得包括以下步骤：
向含有次膦酸和/或其碱金属盐、自由基引发剂的水溶液中通入乙烯和C 4-C 12的烯烃，反应II，得到所述混合物A。
可选地，所述次膦酸和/或其碱金属盐、乙烯、C 4-C 12的烯烃的摩尔比为1：0.24-1.76：1.76-0.24。
实际反应中，由于一些副反应的存在，譬如乙烯和/或C 4-C 12烯烃聚合得到的更长链二烷基次膦酸盐，因此，乙烯和/或C 4-C 12烯烃的消耗量要高于理论值。
可选地，所述次膦酸和/或其碱金属盐、乙烯、C 4-C 12烯烃的摩尔比和按照式(Ⅰ)中x,y,z值计算出来的理论值相同或接近。在次磷酸或其碱金属盐跟乙烯或其它烯烃反应过程中，y值有一个小于1的最大值。决定于烯烃的种类，这个最大值在0.76及以下，常见的在0.66左右。达到这个最大值之后，x或者z增长，因此y无法达到1。如果需要制备y＝1,则需要对反应中间体产物进行分离提纯，去掉二乙基次膦酸和/或其碱金属盐以及R 1基R 2基次膦酸和/或其碱金属盐，对经济性不利。
具体地，在反应II中，乙烯和C 4-C 12烯烃的加入顺序可以互换，也可以同时加入，或者部分先加。
可选地，在反应II中，次磷酸和/或其碱金属盐先与C 4-C 12烯烃反应，获得相应的y,z值后，再与乙烯反应大体完全或完全。大体完全指的是反应混合液中，乙基次膦酸根、R 1基次膦酸根、R 2基次膦酸根、次磷酸根中含有的磷的总和小于反应液中所有磷总和的5％摩尔。
可选地，在所述反应II体系中，所述水的质量为所述水溶液总质量的10-99％。
具体地，在所述反应II体系中，水太少，盐析效应导致烯烃在水里的溶解度低，反应速度变慢，水太多，反应釜的利用率下降。
可选地，在所述反应II体系中，所述水的质量为所述水溶液总质量的20-95％。
可选地，在所述反应II体系中，所述水的质量为所述水溶液总质量的45-92％。
可选地，在所述反应II体系中，所述水的质量为所述水溶液总质量的50-90％。
可选地，在所述反应II体系中，所述水的质量为所述水溶液总质量的55-90％。
可选地，所述反应II的条件为：温度为0-250℃；时间为0.01-50h；压力为0-3MPa。
具体地，所述反应II的温度过低，反应速度慢，温度过高，次磷酸盐容易分解。
可选地，所述反应II的温度为10-200℃。
具体地，所述反应II的压力高于3MPa，对反应设备要求增高，操作困难。
可选地，所述反应II的压力为0.2-1.5MPa。
可选地，所述自由基引发剂与所述次磷酸和/或其碱金属盐的摩尔比为0.001-0.1:1。
可选地，所述自由基引发剂与所述次膦酸和/或其碱金属盐的摩尔比为0.003-0.05:1。
可选地，所述自由基引发剂选自偶氮类引发剂、过氧化物类引发剂、光引发剂中的至少一种。其中自由基引发剂的加入量可根据实际需要确定。
可选地，所述偶氮类引发剂选自阳离子型和/或非阳离子型偶氮类引发剂，包括偶氮二异丁腈、4,4'偶氮双(4-氰基戊酸)、2,2'-偶氮双(2-甲基丁腈)、2,2'-偶氮双(2-脒基丙烷)二氢氯化物、2,2'-偶氮二丙基脒二盐酸盐中的一种或多种。
可选地，所述过氧化物类引发剂优选为无机过氧化物和有机过氧化物，特别优选为过氧化氢、过硫酸氨、过硫酸钾、过硫酸钠、过碳酸钠、过氧化苯甲酰、过氧化二叔丁基、叔丁基过苯甲酸酯、过乙酸中的一种或多种。
优选地，所述自由基引发剂为过氧化物类引发剂。特别优选地，自由基引发剂选自过硫酸氨、过硫酸钾、过硫酸钠中的一种。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入C 4-C 12的烯烃进行反应，待通入的C 4-C 12的烯烃跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入C 4-C 12的烯烃，再继续通入乙烯反应，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入C 4-C 12的烯烃，待所述C 4-C 12的烯烃反应完全或接近完全后，再继续通入乙烯反应，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，次磷酸和/或其碱金属盐与C 4-C 12的烯烃先反应来获得具有或大体上接近y值的单R 1基次膦酸或其碱金属盐，并且控制z小于等于0.76，然后再停止加入C 4-C 12的烯烃，改为加入乙烯，在引发剂存在下继续反应，随后和需要的金属盐反应，得到具有式(Ⅰ)的阻燃剂。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入C 4-C 12的烯烃和部分乙烯，待所述C 4-C 12的烯烃和部分乙烯反应完全或接近完全后，再继续通入剩余部分乙烯反应，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入C 4-C 12的烯烃和部分乙烯进行反应，乙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比小于式(Ⅰ)中的(2x+y)/1，待通入的C 4-C 12的烯烃跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入C 4-C 12的烯烃，再继续通入剩余部分乙烯反应，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入部分乙烯，所述部分乙烯跟次磷酸和/或其碱金属盐总磷的摩尔之比小于等于式(Ⅰ)中的(2x+y)/1，待所述部分乙烯反应完全后，再继续通入C 4-C 12的烯烃进行反应，待通入的C 4-C 12的烯烃跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入C 4-C 12的烯烃，继续通入剩余部分乙烯进行反应，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入部分乙烯，待所述部分乙烯反应完全或接近完全后，再继续通入C 4-C 12的烯烃进行反应，待所述C 4-C 12的烯烃反应完全或接近完全后，通入剩余部分乙烯进行反应，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述乙烯的总量和所述C 4-C 12的烯烃的摩尔比为0.14-7.33:1。
可选地，所述金属元素M源选自金属元素M盐中的至少一种。
可选地，所述金属元素M盐选自金属元素M的硝酸盐、硫酸盐、盐酸盐、醋酸盐、氧化物中的至少一种。
可选地，次磷酸和/或其碱金属盐同时跟C 4-C 12的烯烃和部分乙烯在自由基引发剂存在下进行反应，控制C 4-C 12的烯烃和乙烯的量，待反应体系中乙基R 1基次膦酸或其碱金属盐与R 1基次膦酸或其碱金属盐总和的摩尔百分比接近y值，且R 1基R 2基次膦酸或其碱金属盐摩尔百分比接近z值，且z小于等于0.76，停止加入C 4-C 12的烯烃，继续加入剩余乙烯，在引发剂存在下继续反应至结束，随后和需要的金属盐进行反应，获得具有式(Ⅰ)的二烷基次膦酸杂化盐。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
可选地，所述混合物A的获得包括以下步骤：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入乙烯，控制乙烯的量，待通入的乙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2x)/1之后，停止通入乙烯，继续加入C 4-C 12的烯烃，在引发剂存在下继续反应至结束，得到所述混合物A。这里，C 4-C 12的烯烃可以是纯的C 4-C 12的烯烃或者C 4-C 12的混合烯烃。
具体地，在反应II结束后，无需分离出二乙基次膦酸、乙基R 1基次膦酸、R 1基R 2基次膦酸和/或其碱金属盐，直接进行下一步反应即可。
根据本申请的第三方面，提供了一种阻燃剂，所述阻燃剂选自上述二烷基次膦酸杂化盐、根据上述方法制备得到的二烷基次膦酸杂化盐中的至少一种。
可选地，在所述阻燃剂中，还含有选自磷酸盐、亚磷酸盐、烷基膦酸盐、烷基次膦酸盐中的至少一种,这些含磷的杂质在所述阻燃剂中的摩尔含量小于等于10％，所述阻燃剂的摩尔数以其中含有的磷元素的摩尔数计。
根据本申请的第四方面，提供了一种阻燃材料，所述阻燃材料中包括阻燃剂P和热塑性高分子材料；
所述阻燃剂P选自上述阻燃剂中的至少一种。
可选地，所述阻燃剂P在所述阻燃材料中的质量含量为1-35％。
可选地，所述阻燃材料中包括1-35wt％的阻燃剂P和65-99wt％的热塑性高分子材料。
本申请中热塑性高分子材料指具有加热软化，冷却硬化特性的塑料。
具体地，所述阻燃剂P的用量取决于热塑性高分子材料。
可选地，所述阻燃剂P在所述阻燃材料中的质量含量为3-20％。
可选地，在所述阻燃材料中，还包括功能添加剂；
所述功能添加剂选自增强剂、抗滴落剂、稳定剂、颜料、染料、成炭催化剂、分散剂、成核剂、无机填料、抗氧剂中的至少一种；
优选地，所述功能添加剂在所述阻燃材料中的质量含量为5-40％。
可选地，所述增强剂选自玻璃纤维。
可选地，所述抗滴落剂选自Teflon。
可选地，所述无机填料选自云母石、碳酸钙、氧化钙、硅石中的至少一种。
可选地，在所述阻燃材料中，还包括阻燃剂Q；
所述阻燃剂Q选自氮系阻燃剂、硼系阻燃剂中的至少一种。
可选地，所述氮系阻燃剂选自三聚氰胺氰尿酸酯、三聚氰胺聚磷酸盐、多聚磷酸铵中的至少一种；
所述硼系阻燃剂选自硼酸锌。
可选地，所述阻燃剂Q在所述阻燃材料中的质量含量为0.5-20％。
可选地，所述热塑性高分子材料选自聚酰胺、聚酯中的至少一种。
可选地，所述聚酰胺选自脂肪族聚酰胺、芳香族聚酰胺、半芳香族聚酰胺、半芳香族聚酰胺与脂肪族聚酰胺的共聚物中的至少一种。
根据本领域公知常识，聚酰胺也称锦纶或尼龙，是其结构单元中含-NH-C(O)-酰胺基团的高分子的总称，通过一种或多种二元羧酸和一种或多种二元胺，和/或者一种或多种氨基酸，和/或者一种或多种内酰胺缩合或开环反应合成。根据其主链的成分，聚酰胺一般分为脂肪族聚酰胺、芳香族聚酰胺和半芳香族聚酰胺。半芳香族聚酰胺是指其合成单体中至少一个单体结构中含有芳香基团。
可选地，所述脂肪族聚酰胺任选自聚酰胺6与聚酰胺66的共聚物、聚酰胺6、聚酰胺66中的一 种或几种的混合物。
可选地，所述半芳香族聚酰胺可由任意一种或几种芳香族二元羧酸与任意一种或几种脂肪族二元胺制得，也可由任意一种或几种芳香族二元胺与任意一种或几种脂肪族二元羧酸制得。体系中还可以添加任选自二元羧酸、二元胺、内酰胺和氨基酸中的一种或任意几种，来制备相应性能的聚酰胺共聚物。添加的二元羧酸为芳香族二元羧酸和/或脂肪族二元羧酸；添加的二元胺为芳香族二元胺和/或脂肪族二元胺；添加的内酰胺可以是脂肪族或者芳香族内酰胺。添加的氨基酸可以是芳香族或脂肪族氨基酸。
可选地，所述半芳香族聚酰胺由任选自对苯二甲酸、间苯二甲酸和萘二甲酸中的一种或多种芳香族二元羧酸，与任选自丁二胺、己二胺、辛二胺、癸二胺和2-甲基戊二胺中的一种或多种脂肪族二元胺制得。
可选地，所述半芳香族聚酰胺由脂肪族二元胺、芳香族二元羧酸和脂肪族二元羧酸制得。
可选地，所述半芳香族聚酰胺由脂肪族二元胺与芳香族二元羧酸制得；可选择地，其中还可以添加脂肪族二元羧酸，脂肪族二元羧酸的摩尔分数占二元羧酸总量的0-45％，即脂肪族二元羧酸的摩尔数/(脂肪族二元羧酸的摩尔数+芳香族二元羧酸的摩尔数)＝0-45％。
可选地，所述芳香族二元羧酸任选自对苯二甲酸、间苯二甲酸和萘二甲酸中的一种或多种；所述脂肪族二元胺任选自丁二胺、己二胺、辛二胺、癸二胺和2-甲基戊二胺中的一种或多种；所述脂肪族二元羧酸任选自己二酸、丁二酸、癸二酸、辛二酸中的一种或多种。
可选地，所述聚酰胺任选自聚对苯二甲酰己二胺(简写为PA6T)、聚间苯二甲酰己二胺(简写为PA6I)、对苯二甲酸/己二胺/己内酰胺共聚物(简写为PA6T/6)、对苯二甲酸/己二胺/己二酸的共聚物(简写为PA6T/66)、对苯二甲酸/己二胺/己二酸/间苯二甲酸的共聚物(简写为PA6T/6I/66)、聚对苯二甲酰壬二胺(简写为PA9T)、聚对苯二甲酰癸二胺(简写为PA10T)，聚对苯二甲酰十二碳二胺(简写为PA12T)、对苯二甲酸/己二胺/十二内酰胺共聚物(简写为PA6T/12)、聚己二酰间苯二甲胺(简写为MXD6)、对苯二甲酸/己二胺/2-甲基戊二胺共聚物(简写为PA6T/2-MPMDT)、对苯二甲酸/2,2,4三甲基己二胺/2,4,4-三甲基己二胺共聚物中的一种或几种。
可选地，所述脂肪族聚酰胺选自聚酰胺6、聚酰胺66、聚酰胺6与聚酰胺66的共聚物中的至少一种。
可选地，所述半芳香族聚酰胺选自聚邻苯二甲酰胺(PPA)。
可选地，所述聚酯选自聚对苯二甲酸丁二醇酯(PBT)。
本发明实施例中，式(Ⅰ)中的x,y,z的值不考虑其它含磷杂质的量，x+y+z＝1,且x+z＞0。具有式(Ⅰ)组成的阻燃剂可以包含微量的其它含磷杂质。由于原材料含杂质或者合成工艺生成杂质的原因，一些微量的磷酸盐、亚磷酸盐、烷基膦酸盐、烷基次膦酸盐可能会存在于阻燃剂中。一些由乙烯和/或C 4-C 12的烯烃聚合或共聚而来的调聚物产物，譬如乙基正十四烷基次膦酸盐、乙基十六烷基次膦酸盐也可能会作为杂质存在于具有式(Ⅰ)组成的阻燃剂中。但只要这些其它含磷的酸根离子的总摩尔 量不超过总磷摩尔量的5％，并不影响具有式(Ⅰ)组成的阻燃剂的正常工作。
本申请实施例中，式(Ⅰ)中的x，y，z的比例可以通过碱解或酸解阻燃剂之后，用 31P-NMR(核磁)来确定。二乙基次膦酸根、乙基R 1基次膦酸根、R 1基R 2基次膦酸根离子具有不同的 31P的化学位移，在 31P-NMR谱中多数情况下呈现独立的峰。
这些峰的峰面积分别对应各自二烷基次膦酸根离子的摩尔浓度，其中某些具有相同化学式的二烷基次膦酸根会有同分异构体，因而可以在核磁磷谱中呈现不同的峰，在计算x,y,z值时将这些同分异构体归为一类。例如，当R 1，R 2为丁基时，所得二烷基次膦酸杂化盐的 31P-NMR谱中会出现五组峰，这五组峰分别对应乙基仲丁基次膦酸根离子，正丁基仲丁基次膦酸根离子，二乙基次膦酸根离子，乙基正丁基次膦酸根离子，二正丁基次膦酸根离子。其中二乙基次膦酸根离子摩尔浓度对应x，乙基仲丁基次膦酸根离子和乙基正丁基次膦酸根离子摩尔浓度之和(统称为乙基丁基次膦酸根离子的摩尔浓度)对应y，二正丁基次膦酸根离子和正丁基仲丁基次膦酸根离子摩尔浓度之和(统称为二丁基次膦酸根离子的摩尔浓度)对应z，三者之比就是x，y和z的值。在一些情况下，存在调聚物二烷基次膦酸根离子，它们的量很少，且化学位移接近相应的二烷基次膦酸根离子，因此，积分时将其并入相对应的二烷基次膦酸根离子。
本申请能产生的有益效果包括：
(1)本发明提供的具有式(Ⅰ)组成的二烷基次膦酸杂化盐添加量少，热稳定性高，对高分子材料阻燃效率高，经济性好。其不仅克服了二乙基次膦酸盐和长链二烷基次膦酸盐单独使用时对高分子材料阻燃效率低的缺点，并且克服了长链二烷基次膦酸盐热稳定性低，阻燃烟雾大的缺点，可以广泛应用于需要高温加工的高分子材料的阻燃；
(2)本申请提供了一种二烷基次膦酸杂化盐的制备方法，避免了需要分别独立制备不同二烷基次膦酸的缺点，使用水作为反应溶剂，环保性好。原料易得，经济性高。
附图说明
图1为具有不同x,y,z值的二烷基次膦酸杂化铝盐(对应式(Ⅰ)中R 1和R 2为丁基，且所述反应II中，使用的C 4-C 12的烯烃为丁烯)以及二乙基次膦酸铝和二丁基次膦酸铝的热失重曲线图；
图2a、2b为具有不同x,y,z值的二烷基次膦酸杂化铝盐(对应式(Ⅰ)中R 1和R 2为丁基，且所述反应II中，使用的C 4-C 12的烯烃为丁烯)、二乙基次膦酸铝、二丁基次膦酸铝以及二丁基次膦酸铝和二乙基次膦酸铝物理混合盐的XRD曲线，其中图2b是图2a最强吸收峰的局部放大图；
图3和图4分别为实施例3和实施例4制备的二烷基次膦酸杂化盐(对应式(Ⅰ)中R 1和R 2为丁基，且所述反应II中，使用的C 4-C 12的烯烃为丁烯)碱解后的 31P-NMR谱图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料均通过商业途径购买。
实施例中所用原料如下：
PA66(又称聚酰胺66或尼龙66)：美国杜邦Zytel 70G35HSL NC010，玻璃纤维含量为35％重量百分比；
PA6(又称聚酰胺6或尼龙6):美国杜邦Zytel 73G30L NC010,玻璃纤维含量为30％重量百分比；
ADP：二乙基次膦酸铝，德国科莱恩公司Exolit OP1230；
MPP：三聚氰胺聚磷酸盐，苏州凯马化学科技有限公司；
硼酸锌：国药集团化学试剂有限公司；
抗氧剂1010：四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯，上海麦克林生化科技有限公司；
抗氧剂168：三[2，4-二叔丁基苯基]亚磷酸酯，美国Strem公司；
复配抗氧剂：抗氧剂1010(四[β-(3，5-二叔丁基-4-羟基苯基丙酸]季戊四醇酯)与抗氧剂168(三[2，4-二叔丁基苯基]亚磷酸酯)以1:1重量比例混合；
燃烧测试标准：GB/T 2408-2008标准；
核磁共振(NMR)测试：所用仪器型号AVANCE III 600MHz和AVANCE III 400MHz，德国Bruker公司；
核磁共振磷谱( 31P-NMR)测试方法：预延期D1＝10秒，扫描32次，并以峰面积之比作为各类膦酸根离子摩尔数之比；
X射线衍射(XRD)测试所用仪器型号：D8ADVANCE DAVINCI，德国Bruker公司；
TGA热失重处理所用仪器型号：Q500，美国TA公司，氮气氛围，升温速率10℃/min。
实施例1
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.40,y＝0.56,z＝0.04,M＝Al，n＝3。
将100克一水合次磷酸钠溶解于500克水中，投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充丁烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.25MPa，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，并持续往反应釜通入丁烯，通过气体流量表来计量烯烃的通入量。4小时后，停止通丁烯，开始通入乙烯。12小时后反应釜压力不再下降，降温泄压、N 2吹扫、放料得无色透明反应液。反应中途及最终反应液取样测核磁， 31P-NMR结果如表1所示：
表1
Figure PCTCN2022119947-appb-000002
Figure PCTCN2022119947-appb-000003
注：表中，乙基丁基次膦酸根离子包括乙基仲丁基次膦酸根离子和乙基正丁基次膦酸根离子；二丁基次膦酸根离子包括正丁基仲丁基次膦酸根离子(R 1≠R 2，分别是正丁基和仲丁基)和二正丁基次膦酸根离子(R 1＝R 2＝正丁基)；其它双加成产物：包括二仲丁基次膦酸根离子和由乙烯和或丁烯聚合过来得到的调聚物二烷基次膦酸根离子。丁基次膦酸根离子为仲丁基次膦酸根离子和正丁基次膦酸根离子总和；丁基膦酸根离子为仲丁基膦酸根离子和正丁基膦酸根离子之和，下同。
将上述部分溶液307.59克(含磷0.36摩尔)，常压下慢慢跟10％质量浓度的含39.99克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到48.15克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁,由 31P-NMR谱可知，二乙基次膦酸根离子摩尔含量为40.23％，乙基正丁基次膦酸根离子摩尔含量为51.98％，乙基仲丁基次膦酸根离子摩尔含量为4.10％，二正丁基次膦酸根离子摩尔含量为3.69％。将具有相同化学式次膦酸根离子的摩尔分数相加(即乙基正丁基次膦酸根离子与乙基仲丁基次膦酸根离子的总和对应y值的计算)，计算得到x＝0.40,y＝0.56,z＝0.04。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000004
(100％)。
实施例2
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0,y＝0.24,z＝0.76,M＝Al，n＝3。
将100克一水合次磷酸钠溶解于500克水中，投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充丁烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.25MPa，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，并持续往反应釜通入丁烯，通过气体流量表来计量烯烃的通入量。8.5小时后，停止通丁烯，开始通入乙烯。15小时后反应釜压力不再下降，降温泄压、N 2吹扫、放料得无色透明反应液。反应液取样测核磁， 31P-NMR结果如表2所示：
表2
Figure PCTCN2022119947-appb-000005
将上述部分溶液353.74克(含磷0.36摩尔)，常压下慢慢跟10％质量浓度的含39.99克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到66.54克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁,由 31P-NMR谱可知，乙基仲丁基次膦酸根离子摩尔含量为2.42％，乙基正丁基次膦酸根离子摩尔含量为21.13％，正丁基仲丁基次膦酸根离子摩尔含量为7.25％，二正丁基次膦酸根离子摩尔含量为68.63％，其他含磷杂质如丁基次膦酸根离子、丁基膦酸根离子摩尔含量总和为0.57％。将具有相同化学式次膦酸根离子的摩尔分数相加(即乙基正丁基次膦酸根离子与乙基仲丁基次膦酸根离子摩尔分数相加用于计算y值；正丁基仲丁基次膦酸根离 子与二正丁基次膦酸根离子以及二烷基次膦酸调聚物摩尔分数相加用于计算z值。)，归一化后得到x＝0,y＝0.24,z＝0.76。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000006
(100％)。
实施例3
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0,y＝0.32,z＝0.68,M＝Al，n＝3。
将100克一水合次磷酸钠溶解于500克水中，投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充丁烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.25MPa，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，并持续往反应釜通入丁烯，通过气体流量表来计量烯烃的通入量。7小时后，停止通丁烯，开始通入乙烯。15.5小时后反应釜压力不再下降，降温泄压、N 2吹扫、放料得无色透明反应液。反应液取样测核磁， 31P-NMR结果如表3所示：
表3
Figure PCTCN2022119947-appb-000007
将上述部分溶液334.45克(含磷0.36摩尔)，常压下慢慢跟10％质量浓度的含39.99克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到64.81克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁, 31P-NMR图谱如图3所示。由 31P-NMR谱可知，乙基仲丁基次膦酸根离子摩尔含量为2.45％，乙基正丁基次膦酸根离子摩尔含量为29.44％，正丁基仲丁基次膦酸根离子摩尔含量为6.83％，二正丁基次膦酸根离子摩尔含量为61.28％。将具有相同化学式次膦酸根离子的摩尔分数相加(即乙基正丁基次膦酸根离子与乙基仲丁基次膦酸根离子摩尔分数相加用于计算y值；正丁基仲丁基次膦酸根离子与二正丁基次膦酸根离子摩尔分数相加用于计算z值)，归一化后得到x＝0,y＝0.32,z＝0.68。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000008
(100％)。
实施例4
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.02,y＝0.63,z＝0.35,M＝Al，n＝3。
将100克一水合次磷酸钠溶解于500克水中，投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充丁烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.25MPa，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，并持续往反应釜通入丁烯，通过气体流量表来计量烯烃的通入量。5.5小时后，停止通丁烯，开始通入乙烯。13小时后反应釜压力不再下降，降温泄压、N 2吹扫、放料得无色透明反应液。反应液取样测核磁， 31P-NMR结果如表4所示：
表4
Figure PCTCN2022119947-appb-000009
将上述部分溶液329.57克(含磷0.36摩尔)，常压下慢慢跟10％质量浓度的含39.99克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到59.60克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁, 31P-NMR图谱如图4所示。由 31P-NMR谱可知，二乙基次膦酸根离子摩尔含量为1.99％，乙基仲丁基次膦酸根离子摩尔含量为4.30％，乙基正丁基次膦酸根离子摩尔含量为58.22％，正丁基仲丁基次膦酸根离子摩尔含量为3.44％，二正丁基次膦酸根离子摩尔含量为30.67％，其他含磷杂质如乙基次膦酸根离子、丁基次膦酸根离子、乙基膦酸根离子、丁基膦酸根离子摩尔含量总和为1.38％。将具有相同化学式次膦酸根离子的摩尔分数相加(即乙基正丁基次膦酸根离子与乙基仲丁基次膦酸根离子摩尔分数相加用于计算y值；正丁基仲丁基次膦酸根离子与二正丁基次膦酸根离子以及二烷基次膦酸调聚物摩尔分数相加用于计算z值。此处将二烷基次膦酸调聚物也并入邻近的二正丁基次膦酸根离子中)，归一化后得到x＝0.02,y＝0.63,z＝0.35。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000010
(100％)。
实施例5
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.22,y＝0.67,z＝0.11,M＝Al，n＝3。
将100克一水合次磷酸钠溶解于500克水中，投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充丁烯。对反应液加热至90℃左右，此时压力表显示为0.15MPa，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，并持续往反应釜通入丁烯，通过气体流量表来计量烯烃的通入量。7.5小时后，停止通丁烯，开始通入乙烯。21小时后反应釜压力基本不再下降，降温泄压、N 2吹扫、放料得无色透明反应液。反应液取样测核磁， 31P-NMR结果如表5所示：
表5
Figure PCTCN2022119947-appb-000011
将上述部分溶液374.84克(含磷0.36摩尔)，常压下慢慢跟10％质量浓度的含39.99克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到52.13克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁,由 31P-NMR谱可知，二乙基次膦酸根离子摩尔含量为21.32％，乙基仲丁基次膦酸根离子摩尔含量为4.52％，乙基正丁基次膦酸根离子摩尔含量为62.02％，正丁基仲丁基次膦酸根离子摩尔含量为1.11％，二正丁基次膦酸根离子摩尔含量为9.66％， 其他含磷杂质如乙基次膦酸根离子、丁基次膦酸根离子、乙基膦酸根离子、丁基膦酸根离子、亚磷酸根离子摩尔含量总和为1.37％。将具有相同化学式的次膦酸根离子的摩尔分数相加(即乙基正丁基次膦酸根离子与乙基仲丁基次膦酸根离子摩尔分数相加用于计算y值；正丁基仲丁基次膦酸根离子与二正丁基次膦酸根离子摩尔分数相加用于计算z值。)，归一化后得到x＝0.22,y＝0.67,z＝0.11。对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000012
(100％)。
实施例6
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.59,y＝0.39,z＝0.02,M＝Al，n＝3。
将100克一水合次磷酸钠溶解于500克水中，与39.7克己烯一同投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充入部分乙烯。对反应液加热至90℃左右，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，反应8.5小时后，开始通入剩余部分乙烯。14.5小时后反应釜压力不再下降，降温泄压、N 2吹扫、放料得无色透明反应液。反应液取样测核磁， 31P-NMR结果如表6所示：
表6
Figure PCTCN2022119947-appb-000013
注：表中，乙基己基次膦酸根离子包括乙基仲己基次膦酸根离子和乙基正己基次膦酸根离子；二己基次膦酸根离子包括正己基仲己基次膦酸根离子(R 1≠R 2，分别是正己基和仲己基)和二正己基次膦酸根离子(R 1＝R 2＝正己基)；己基次膦酸根离子为仲己基次膦酸根离子和正己基次膦酸根离子；己基膦酸根离子为仲己基膦酸根离子和正己基膦酸根离子之和。
将上述部分溶液367.37克(含磷0.36摩尔)，常压下慢慢跟10％质量浓度的含39.99克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到50.35克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁,由 31P-NMR谱可知，二乙基次膦酸根离子摩尔含量为57.54％，乙基己基次膦酸根离子摩尔含量为38.19％，二己基次膦酸根离子摩尔含量为2.21％，其他含磷杂质如乙基次膦酸根离子、己基次膦酸根离子、乙基膦酸根离子、己基膦酸根离子、亚磷酸根离子摩尔含量总和为2.06％。归一化后得到x＝0.59,y＝0.39,z＝0.02。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000014
(100％)。
实施例7
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.01,y＝0.52,z＝0.47,M＝Cu，n＝2。
将上述实施例4中第一步所得部分溶液137.32克(含磷0.15摩尔)，常压下慢慢跟25％质量浓度的含18.73克五水合硫酸铜的水溶液混合，控制反应温度为70℃，调节pH值小于4，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干， 得到19.53克固体，产率70％。将样品溶解于氢氧化钠的水溶液中，做磷核磁,由 31P-NMR谱可知，二乙基次膦酸根离子摩尔含量为0.80％，乙基仲丁基次膦酸根离子摩尔含量为2.76％，乙基正丁基次膦酸根离子摩尔含量为49.60％，正丁基仲丁基次膦酸根离子摩尔含量为4.48％，二正丁基次膦酸根离子摩尔含量为42.36％。将具有相同化学式次膦酸根离子的摩尔分数相加(即乙基正丁基次膦酸根离子与乙基仲丁基次膦酸根离子的总和对应y值的计算)，计算得到x＝0.01,y＝0.52,z＝0.47。因不同二烷基次膦酸铜盐溶解度的差异，导致本实施例收率较低，最终得到的杂化盐中x,y,z值与相同磷原料得到的其他金属杂化盐的x,y,z值相差较大。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000015
(100％)。
图1是具有不同x,y,z值的杂化盐(实施例1，实施例4，实施例5)以及二乙基次膦酸铝和二丁基次膦酸铝(对比例1)的热失重曲线图(TGA)。由图可知，z值越大杂化盐的热稳定性越低，x越大热稳定性越高。
图2a是具有不同x,y,z值的杂化盐(实施例1-5)，二丁基次膦酸铝(对比例1)，二乙基次膦酸铝(ADP)及二丁基次膦酸铝和二乙基次膦酸铝物理混合盐的XRD图。图2b是图2a中最强吸收峰的局部放大图，从图2b中可知，简单的物理混合盐在XRD谱图中，在最强的吸收峰区域，具有2个独立的峰，且它们的d值分别接近二乙基次膦酸铝和二丁基次膦酸铝的d值，具有式(Ⅰ)组成的杂化盐只有一个峰或重叠峰，且d值基本介于二乙基次膦酸铝和二丁基次膦酸铝的d值之间。这说明本发明所述具有式(Ⅰ)组成的二烷基次膦酸杂化盐不是简单的二乙基次膦酸铝、乙基丁基次膦酸铝、二丁基次膦酸铝的混合物，而是包含了二乙基次膦酸根、乙基丁基次膦酸根、二丁次膦酸根中至少二个酸根离子跟同一个铝原子配对的结构的杂化盐。
实施例8
将聚酰胺PA66、由实施例1制备过来的杂化盐以及复配抗氧剂按照79.6:20:0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。然后将其填充于模具中，在280℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。1.6mm样品的阻燃级别为UL94V-0。
实施例9
将聚酰胺PA6、由实施例1制备所得杂化盐以及复配抗氧剂按照79.6:20:0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为260℃，5分钟后取出冷却、干燥。然后将其填充于模具中，在260℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。1.6mm样品的阻燃级别为UL94V-0。
实施例10-22
将实施例1-7制备的杂化盐分别在聚酰胺PA66，PA6中按照实施例8、9的方式进行制样和测试，结果见表7。
对比例1 制备二丁基次膦酸铝
将100克一水合次磷酸钠溶解于500克水中，投入到1L不锈钢压力釜，反应釜用氮气置换两次，抽真空之后，充丁烯至压力不再上升。对反应液加热至90℃左右，然后以10ml/h的速度匀速打入4％质量浓度的过硫酸钠水溶液，并持续往反应釜通入丁烯，通过气体流量表来计量丁烯的通入量。25.5小时后体系压力不再下降，停止反应，降温泄压、N 2吹扫、放料得透明反应液。反应液取样做核磁， 31P-NMR结果显示：正丁基仲丁基次膦酸摩尔含量10.56％，二正丁基次膦酸摩尔含量84.92％，二丁基次膦酸调聚物摩尔含量3.52％，其余1.00％为丁基次膦酸、丁基膦酸和亚磷酸等副产。
将部分上述溶液394克(含磷0.3996摩尔)，常压下慢慢跟10％质量浓度的含44.38克十八水合硫酸铝的水溶液混合，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。加料混合完毕之后，保温0.5小时。趁热过滤，过滤较慢，滤饼用清水洗至pH＞4.5。之后滤饼在120℃下烘干，得到67.28克白色固体。
对样品进行XRD测试，所得XRD测定的相对强度最高的特征峰对应的层间距为
Figure PCTCN2022119947-appb-000016
(100％)。
对比例2
将聚酰胺PA66、对比例1制备的二丁基次膦酸铝、复配抗氧剂按照79.6:20:0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。然后将其填充于模具中，在280℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。1.6mm样品的阻燃级别为UL94无等级。
对比例3
将聚酰胺PA6、对比例1制备的二丁基次膦酸铝、复配抗氧剂按照79.6:20:0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为260℃，5分钟后取出冷却、干燥。然后将其填充于模具中，在260℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。1.6mm样品的阻燃级别为UL-94V-1。
对比例4
将聚酰胺PA66、二乙基次膦酸铝、复配抗氧剂按照79.6:20:0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。然后将其填充于模具中，在280℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。1.6mm样品的阻燃级别为UL94无等级。
对比例5
将聚酰胺PA6、二乙基次膦酸铝、复配抗氧剂按照79.6:20:0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为260℃，5分钟后取出冷却、干燥。然后将其填充于模具中，在260℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。1.6mm样品的阻燃级别为UL-94无等级。
表7 实施例10-22测试结果
Figure PCTCN2022119947-appb-000017
Figure PCTCN2022119947-appb-000018
实施例8-22说明含有本发明所述二烷基次膦酸杂化盐的阻燃剂对聚酰胺具有突出的阻燃效率。所制备的阻燃PA66样条韧性好，无明显降解。且在阻燃聚酰胺燃烧测试时候，无明显烟雾。对比例2-3显示出二丁基次膦酸盐对聚酰胺的阻燃效率不如本发明所述具有式(Ⅰ)结构的杂化盐，并且在阻燃聚酰胺燃烧时候，烟雾大，对逃生不利。另外从图1中可知，其热稳定性过低，所制备的阻燃PA66脆性较大，说明有降解。对比例4-5说明纯的二乙基次膦酸铝对聚酰胺阻燃效率低。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (25)

  1. 一种二烷基次膦酸杂化盐，其特征在于，所述二烷基次膦酸杂化盐选自具有式(I)所示化学式的化合物中的至少一种；
    Figure PCTCN2022119947-appb-100001
    其中，M为中心原子；R 1、R 2均独立地选自C 4-C 12的烷基，且R 1、R 2中至少一个不为异丁基；
    二乙基次膦酸根离子、乙基R 1基次膦酸根离子、R 1基R 2基次膦酸根离子均为配体；
    M选自金属元素；所述金属元素选自第ⅡA、ⅢA、ⅣA、ⅤA族金属元素、过渡金属元素、镧系金属元素中的至少一种；
    n为金属元素M的价态；n选自2，3或4；
    乙基R 1基次膦酸根离子、二乙基次膦酸根离子、R 1基R 2基次膦酸根离子中至少两种酸根离子与同一个中心原子M配对；且其中一个与中心原子M配对的配体为乙基R 1基次膦酸根离子；
    0≤x≤0.76；0.05≤y≤0.76；0≤z≤0.76,且x+y+z＝1。
  2. 根据权利要求1所述的二烷基次膦酸杂化盐，其特征在于，所述第ⅡA族金属元素选自Be、Mg、Ca、Sr、Ba中的至少一种；
    所述第ⅢA族金属元素为Al；
    所述第ⅣA族金属元素为Sn；
    所述第ⅤA族金属元素为Sb；
    所述过渡金属元素选自Fe、Zn、Cu、Ti、Zr、Mn中的至少一种；
    所述镧系金属元素为Ce。
  3. 根据权利要求1所述的二烷基次膦酸杂化盐，其特征在于，0≤x≤0.76；0.05≤y≤0.67；0.005≤z≤0.76。
  4. 根据权利要求1所述的二烷基次膦酸杂化盐，其特征在于，0≤x≤0.70；0.05≤y≤0.67；0.005≤z≤0.70；
    优选地，0.1≤x≤0.65；0.30≤y≤0.67；0.01≤z≤0.50；
    优选地，0.30≤x≤0.65；0.30≤y≤0.65；0.02≤z≤0.40。
  5. 根据权利要求1所述的二烷基次膦酸杂化盐，其特征在于，M＝Al，n＝3。
  6. 权利要求1至5任一项所述的二烷基次膦酸杂化盐的制备方法，其特征在于，所述制备方法包括：
    将含有混合物A和金属元素M源的物料在水相中进行反应I，得到所述二烷基次膦酸杂化盐；
    所述混合物A中包含二乙基次膦酸和/或其碱金属盐、乙基R 1基次膦酸和/或其碱金属盐与R 1基R 2基次膦酸和/或其碱金属盐。
  7. 根据权利要求6所述的制备方法，其特征在于，所述反应I的条件为：温度为0-250℃；压力为0.1MPa-10MPa；时间为0.01-20h。
  8. 根据权利要求6所述的制备方法，其特征在于，所述反应I在pH为0～4下进行。
  9. 根据权利要求6所述的制备方法，其特征在于，所述混合物A的获得包括以下步骤：
    向含有次膦酸和/或其碱金属盐、自由基引发剂的水溶液中通入乙烯和C 4-C 12的烯烃，反应II，得到所述混合物A。
  10. 根据权利要求9所述的制备方法，其特征在于，所述次膦酸和/或其碱金属盐、乙烯、C 4-C 12的烯烃的摩尔比为1：0.24-1.76：1.76-0.24。
  11. 根据权利要求9所述的制备方法，其特征在于，在所述水溶液中，所述水的质量为所述水溶液总质量的10-99％。
  12. 根据权利要求9所述的制备方法，其特征在于，所述反应II的条件为：温度为0-250℃；时间为0.01-50h；压力为0-3MPa。
  13. 根据权利要求9所述的制备方法，其特征在于，所述自由基引发剂与所述次磷酸和/或其碱金属盐的摩尔比为0.001-0.1:1；
    优选地，所述自由基引发剂与所述次磷酸和/或其碱金属盐的摩尔比为0.003-0.05:1。
  14. 根据权利要求9所述的制备方法，其特征在于，所述混合物A的获得包括以下步骤：
    向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入C 4-C 12的烯烃进行反应，待通入的C 4-C 12的烯烃跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入C 4-C 12的烯烃，再继续通入乙烯反应，得到所述混合物A。
  15. 根据权利要求9所述的制备方法，其特征在于，所述混合物A的获得包括以下步骤：
    向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入C 4-C 12的烯烃和部分乙烯进行反应，乙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比小于式(Ⅰ)中的(2x+y)/1，待通入的C 4-C 12的烯烃跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入C 4-C 12的烯烃，再继续通入剩余部分乙烯反应，得到所述混合物A。
  16. 根据权利要求9所述的制备方法，其特征在于，所述混合物A的获得包括以下步骤：
    向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入部分乙烯，所述部分乙烯跟次磷酸和/或其碱金属盐总磷的摩尔之比小于等于式(Ⅰ)中的(2x+y)/1，待所述部分乙烯反应完全后，再继续通入C 4-C 12的烯烃进行反应，待通入的C 4-C 12的烯烃跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入C 4-C 12的烯烃，继续通入剩余部分乙烯进行反应，得到所述混合物A。
  17. 根据权利要求9至16任一项所述的制备方法，其特征在于，所述乙烯的总量和所述C 4-C 12的烯烃总量的摩尔比为0.14-7.33:1。
  18. 根据权利要求6所述的制备方法，其特征在于，所述金属元素M源选自金属元素M盐中的至少一种；
    优选地，所述金属元素M盐选自金属元素M的硝酸盐、硫酸盐、盐酸盐、醋酸盐、氧化物中的至少一种。
  19. 一种阻燃剂，其特征在于，所述阻燃剂选自权利要求1至5任一项所述的二烷基次膦酸杂化盐、根据权利要求6至18任一项所述方法制备得到的二烷基次膦酸杂化盐中的至少一种。
  20. 一种阻燃材料，其特征在于，所述阻燃材料中包括阻燃剂P和热塑性高分子材料；
    所述阻燃剂P选自权利要求19所述的阻燃剂中的至少一种。
  21. 根据权利要求20所述的阻燃材料，其特征在于，所述阻燃剂P在所述阻燃材料中的质量含量为1-35％。
  22. 根据权利要求20所述的阻燃材料，其特征在于，在所述阻燃材料中，还包括功能添加剂；
    所述功能添加剂选自增强剂、抗滴落剂、稳定剂、颜料、染料、成炭催化剂、分散剂、成核剂、无机填料、抗氧剂中的至少一种；
    优选地，所述功能添加剂在所述阻燃材料中的质量含量为5-40％。
  23. 根据权利要求22所述的阻燃材料，其特征在于，在所述阻燃材料中，还包括阻燃剂Q；
    所述阻燃剂Q选自氮系阻燃剂、硼系阻燃剂中的至少一种。
  24. 根据权利要求23所述的阻燃材料，其特征在于，所述阻燃剂Q在所述阻燃材料中的质量含量为0.5-20％。
  25. 根据权利要求20所述的阻燃材料，其特征在于，所述热塑性高分子材料选自聚酰胺、聚酯中的至少一种。
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CN1280583A (zh) * 1997-11-28 2001-01-17 科莱恩有限公司 制备二烷基次膦酸的盐的方法
CN103073577A (zh) * 2012-09-19 2013-05-01 广州金凯新材料有限公司 一种二烷基次膦酸盐及其制备方法
CN103172670A (zh) * 2013-03-04 2013-06-26 广州金凯新材料有限公司 一种单烷基/二烷基次膦酸盐及其制备方法
WO2018015251A1 (de) * 2016-07-20 2018-01-25 Clariant Plastics & Coatings Ltd Diorganylphosphinsäuresalze, ein verfahren zu deren herstellung und ihre verwendung
CN111662323A (zh) * 2019-03-07 2020-09-15 黎杰 二烷基次膦酸-烷基亚磷酸金属复合盐,其制备方法和用途
CN111825883A (zh) * 2019-04-15 2020-10-27 黎杰 多二烷基次膦酸金属复合盐和/或其混合物，和其用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1280583A (zh) * 1997-11-28 2001-01-17 科莱恩有限公司 制备二烷基次膦酸的盐的方法
CN103073577A (zh) * 2012-09-19 2013-05-01 广州金凯新材料有限公司 一种二烷基次膦酸盐及其制备方法
CN103172670A (zh) * 2013-03-04 2013-06-26 广州金凯新材料有限公司 一种单烷基/二烷基次膦酸盐及其制备方法
WO2018015251A1 (de) * 2016-07-20 2018-01-25 Clariant Plastics & Coatings Ltd Diorganylphosphinsäuresalze, ein verfahren zu deren herstellung und ihre verwendung
CN111662323A (zh) * 2019-03-07 2020-09-15 黎杰 二烷基次膦酸-烷基亚磷酸金属复合盐,其制备方法和用途
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