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WO2023060590A1 - 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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Publication number
WO2023060590A1
WO2023060590A1 PCT/CN2021/124204 CN2021124204W WO2023060590A1 WO 2023060590 A1 WO2023060590 A1 WO 2023060590A1 CN 2021124204 W CN2021124204 W CN 2021124204W WO 2023060590 A1 WO2023060590 A1 WO 2023060590A1
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flame retardant
acid
salt
alkali metal
preparation
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PCT/CN2021/124204
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English (en)
French (fr)
Inventor
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 KR1020247012822A priority Critical patent/KR20240074798A/ko
Priority to PCT/CN2021/124204 priority patent/WO2023060590A1/zh
Priority to JP2024521757A priority patent/JP2024536906A/ja
Priority to EP21960320.6A priority patent/EP4403561A1/en
Priority to MX2024004464A priority patent/MX2024004464A/es
Publication of WO2023060590A1 publication Critical patent/WO2023060590A1/zh
Priority to US18/629,897 priority patent/US20240279436A1/en

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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)]
    • 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
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C07F19/005—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 without metal-C linkages
    • 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)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the application relates to a dialkyl phosphinic acid hybrid salt and its preparation method and application, belonging to the field of preparation of flame-retardant polymer materials.
  • Dialkylphosphinate especially aluminum diethylphosphinate, has been widely used as a halogen-free flame retardant for polymer materials.
  • the density of dialkylphosphinate flame retardant products is low, and the amount of flame retardant Small, good mechanical properties, but the flame retardant efficiency of the existing dialkylphosphinate as a flame retardant is limited, such as polydialkylphosphinate can be used as a flame retardant for non-glass fiber reinforced nylon, retardant
  • the combustion efficiency is low, and when used, it will have a greater adverse effect on the physical properties of flame-retardant polymer materials. It is also reported that aluminum diisobutylphosphinate is used for flame retardancy of nylon.
  • Aluminum diisobutylphosphinate has a very high flame retardancy efficiency, but its thermal stability is low, and it begins to degrade and volatilize in large quantities at 300°C. , which is unfavorable to engineering plastics that require high temperature processing. And aluminum diisobutylphosphinate has poor flame retardant effect on polyester. At the same time, its plasticity is relatively large, which is unfavorable to the physical properties of flame-retardant polymers.
  • the application provides a dialkyl phosphinic acid hybrid salt and its preparation method and application.
  • the dialkyl phosphinic acid hybrid salt has a dialkyl
  • the amount of phosphonic acid hybrid salt added is small, and it has high flame retardant efficiency for various polymer materials and good economy.
  • a hybrid salt of dialkylphosphinic acid is provided, and the hybrid salt of dialkylphosphinic acid is selected from at least one of the compounds represented by formula (I) :
  • M is the central atom, and diethylphosphinate ion, ethylisobutylphosphinate ion and diisobutylphosphinate ion are all ligands;
  • M is selected from metal elements; the metal elements are selected from at least one of Group IIA, IIIA, IVA, and VA metal elements, transition metal elements, and lanthanide metal elements;
  • n is the valence state of the metal M; n is selected from 2, 3 or 4;
  • the lower limit of x is independently selected from 0, 0.15, 0.2, 0.25, 0.3, 0.35, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.03; the upper limit is independently selected from 0.95, 0.9, 0.85, 0.87, 0.7.
  • the lower limit of y is independently selected from 0.05, 0.1, 0.15, 0.2, 0.13, 0.29; the upper limit is independently selected from 0.8, 0.7, 0.6, 0.5, 0.4, 0.35, 0.3, 0.25, 0.68.
  • the lower limit of z is independently selected from 0, 0.02; the upper limit is independently selected from 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, 0.05.
  • the Group IIA metal element is selected from at least one of Be, Mg, Ca, Sr, 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, Mn;
  • the lanthanide metal element is Ce.
  • the metal element is selected from at least one of Al, Zn, Ca, and Fe.
  • the larger the z value the earlier the thermal weight loss of the dialkylphosphinic acid hybrid salt.
  • the hybrid salt of dialkylphosphinate in this application is not a simple physical mixture of different dialkylphosphinates, for example, it is not composed of aluminum diethylphosphinate and aluminum ethylisobutylphosphinate
  • the mixture is simply mixed, but contains a hybrid salt composed of diethylphosphinate ion, ethylisobutylphosphinate ion, and diisobutylphosphinate ion coordinated to the same aluminum atom .
  • the X ⁇ ray diffraction (XRD) patterns of these hybrid salts are very different from those of the simple physically mixed salts of dialkylphosphinates.
  • the dialkylphosphinic acid hybrid salt having the composition of formula (I) shows a single peak or overlapping double peaks in the strongest absorption peak area in the XRD spectrum. And the interplanar spacing peaks shown by the largest peaks are also different from those of aluminum diethylphosphinate and aluminum diisobutylphosphinate.
  • dialkylphosphinic acid hybrid salt having the composition of formula (I) and aluminum diethylphosphinate two independent peaks also appear in their XRD patterns .
  • the dialkylphosphinic acid hybrid salt with formula (I) obtained by the present invention is not simple aluminum diethylphosphinate, ethylisobutylaluminumphosphinate, diisobutylaluminum A mixture of aluminum phosphinates, but containing diethylphosphinate, ethylisobutylphosphinate, and diisobutylphosphinate paired with the same aluminum atom.
  • the flame retardant effect of pure diethylphosphinate or diisobutylphosphinate is far inferior to that containing both diethylphosphinate and ethylisobutyl Hybrid salts of phosphinate groups.
  • the flame retardancy is also related to the content of ethyl isobutyl phosphinate. Only the composition of y within a specific range can have good flame retardancy, thermal performance and good economy.
  • a method for preparing the above-mentioned hybrid salt of dialkylphosphinic acid comprising:
  • the material containing the mixture A and the metal element M source is subjected to reaction I in the water phase to obtain the hybrid salt of dialkylphosphinic acid;
  • Said mixture A comprises diethylphosphinic acid and/or its alkali metal salt, ethyl isobutylphosphinic acid and/or its alkali metal salt and diisobutylphosphinic acid and/or its alkali metal salt .
  • the diethylphosphinic acid and/or its alkali metal salt, ethylisobutylphosphinic acid and/or its alkali metal salt, diisobutylphosphinic acid and/or its alkali metal salt The molar ratio to the metal element M source is close to x:y:z:q;
  • the solubility of hybrid salts in water is not the same.
  • diethylphosphinic acid and/or its alkali metal salt, ethylisobutylphosphinic acid and/or its alkali metal salt, diisobutylphosphinic acid and/or The values of x, y, and z in the alkali metal salt and the hybrid salt are different, so the molar ratio with the M source will also change.
  • the molar ratio of reactants x, y, z and M can also exceed the theoretically calculated value.
  • diethylphosphinic acid and/or its alkali metal salt diethylphosphinic acid and/or its alkali metal salt, ethyl isobutylphosphinic acid and/or its alkali metal salt and diisobutylphosphinic acid and/or its
  • the molar ratio of the alkali metal salt is the same or substantially the same as the ratio of x, y, z in formula (I).
  • reaction I is as follows: temperature is 0-250°C; pressure is 0.1MPa-10MPa; time is 0.1-20h.
  • the obtaining of the mixture A comprises the following steps:
  • the molar ratio of phosphinic acid and/or its alkali metal salt, ethylene, and isobutylene is 1:0.05-1.95:0.5-1.5.
  • the molar ratios of phosphinic acid and/or its alkali metal salt, ethylene, and isobutylene are the same or close to the values of x, y, and z in formula (I).
  • the reaction rate depends on the values of x, y, z. The larger the z value, the slower the reaction rate, so in order to obtain economy, the z value needs to be controlled.
  • hypophosphorous acid and/or its alkali metal salt first reacts with isobutene to obtain corresponding y, z values, and then reacts with ethylene substantially completely or completely.
  • substantially complete means that in the reaction mixture, the sum of phosphorus contained in ethyl phosphinate, isobutyl phosphinate and hypophosphite is less than 5 mol% of the sum of all phosphorus in the reaction liquid.
  • reaction I there is no need to isolate diethylphosphinic acid, ethyl isobutylphosphinic acid, diisobutylphosphinic acid or their alkali metal mixture, and the next reaction can be carried out directly .
  • the mass of the water is 10-99% of the total mass of the free radical initiator and the phosphinic acid and/or its alkali metal salt.
  • the salting-out effect will lead to low solubility of olefins in water, 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 free radical initiator and the phosphinic acid and/or its alkali metal salt.
  • the mass of the water is 45-92% of the total mass of the free radical initiator and the phosphinic acid and/or its alkali metal salt.
  • the mass of the water is 50-90% of the total mass of the free radical initiator and the phosphinic acid and/or its alkali metal salt.
  • the mass of the water is 55-90% of the total mass of the free radical initiator and the phosphinic acid and/or its alkali metal salt.
  • the conditions of the reaction II are: the temperature is 0-250°C; the time is 0.01-50h; the pressure is 0-3MPa.
  • the temperature of the reaction II is too low, the reaction speed is slow, and the temperature is too high, the phosphinate is easy to decompose.
  • the temperature of the reaction II is 10-200°C.
  • the pressure of the reaction II is higher than 3MPa, which requires higher requirements for reaction equipment and difficult operation.
  • the pressure of the reaction II is 0.2-1.5 MPa.
  • the molar ratio of the free radical initiator to the phosphinic acid and/or its alkali metal salt is 0.001-0.1:1.
  • the free radical initiator is selected from at least one of azo initiators, peroxide initiators, and photoinitiators. Wherein the addition amount of radical initiator 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'-azobisisobutylamidine One or more of dihydrochlorides.
  • the peroxide initiator is preferably an inorganic peroxide and an organic peroxide radical initiator, particularly preferably hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, sodium percarbonate , one or more of benzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, and peracetic acid.
  • an organic peroxide radical initiator particularly preferably hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, sodium percarbonate , one or more of benzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, and peracetic acid.
  • the free radical initiators are peroxides.
  • the free radical initiator is selected from one of ammonium persulfate, potassium persulfate and sodium persulfate.
  • the molar ratio of the free radical initiator to the phosphinic acid and/or its alkali metal salt is 0.003-0.05:1.
  • the obtaining of the mixture A comprises the following steps:
  • the obtaining of the mixture A comprises the following steps:
  • phosphinic acid and/or its alkali metal salt is first reacted with isobutene to obtain monoisobutylphosphinic acid or its alkali metal salt having or substantially close to the value of y, and controlling z to be less than or equal to 0.5, and then Stop adding isobutylene, add ethylene instead, continue the reaction in the presence of an initiator, and then react with the required metal salt to obtain a flame retardant with formula I.
  • the obtaining of the mixture A comprises the following steps:
  • the ratio of ethylene and the total phosphorus mole of phosphinic acid and/or its alkali metal salt is less than formula ( (2x+y)/1 in I)
  • the total phosphorus molar ratio of the isobutylene to be passed into with phosphinic acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I)
  • Stop feeding the isobutylene then continue feeding the remaining part of ethylene to react to obtain the mixture A.
  • the obtaining of the mixture A comprises the following steps:
  • the molar ratio of the total amount of ethylene to the isobutylene is 0.33-39:1.
  • the obtaining of the mixture A comprises the following steps:
  • the molar ratio of described part ethylene with phosphinic acid and/or its alkali metal salt total phosphorus is less than formula (I ) in (2x+y)/1, after the part of the ethylene reaction is complete, continue to feed isobutene to react, the ratio of the total phosphorus moles of the isobutene to be fed to phosphinic acid and/or its alkali metal salt After reaching (y+2z)/1 in the formula (I), stop feeding isobutene, continue feeding the remaining part of ethylene for reaction, and obtain the mixture A.
  • the obtaining of the mixture A comprises the following steps:
  • the molar ratio of the total amount of ethylene to the isobutylene is 0.33-39:1.
  • the source of the metal element M is at least one selected from metal element M salts.
  • the metal element M salt is selected from at least one of metal element M nitrates, sulfates, hydrochlorides, acetates, and oxides.
  • phosphinic acid and/or its alkali metal salt react with isobutene and part of ethylene at the same time in the presence of a free radical initiator to control the amount of isobutene and ethylene, isobutylphosphinic acid or its base in the reaction system
  • the molar percentage of the metal salt is close to the y value
  • the molar percentage of diisobutylphosphinic acid or its alkali metal salt is close to the z value
  • z is less than or equal to 0.5
  • stop adding isobutylene continue to add the remaining ethylene, and continue to react in the presence of the initiator to End, followed by reaction with the desired metal salt to obtain a hybrid salt of dialkylphosphinic acid having formula (I).
  • a flame retardant which includes at least one of the above-mentioned hybrid salts of dialkylphosphinic acid.
  • the flame retardant also contains at least one selected from phosphate ions, phosphite ions, alkyl phosphonate ions, and alkyl phosphinate ions.
  • phosphate ions phosphite ions
  • alkyl phosphonate ions alkyl phosphinate ions.
  • alkyl phosphinate ions alkyl phosphinate ions.
  • phosphorus-containing acid ions are The molar content of the flame retardant is less than or equal to 10 mole percent of the flame retardant, and the molar number of the flame retardant is calculated by the molar number of phosphorus contained therein.
  • a flame retardant material which includes a flame retardant P and a thermoplastic polymer material;
  • the flame retardant P is selected from the application of at least one of the above-mentioned dialkylphosphinic acid hybrid salts and the above-mentioned flame retardants in flame-retardant materials.
  • the mass content of the flame retardant P in the flame retardant material is 1-35%.
  • the flame retardant material includes 1-35wt% of flame retardant P and 65-99wt% of thermoplastic polymer material.
  • Thermoplastic polymer materials in this application refer to plastics that soften when heated and harden 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 functional additive is at least one selected from reinforcing agents, anti-dripping agents, stabilizers, pigments, dyes, carbon-forming catalysts, dispersants, nucleating agents, inorganic fillers, and antioxidants.
  • the reinforcing agent is selected from glass fibers.
  • the anti-dripping agent is selected from Teflon.
  • the inorganic filler is at least one selected from mica stone, calcium carbonate, calcium oxide and silica.
  • the mass content of the functional additive in the flame retardant material is 5-40%.
  • a flame retardant Q is also included in the flame retardant material.
  • the flame retardant Q is at least one selected from 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 of aliphatic polyamides, aromatic polyamides, semi-aromatic polyamides, and copolymers of semi-aromatic polyamides and aliphatic polyamides.
  • flame retardants B can be added to the flame retardant material according to specific needs, such as nitrogen flame retardants, including melamine cyanurate; phosphorus-nitrogen flame retardants, including melamine polyphosphate, ammonium polyphosphate, etc.; and boron-based flame retardants, including zinc borate, etc.
  • nitrogen flame retardants including melamine cyanurate
  • phosphorus-nitrogen flame retardants including melamine polyphosphate, ammonium polyphosphate, etc.
  • boron-based flame retardants including zinc borate, etc.
  • the flame retardant material includes reinforced glass fibers in an amount of 5-40% by weight.
  • Other additives such as stabilizers, anti-dripping agents, pigments, dyes, carbon-forming catalysts, dispersants, flame retardants, nucleating agents and inorganic fillers such as mica stone, calcium carbonate, calcium oxide, silica or their mixtures are also available Inclusive, all ingredients add up to 100% by weight.
  • polyamide also known as nylon or nylon
  • nylon is a general term for polymers containing -NH-C(O)-amide groups in its structural units, through one or more dicarboxylic acids and one or multiple diamines, and/or one or more amino acids, and/or one or more lactam condensation or ring-opening reactions.
  • polyamides are generally classified into aliphatic polyamides, aromatic polyamides and semi-aromatic polyamides.
  • Semi-aromatic polyamide means that at least one monomer structure in its synthetic monomer contains an aromatic group.
  • the aliphatic polyamide is selected from one or a mixture of polyamide 6 and polyamide 66 copolymer, polyamide 6, and polyamide 66.
  • the semi-aromatic polyamide can be prepared from any one or several aromatic dicarboxylic acids and any one or several aliphatic diamines, and can also be prepared from any one or several aromatic dicarboxylic acids. It can be prepared from primary amine and any one or several aliphatic dicarboxylic acids.
  • One or more selected from dicarboxylic acid, diamine, lactam and amino acid can also be added to the system to prepare polyamide copolymer 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 Aromatic 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 terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid, and optionally selected from butanediamine, One or more aliphatic diamines in hexamethylenediamine, octanediamine, decanediamine and 2-methylpentamethylenediamine.
  • the semi-aromatic polyamide is prepared from aliphatic diamine, aromatic dicarboxylic acid and aliphatic dicarboxylic acid.
  • the semi-aromatic polyamide is prepared from aliphatic diamine and aromatic dicarboxylic acid; optionally, aliphatic dicarboxylic acid can also be added, the mole of aliphatic dicarboxylic acid
  • the aromatic dicarboxylic acid is optionally selected from one or more of terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid;
  • the aliphatic diamine is optionally selected from butanediamine, One or more in hexamethylenediamine, octyldiamine, decanediamine and 2-methylpentamethylenediamine;
  • the aliphatic dicarboxylic acid is optionally adipic acid, succinic acid, sebacic acid, octane One or more of the 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), copolymer of terephthalic acid/hexanediamine/adipic acid (abbreviated as PA6T/66), terephthalic acid/hexanediamine/adipic acid/isophthalic acid Copolymer of formic acid (abbreviated as PA6T/6I/66), polynonanediamine terephthalamide (abbreviated as PA9T), polydecanediamide terephthalamide (abbreviated as PA10T), polyterephthalamide Dodecyl diamine (abbreviated as PA12T), terephthalic acid/hexamethylenediamine/laurolactam copolymer (abbreviated as PA6
  • the aliphatic polyamide is selected from at least one of polyamide 6, polyamide 66, and a copolymer 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
  • the flame retardants having the composition of formula (I) may contain trace amounts of other phosphorus-containing ions. Due to the impurities in the raw materials or the impurities generated in the synthesis process, some traces of phosphate ions, phosphite ions, alkylphosphonate ions, and alkylphosphinate ions may exist in the flame retardant.
  • Some oligomer products from the polymerization of ethylene such as ethyl n-butyl phosphinate ion, ethyl hexyl phosphinate ion, butyl butyl phosphinate ion, butyl hexyl phosphinate ion will also serve as Impurities are present in the flame retardant having the composition of formula (I).
  • the total amount of these other phosphorus-containing acid radical ions does not exceed 10% mole of the total phosphorus, it will not affect the normal operation of the flame retardant composed of formula (I).
  • the proportions of x, y, and z in formula (I) can be determined by 31 P-NMR (nuclear magnetic field) after alkali hydrolysis or acid hydrolysis of the flame retardant.
  • Diethyl phosphinate, ethyl isobutyl phosphinate, and diisobutyl phosphinate have different 31 P chemical shifts, and present three independent peaks in the 31 P-NMR spectrum. These three peaks The peak areas of are corresponding to the molar concentrations of the three phosphinates, therefore, the values of x, y, and z can be easily calculated through the ratio of the peak areas.
  • the dialkylphosphinic acid hybrid salt having the formula (I) provided by the present invention has a small amount of addition, high flame retardant efficiency for various polymer materials, and good economical efficiency. It not only overcomes the shortcomings of diethylphosphinate, which has low flame retardant efficiency for polymer materials, but also overcomes the shortcomings of diisobutylphosphinate's high volatility and low flame retardant efficiency for polyester, and can Widely used in the flame retardancy of various polymer materials that require high temperature processing;
  • the present application provides a method for preparing a hybrid salt of dialkylphosphinic acid, which avoids the disadvantage of independently preparing dialkylphosphinic acid, uses water as a reaction solvent, and has good environmental protection.
  • the raw material is easy to get, and the economy is high.
  • Fig. 1 is to have different x, y, the thermogravimetric curve graph of the hybrid salt of dialkylphosphinic acid and aluminum diethylphosphinate and aluminum diisobutylphosphinate of z value (for the convenience of showing, table The value displayed on the head is 100 times of x, y, z);
  • Figure 2 is the XRD curves of dialkylphosphinic acid hybrid salts, aluminum diethylphosphinate and aluminum diisobutylphosphinate with different x, y, z values (for the sake of convenience, the table header shows The value of x, y, z is 100 times, physical mixing refers to the mixing of aluminum diethylphosphinate and aluminum diisobutylphosphinate);
  • Fig. 3 is the 31 P-NMR figure of dialkyl phosphinic acid hybrid salt alkali hydrolysis in embodiment 3.
  • the raw materials used in the implementation are as follows:
  • 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;
  • PPA high temperature nylon: American DuPont HTN 51G35HSL NC010, glass fiber content is 35% by weight;
  • PBT polybutylene terephthalate
  • ADP aluminum diethylphosphinate, Exolit OP1230 from Clariant, Germany;
  • ABP aluminum diisobutylphosphinate, prepared according to U.S. Patent No. 7,807,737;
  • MPP melamine polyphosphate, Suzhou Kaima Chemical Technology Co., Ltd.;
  • Antioxidant 1010 Tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, Shanghai Macklin Biochemical Technology Co., Ltd.
  • Antioxidant 168 Tris[2,4-di-tert-butylphenyl] phosphite, Strem Company, USA.
  • Antioxidant 1010 tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid] pentaerythritol ester
  • antioxidant 168 tri[2,4-di-tert butylphenyl] phosphite
  • Combustion test standard GB/T 2408 ⁇ 2008 standard
  • Nuclear Magnetic Resonance (NMR) test the instrument model used is AVANCE III 400MHz, Bruker Company, Germany.
  • X-ray diffraction (XRD) test instrument model D8ADVANCE DAVINCI, German Bruker company.
  • Carry out XRD test to sample, gained XRD result is shown in Table 5:
  • the hybrid salt obtained in the present embodiment is alkaline hydrolyzed, and the 31 P-NMR (nuclear magnetic field) collection of spectra is shown in Figure 3, and the peak areas of these three peaks correspond to the molar concentrations of three phosphinate radicals respectively, therefore, by peak area The ratio of x, y, and z can be easily calculated.
  • Example 4a 49.46 grams of the reaction solution was taken and slowly added to a 15% aqueous solution containing 5.41 g of ferric chloride hexahydrate, the reaction temperature was controlled at 70° C., and the pH value was adjusted to be less than or equal to 2.0 to obtain a large amount of precipitation. After 1 hour the dropwise addition was complete. Filter while hot, and wash the filter cake with water until the pH>4.0. Afterwards, the filter cake was dried at 120° C. to obtain 8.40 g, with a yield of 93.7%.
  • *Long-chain alkyl includes ethyl n-butylphosphinate and butylbutylphosphinate.
  • Example 5a 51.3 grams of the reaction solution was taken and slowly added to a 15% aqueous solution containing 5.41 grams of ferric chloride hexahydrate, the reaction temperature was controlled at 70° C., and the pH value was adjusted to be less than or equal to 2.0 to obtain a large amount of precipitation. After 1 hour the dropwise addition was complete. Filter while hot, and wash the filter cake with water until the pH>4.0. Afterwards, the filter cake was dried at 120° C. to obtain 8.70 g, with a yield of 94.7%.
  • the above solution is first oxidized with a sufficient amount of 30% hydrogen peroxide to oxidize the mono-addition product, and then slowly added to a 10% aqueous solution containing 104.79 grams of aluminum sulfate octadecahydrate, the reaction temperature is controlled at 70°C, and the pH value is adjusted to be less than or equal to 2.9 , a large amount of precipitation was obtained. After 1 hour the dropwise addition was complete. Filter while hot, and wash the filter cake with water until the pH>4.5. Afterwards, the filter cake was dried at 120° C. to obtain 124.99 g, with a yield of 91.7%.
  • the above solution is first oxidized with a sufficient amount of 30% hydrogen peroxide to the mono-addition product, then take 500 grams of the solution, slowly add it to a 10% aqueous solution containing 13.33 grams of aluminum sulfate octadecahydrate, control the reaction temperature at 70 ° C, adjust When the pH value is less than or equal to 2.9, a large amount of precipitation is obtained. After 1 hour the dropwise addition was complete. Filter while hot, and wash the filter cake with water until the pH>4.5. Afterwards, the filter cake was dried at 120° C. to obtain 19.05 g, with a yield of 94%.
  • the dialkylphosphinic acid hybrid salt that obtains in embodiment 1, embodiment 2a, embodiment 4a, embodiment 7, embodiment 8, embodiment 9 is carried out TGA test, and the result is as shown in Figure 1, and Figure 1 is Thermogravimetric graphs (TGA) of hybrid salts with different x,y,z values and aluminum diethylphosphinate (ADP) and aluminum diisobutylphosphinate (ABP). It can be seen from the figure that aluminum diisobutylphosphinate has the earliest thermal weight loss and the lowest thermal stability. The larger the z value, the earlier the thermal weight loss of the hybrid salt.
  • Embodiment 10 (comparative example) iron diethylphosphinate
  • the flammability rating of the 1.6mm sample is UL94 V-0.
  • Example 2-9 The flame retardant of Example 2-9 was prepared and tested in polyamide PA66, PA6, PPA, and PBT according to the method of Example 11-13, and the results are shown in Table 23 and Table 24.
  • the polyamide PA66, the hybrid salt prepared by Example 8, MPP and compound antioxidant are mixed according to the weight ratio of 82.6:12:5:0.4 in an internal mixer whose rotation speed is 50 rpm, and set The temperature was 280°C, and after 5 minutes, it was taken out to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 280°C for 10 minutes, hold the pressure at 10MPa for 5 minutes, and then cold press it. Cut samples and test after cooling down.
  • the flammability rating of the 1.6mm sample is UL94 V-0.
  • Polyamide PA66, ferric diethylphosphinate prepared by Example 10, compound antioxidant according to the weight ratio of 79.6:20:0.4 are mixed in a internal mixer with a rotating speed of 50 rpm, set The temperature was 280°C, and after 5 minutes, it was taken out to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 280°C for 10 minutes, hold the pressure at 10MPa for 5 minutes, and then cold press it. Cut samples and test after cooling down.
  • the flame retardant grade of the 1.6mm sample is UL94 without grade.
  • Polyester PBT aluminum diisobutylphosphinate (ABP), compound antioxidant according to the weight ratio of 84.6:15:0.4, mixed in the internal mixer whose rotating speed is 50 rev/min, and the setting temperature is 260 °C, after 5 minutes, take it out to cool and dry. Then fill it into a mold, preheat it in a flat vulcanizing machine at 260°C for 10 minutes, hold the pressure at 10MPa for 5 minutes, and then cold press it. Cut samples and test after cooling down.
  • the flammability rating of the 1.6mm sample is UL94 V ⁇ 2.
  • Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
  • Example 11-41 illustrates that the flame retardant containing the hybrid salt of dialkylphosphinic acid of the present invention has outstanding flame retardant efficiency for both polyamide and polyester.
  • Comparative Example 1 illustrates that pure iron diethylphosphinate is less effective in flame retardant against polyamide and polyester.
  • Comparative examples 2-4 show that the flame retardant efficiency of pure aluminum diethylphosphinate is low for polyamide and polyester.
  • Comparative Example 5 shows that pure aluminum diisobutylphosphinate has a low flame retardant effect on polyester.
  • Comparative Example 6 shows that under the same amount of addition, pure aluminum diisobutylphosphinate is not as good as a hybrid salt containing ethylisobutylphosphinate for polyamide flame retardancy, see Examples 20, 26, 32 and 37. At the same time, it was found in the examples that for the hybrid salt containing diisobutylphosphinate, the more the content, the darker the color of the flame retardant sample, indicating more degradation. The polymer material sample obtained from pure diisobutylaluminum phosphinate has the darkest color.

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Abstract

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。具有式(Ⅰ)组成的二烷基次膦酸杂化盐对各类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对高分子材料阻燃效率低的缺点，并且克服了二异丁基次膦酸盐挥发性过高及其对聚酯阻燃效率低的缺点，可以广泛应用于各类需要高温加工的高分子材料的阻燃；式（I）结构式如下

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，二烷基次膦酸盐类阻燃产品密度较低，阻燃剂用量较小，机械性能好，但是现有的二烷基次膦酸盐作为阻燃剂的阻燃效率有限，如聚二烷基次膦酸盐可以作为无玻璃纤维增强尼龙的阻燃剂，阻燃效率低，并且使用时会给阻燃高分子材料的物理性能带来较大的不利影响。还有报道使用二异丁基次膦酸铝用于尼龙的阻燃，二异丁基次膦酸铝阻燃效率非常高，但其热稳定性较低，在300℃下就开始大量降解挥发，对需要高温加工的工程塑料不利。且二异丁基次膦酸铝对聚酯的阻燃效果不佳。同时，其塑化性较大，对阻燃高分子的物理性能不利。
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、应用，所述二烷基次膦酸杂化盐具有式(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，经济性好。
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 PCTCN2021124204-appb-000001
其中，M为中心原子，二乙基次膦酸根离子、乙基异丁基次膦酸根离子、二异丁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M的价态；n选自2,3或4；
0≤x≤0.95；0.05≤y≤0.8；0≤z≤0.5,且x+y+z＝1，x+z＞0。
本申请实施例中，在式(Ⅰ)中，y若小于0.05，阻燃效果不佳，y大于0.8，制备成本高，经济性差，并且二烷基次膦酸杂化盐的热稳定性会下降，对阻燃高分子材料的制备和物理性能不利。x若大于0.95，阻燃性能不佳。z若大于0.5，制备成本高，经济性差，并且热稳定性下降，对阻燃高分子材料制备和物理性能不利。
可选地，x的下限独立地选自0、0.15、0.2、0.25、0.3、0.35、0.45、0.5、0.55、0.6、0.65、0.7、0.03；上限独立地选自0.95、0.9、0.85、0.87、0.7。
可选地，y的下限独立地选自0.05、0.1、0.15、0.2、0.13、0.29；上限独立地选自0.8、0.7、0.6、0.5、0.4、0.35、0.3、0.25、0.68。
可选地，z的下限独立地选自0、0.02；上限独立地选自0.5、0.45、0.4、0.35、0.3、0.25、0.2、0.15、0.1、0.05。
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，0.03≤x≤0.87；0.13≤y≤0.68；0≤z≤0.45。
可选地，0.03≤x≤0.7；0.29≤y≤0.68；0.01≤z≤0.45。
可选地，0.5≤x≤0.7；0.29≤y≤0.48；0.01≤z≤0.21。
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，不是由二乙基次膦酸铝和乙基异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、乙基异丁基次膦酸根离子、二异丁基次膦酸离子组成的杂化盐。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，呈现单峰或重叠双峰。并且最大峰显示的晶面间距峰也与二乙基次 膦酸铝和二异丁基次膦酸铝的不同。二乙基次膦酸铝的最大峰显示晶面间距d＝9.663,二异丁基次膦酸铝的d＝12.084，而具有式(Ⅰ)二烷基次膦酸杂化盐的晶面间距d值介于上述两者之间。即使是重叠双峰，它们的d值也表明不是简单的二乙基次膦酸铝或者二异丁基次膦酸铝。但由二乙基次膦酸铝和二异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异丁基次膦酸铝的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通过简单的物理混合后，它们的XRD图谱中也出现2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、乙基异丁基次膦酸铝、二异丁基次膦酸铝的混合物，而是包含了二乙基次膦酸根、乙基异丁基次膦酸根以及二异丁基次膦酸根跟同一个铝原子配对的结构。
本申请实施例中，在相同的用量下，纯的二乙基次膦酸盐或者二异丁基次膦酸盐的阻燃效果远远不如同时含有二乙基次膦酸根和乙基异丁基次膦酸根的杂化盐。另外阻燃性能也跟乙基异丁基次膦酸根的含量有关，y只有在特定范围内的组成才具备良好的阻燃性能和热性能以及良好的经济性。
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、乙基异丁基次膦酸和/或其碱金属盐与二异丁基次膦酸和/或其碱金属盐。
可选地，所述二乙基次膦酸和/或其碱金属盐、乙基异丁基次膦酸和/或其碱金属盐、二异丁基次膦酸和/或其碱金属盐与金属元素M源的摩尔比接近为x:y:z:q；
其中，q＝1/n。
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，溶液当中二乙基次膦酸和/或其碱金属盐、乙基异丁基次膦酸和/或其碱金属盐、二异丁基次膦酸和/或其碱金属盐与杂化盐中的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，反应物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中二乙基次膦酸和/或其碱金属盐、乙基异丁基次膦酸和/或其碱金属盐与二异丁基次膦酸和/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。
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0.1-20h。
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异丁烯，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、异丁烯的摩尔比为1：0.05-1.95：0.5-1.5。
实际反应中，由于一些副反应的存在，譬如乙烯聚合得到的长链二烷基次膦酸盐，因此，烯烃的消耗量要高于理论比值。
可选地，所述次膦酸和/或其碱金属盐、乙烯、异丁烯的摩尔比和式(Ⅰ)中x,y,z值相同或接近。可选地，在所述反应II中，反应速率决定于x,y,z的值。z值越大，反应速度越慢，因此为了获得经济性，z值需要加以控制。同时，发现在次磷酸或其碱金属盐跟乙烯或异丁烯反应过程中，y值有一个小于1的最大值，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/或二异丁基次膦酸或者它们的盐，对经济性不利。
具体地，在反应II中，乙烯和异丁烯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/或其碱金属盐先与异丁烯反应，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、异丁基次膦酸根、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。
具体地，在反应I结束后，无需分离出二乙基次膦酸、乙基异丁基次膦酸、二异丁基次膦酸或它们的碱金属的混合物，直接进行下一步反应即可。
可选地，在所述水溶液中，所述水的质量为所述自由基引发剂与所述次膦酸和/或其碱金属盐的总质量的10‐99％。
具体地，在所述水溶液中，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，在所述水溶液中，所述水的质量为所述自由基引发剂与所述次膦酸和/或其碱金属盐的总质量的20‐95％。
可选地，在所述水溶液中，所述水的质量为所述自由基引发剂与所述次膦酸和/或其碱金属盐的总质量的45‐92％。
可选地，在所述水溶液中，所述水的质量为所述自由基引发剂与所述次膦酸和/或其碱金属盐的总质量的50‐90％。
可选地，在所述水溶液中，所述水的质量为所述自由基引发剂与所述次膦酸和/或其碱金属盐的总质量的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，次膦酸盐容易分解。
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膦酸和/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'‐偶氮二异丁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自由基引发剂，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，自由基引发剂为过氧化物类。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异丁烯进行反应，待通入的异丁烯跟次膦酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入异丁烯，再继续通入乙烯反应，得到所述混合物A。
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异丁烯，待所述异丁烯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。
可选地，次膦酸和/或其碱金属盐与异丁烯先反应来获得具有或大体上接近y值的单异丁基次膦酸或其碱金属盐，并且控制z小于等于0.5，然后再停止加入异丁烯，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。
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异丁烯和部分乙烯进行反应，乙烯跟次膦酸和/或其碱金属盐的总磷摩尔之比小于式(Ⅰ)中的(2x+y)/1，待通入的异丁烯跟次膦酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入异丁烯，再继续通入剩余部分乙烯反应，得到所述混合物A。
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异丁烯和部分乙烯，待所述异丁烯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；
所述乙烯的总量和所述异丁烯的摩尔比为0.33‐39:1。
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部分乙烯，所述部分乙烯跟次膦酸和/或其碱金属盐总磷的摩尔之比小于式(Ⅰ)中的(2x+y)/1，待所述部分乙烯反应完全后，再继续通入异丁烯进行反应，待通入的异丁烯跟次膦酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入异丁烯，继续通入剩余部分乙烯进行反应，得到所述混合物A。
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，再继续通入异丁烯进行反应，待所述异丁烯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；
所述乙烯的总量和所述异丁烯的摩尔比为0.33‐39:1。
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，次膦酸和/或其碱金属盐同时跟异丁烯和部分乙烯在自由基引发剂存在下进行反应，控制异丁烯和乙烯的量，待反应体系中异丁基次膦酸或其碱金属盐摩尔百分比接近y值，且二异丁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0.5，停止加入异丁烯，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。
根据本申请的第三方面，还提供了一种阻燃剂，所述阻燃剂包括上述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，还含有选自磷酸根离子、亚磷酸根离子、烷基膦酸根离子、烷基次膦酸根离子中的至少一种,这些含磷的酸根离子在所述阻燃剂中的摩尔含量小于等于10％摩尔阻燃剂，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选自上述二烷基次膦酸杂化盐、上述阻燃剂中的至少一种在阻燃材料中的应用。
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。
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，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，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。
本领域技术人员可根据具体需要，可以在阻燃材料中添加其它阻燃剂B，譬如氮类阻燃剂，包括三聚氰胺氰尿酸酯；磷-氮类阻燃剂，包括三聚氰胺聚磷酸盐，多聚磷酸铵等；以及硼系阻燃剂，包括硼酸锌等。
可选地，所述阻燃材料中包括用量为5-40％重量百分比的增强玻璃纤维。其他助剂譬如稳定剂、抗滴落剂、颜料、染料、成炭催化剂、分散剂、阻燃剂、成核剂以及无机填料譬如云母石、碳酸钙、氧化钙、硅石或它们的混合物也可以包含在内，所有成分加起来为100％重量百分比。
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的离子。由于原材料含杂质或者合成工艺生成杂质的原因，一些微量的磷酸根离子、亚磷酸根离子、烷基膦酸根离子、烷基次膦酸根离子可能会存在于阻燃剂中。一些由乙烯聚合而来的齐聚物产物，譬如乙基正丁基次膦酸根离子、乙基己基次膦酸根离子、丁基丁基次膦酸根离子、丁基己基次膦酸根离子也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量不超过总磷的10％摩尔，并不影响式(Ⅰ)组成阻燃剂的正常工作。
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、乙基异丁基次膦酸根、二异丁基次膦酸根具有不同的 31P的化学位移，在 31P‐NMR谱中呈现独立地三个峰，这三个峰的峰面积分别对应三个次膦酸根的摩尔浓度，因此，通过峰面积的比例，可以很方便地计算出x,，y，和z的值。
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，对各类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对高分子材料阻燃效率低的缺点，并且克服了二异丁基次膦酸盐挥发性过高及其对聚酯阻燃效率低的缺点，可以广泛应用于各类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，避免了需要独立制备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盐以及二乙基次膦酸铝和二异丁基次膦酸铝的热失重曲线图(为显示方便起见，表头显示的数值是x,y,z的100倍)；
图2为具有不同x,y,z值的二烷基次膦酸杂化盐、二乙基次膦酸铝和二异丁基次膦酸铝的XRD曲线(为显示方便起见，表头显示的数值是x,y,z的100倍，物理混合指的是二乙基次膦酸铝和二异丁基次膦酸铝的混合)；
图3为实施例3中的二烷基次膦酸杂化盐碱解后的 31P‐NMR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；
PPA(高温尼龙)：美国杜邦HTN 51G35HSL NC010，玻璃纤维含量为35％重量百分比；
PBT(聚对苯二甲酸丁二醇酯):美国杜邦Crastin SK605NC010，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；
ABP:二异丁基次膦酸铝，根据美国专利7807737制备；
MPP:三聚氰胺聚磷酸盐，苏州凯马化学科技有限公司；
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 400MHz，德国Bruker公司。
核磁共振磷谱( 31P‐NMR)测试方法：以85％磷酸的化学位移为0，预延期D1＝10秒，扫描32次，并以峰面积之比作为二乙基次膦酸根，乙基异丁基次膦酸根，二异丁基次膦酸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。
实施例1
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.87,y＝0.13,z＝0,M＝Al，n＝3的制备
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，充异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0.3MPa，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 续往反应釜通入异丁烯，通过气体流量表来计量烯烃的通入量。0.3小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。9.0小时后停止通乙烯，但继续打入引发剂，半小时后反应釜压力不再下降，说明反应完全，降温泄压、N 2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁， 31P‐NMR结果如表1所示：
表1
Figure PCTCN2021124204-appb-000002
*长链烷基次膦酸根：包括乙基正丁基次膦酸根，乙基己基次膦酸根，丁基丁基次膦酸根。
将上述部分溶液690克，慢慢加入到20％质量浓度的含89.97克十八水合硫酸铝的水溶液，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。1小时后滴加完全。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106.75克，收率92.9％。将样品溶解于氢氧化钠的水溶液中，做磷核磁,得到二乙基次膦酸根85.79％，乙基异丁基次膦酸根12.36％，二异丁基次膦酸根0.45％，剩余的为长链烷基次膦酸根、乙基膦酸根以及亚磷酸根杂质，归一化后得到x＝0.87,y＝0.13,z＝0。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000003
(100％)；
Figure PCTCN2021124204-appb-000004
(66.1％)，结果如表2所示。
表2
Figure PCTCN2021124204-appb-000005
实施例2a 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.83,y＝0.16,z＝0.01,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，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异丁烯，通过气体流量表来计量烯烃的通入量。1.0小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。9.0小时后停止通乙烯，但继续打入引发剂，半小时后反应釜压力不再下降，说明反应完全，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 PCTCN2021124204-appb-000006
将上述部分溶液766克，慢慢加入到20％质量浓度的含89.97克十八水合硫酸铝的水溶液，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。1小时后滴加完全。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95.2克白色粉末状产品，收率90.7％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，得到二乙基次膦酸根80.35％，乙基异丁基次膦酸根16.05％，二异丁基次膦酸根0.70％，剩余的为长链烷基次膦酸根、乙基膦酸根、以及亚磷酸根杂质，归一化之后得到x＝0.83,y＝0.16,z＝0.01。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000007
(100％)；
Figure PCTCN2021124204-appb-000008
(86.7％)，结果如表4所示。
表4
Figure PCTCN2021124204-appb-000009
实施例2b 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.83,y＝0.16,z＝0.01,M＝Cu，n＝2的制备
按照实施例2a的方法,用硫酸铜代替硫酸铝，获得铜的杂化盐，x＝0.83,y＝0.16,z＝0.01。对样品进行XRD测试，所得XRD结果如表5所示：
表5
Figure PCTCN2021124204-appb-000010
实施例3 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.70,y＝0.29,z＝0.01,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异丁烯至压力不再 上升。对反应液加热至90℃左右，此时压力表显示为0.3MPa，然后以10ml/h的速度匀速打入3.0％质量浓度过硫酸钠水溶液，并持续往反应釜通入异丁烯，通过气体流量表来计量烯烃的通入量。1.5小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。10.5小时后停止通乙烯，但继续打入引发剂，半小时后反应釜压力不再下降，说明反应完全。降温泄压、N 2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁的结果如表6所示：
表6
Figure PCTCN2021124204-appb-000011
取上述溶液724克，慢慢加入到20％质量浓度的含104.79克十八水合硫酸铝的水溶液，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。1小时后滴加完全。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117.5克，收率90.2％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，得到二乙基次膦酸根69.15％，乙基异丁基次膦酸根28.57％，二异丁基次膦酸根1.12％，剩余的为长链烷基次膦酸根杂质，归一化之后得到x＝0.70,y＝0.29,z＝0.01。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000012
(100％)；
Figure PCTCN2021124204-appb-000013
(47.4％)，结果如表7所示。
表7
Figure PCTCN2021124204-appb-000014
将本实施例中得到的杂化盐碱解， 31P‐NMR(核磁)图谱如图3所示，这三个峰的峰面积分别对应三个次膦酸根的摩尔浓度，因此，通过峰面积的比例，可以很方便地计算出x,，y，和z的值。
实施例4a 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.60,y＝0.38,z＝0.02,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，然后以10ml/h的速度匀速打入3.0％质量浓度过硫酸钠水溶液，并持续往反应釜通入异丁烯，通过气体流量表来计量烯烃的通入量。2.0小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。15.5小时后停止通乙烯，但继续打入引发剂，半小时后反应釜压力不再下降，说明反应完全。降温泄压、N 2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁的结果如表8所示：
表8
Figure PCTCN2021124204-appb-000015
取上述溶液847克慢慢加入到20％质量浓度的含104.79克十八水合硫酸铝的水溶液，控制反应温度为70℃，调节pH值小于等于3.0，得到大量沉淀。1小时后滴加完全。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126.1克，收率94.9％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，得到二乙基次膦酸根60.29％，乙基异丁基次膦酸根38.24％，二异丁基次膦酸根1.47％，即x＝0.60,y＝0.38,z＝0.02。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000016
(100％)；
Figure PCTCN2021124204-appb-000017
(14.2％)，结果如表9所示。
表9
Figure PCTCN2021124204-appb-000018
实施例4b 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.63,y＝0.36,z＝0.01,M＝Fe，n＝3的制备
按照实施例4a，取反应溶液49.46克，慢慢加入到15％的含5.41g六水氯化铁的水溶液中，控制反应温度70℃，调节pH值小于等于2.0，得到大量沉淀。1小时后滴加完全。趁热过滤，滤饼用清水洗至pH＞4.0。之后滤饼在120℃下烘干，得到8.40克，收率93.7％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，得到二乙基次膦酸根63.26％，乙基异丁基次膦酸根35.82％，二异丁基次膦酸根0.92％，即x＝0.63,y＝0.36,z＝0.01。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000019
(100％)；
Figure PCTCN2021124204-appb-000020
(8.0％)，结果如表10所示。
表10
Figure PCTCN2021124204-appb-000021
实施例4c 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.62,y＝0.37,z＝0.01,M＝Zn，n＝2的制备
按照实施例4a，取反应溶液197.85克，慢慢加入到15％的含34.51克七水硫酸锌的水溶液中，控制反应温度70℃，滴加完毕之后， 降温，烘干,得到白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁，得到二乙基次膦酸根62.0％，乙基异丁基次膦酸根36.7％，二异丁基次膦酸根1.3％，即x＝0.62,y＝0.37,z＝0.01。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000022
(100％)；
Figure PCTCN2021124204-appb-000023
(57.6％)，结果如表11所示。
表11
Figure PCTCN2021124204-appb-000024
实施例5a 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.45,y＝0.52,z＝0.03,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，然后以10ml/h的速度匀速打入3.0％质量浓度过硫酸钠水溶液，并持续往反应釜通入异丁烯。5.5小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。17小时后反应完全，停止通乙烯，降温泄压、N 2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁的结果如表12所示：
表12
Figure PCTCN2021124204-appb-000025
*长链烷基：包括乙基正丁基次膦酸根和丁基丁基次膦酸根。
取上述溶液445克，慢慢加入到10％的含59.98克十八水合硫酸铝的水溶液中，控制反应温度70℃，调节pH值小于等于2.9，得到大量沉淀。1小时后滴加完全。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69.3克，收率89％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，结果如下：二乙基次膦酸根44.18％，乙基异丁基次膦酸根50.45％，二异丁基次膦酸根3.24％，剩余的为长链烷基次膦酸根和乙基膦酸根杂质。归一化之后得x＝0.45,y＝0.52,z＝0.03。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000026
(100％)；
Figure PCTCN2021124204-appb-000027
(12.7％)，结果如表13所示。
表13
Figure PCTCN2021124204-appb-000028
Figure PCTCN2021124204-appb-000029
实施例5b 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.48,y＝0.49,z＝0.03,M＝Fe，n＝3的制备
按照实施例5a，取反应溶液51.3克，慢慢加入到15％的含5.41克六水氯化铁的水溶液中，控制反应温度70℃，调节pH值小于等于2.0，得到大量沉淀。1小时后滴加完全。趁热过滤，滤饼用清水洗至pH＞4.0。之后滤饼在120℃下烘干，得到8.70克，收率94.7％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，结果如下：二乙基次膦酸根47.22％，乙基异丁基次膦酸根48.25％，二异丁基次膦酸根2.13％，剩余的为长链烷基次膦酸根和乙基膦酸根杂质。归一化之后得x＝0.48,y＝0.49,z＝0.03。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000030
(100％)；
Figure PCTCN2021124204-appb-000031
(11.2％)，结果如表14所示。
表14
Figure PCTCN2021124204-appb-000032
实施例6 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.31,y＝0.64,z＝0.05,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，然后以10ml/h的速度匀速打入4.0％2,2'‐偶氮双(2‐脒基丙烷)二氢氯化物水溶液，并持续往反应釜通入异丁烯。9.5小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。20小时后反应完全，停止通乙烯，降温泄压、N2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁的结果如表15所示：
表15
Figure PCTCN2021124204-appb-000033
取上述溶液512克，慢慢加入到10％的含59.98克十八水合硫酸铝的水溶液中，控制反应温度70℃，调节pH值小于等于2.9，得到大量沉淀。1小时后滴加完全。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74.46克，收率93.7％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，结果如下：二乙基次膦酸根30.76％，乙基异丁基次膦酸根63.27％，二异丁基次膦酸根4.60％，剩余的为长链烷基次膦酸根和乙基膦酸根杂质。归一化之后得x＝0.31,y＝0.64,z＝0.05。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000034
(100％)；
Figure PCTCN2021124204-appb-000035
(9.9％)，结 果如表16所示。
表16
Figure PCTCN2021124204-appb-000036
实施例7 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.28,y＝0.68,z＝0.04,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，然后以10ml/h的速度匀速打入3.0％质量浓度过硫酸钠水溶液，并持续往反应釜通入异丁烯。10.5小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。21小时后反应基本完全，停止通乙烯，降温泄压、N 2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁的结果如表17所示：
表17
Figure PCTCN2021124204-appb-000037
将上述溶液用足量的30％双氧水将单加成产物先氧化，然后慢慢加入到10％的含104.79克十八水合硫酸铝的水溶液中，控制反应温度70℃，调节pH值小于等于2.9，得到大量沉淀。1小时后滴加完全。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124.99克，收率91.7％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，结果如下：二乙基次膦酸根27.78％，乙基异丁基次膦酸根66.83％，二异丁基次膦酸根4.00％，其余为其他含磷杂质。归一化之后得x＝0.28,y＝0.68,z＝0.04。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000038
(100％)；
Figure PCTCN2021124204-appb-000039
(12.6％)，结果如表18所示。
表18
Figure PCTCN2021124204-appb-000040
实施例8 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.03,y＝0.58,z＝0.39,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，然后以10ml/h的速度匀速打入3.0％质量浓度过硫酸钠水溶液，并持续往反应釜通入异丁烯。13小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。25小时后停止通乙烯，降温泄压、N2吹扫、放料得无色透明反应液。
将上述溶液用足量的30％双氧水将单加成产物先氧化，然后取500克溶液，慢慢加入到10％的含13.33克十八水合硫酸铝的水溶液中，控制反应温度70℃，调节pH值小于等于2.9，得到大量沉淀。1小时后滴加完全。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19.05克，收率94％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，结果如下：二乙基次膦酸根2.69％，乙基异丁基次膦酸根52.89％，二异丁基次膦酸根35.84％。归一化之后得x＝0.03，y＝0.58,z＝0.39。
对样品进行XRD测试，所得XRD测定的相对强度最高和次高的特征峰对应的层间距分别为
Figure PCTCN2021124204-appb-000041
(100％)；
Figure PCTCN2021124204-appb-000042
(11.7％)，结果如表19所示。
表19
Figure PCTCN2021124204-appb-000043
实施例9 具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.03,y＝0.52,z＝0.45,M＝Al，n＝3的制备
将100克一水次磷酸钠溶解于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，充异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0.3MPa，然后以10ml/h的速度匀速打入3.0％质量浓度过硫酸钠水溶液，并持续往反应釜通入异丁烯。15小时后，停止通异丁烯，开始通入乙烯，并增加压力到0.8MPa。27小时后反应完全，停止通乙烯，降温泄压、N 2吹扫、放料得无色透明反应液。
反应中间过程取样，做核磁的结果如表20所示：
表20
Figure PCTCN2021124204-appb-000044
取上述溶液280克，慢慢加入到10％的含7.46克十八水合硫酸铝的水溶液中，控制反应温度70℃，调节pH值小于等于2.9，得到大量沉淀。1小时后滴加完全。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10.7克，收率94.3％。
将样品溶解于氢氧化钠的水溶液中，做磷核磁，结果如下：二乙基次膦酸根2.9％，乙基异丁基次膦酸根51.0％，二异丁基次膦酸根43.5％。归一化之后得x＝0.03,y＝0.52,z＝0.45。
对干燥后的样品进行XRD测试，所得X‐射线衍射(XRD)结果如下表1，从表1中相对强度最高的特征峰可知，层间距主要为
Figure PCTCN2021124204-appb-000045
Figure PCTCN2021124204-appb-000046
结果如表21所示。
表21
Figure PCTCN2021124204-appb-000047
对实施例1、实施例2a、实施例4a、实施例7、实施例8、实施例9中得到的二烷基次膦酸杂化盐进行TGA测试，结果如图1所示，图1是具有不同x,y,z值的杂化盐以及二乙基次膦酸铝(ADP)和二异丁基次膦酸铝(ABP)的热失重曲线图(TGA)。由图可知，二异丁基次膦酸铝热失重最早，热稳定性最低。z值越大，杂化盐的热失重越早。
实施例10 (对比实例)二乙基次膦酸铁
将93.82克18.4％重量的二乙基次膦酸钠水溶液(含乙基丁基次膦酸钠2.1摩尔％以及乙基膦酸钠0.5摩尔％)慢慢加入到15％质量浓度含10.81克六水氯化铁的水溶液中，保持反应温度70℃，pH＝2,半小时加完，保温半小时。趁热过滤，滤饼用清水洗至pH＞4。之后滤饼在120℃下烘干，得到15.5克，收率92.5％。
对样品进行XRD测试,结果如表22所示：
表22
Figure PCTCN2021124204-appb-000048
实施例11
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UL94 V‐1。
实施例12
将聚酰胺PA6、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UL94 V‐1。
实施例13
将聚酯PBT、由实施例1制备过来的杂化盐、复配抗氧剂按照84.6:15：0.4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UL94 V‐0。
实施例14‐40
将实施例2‐9阻燃剂分别在聚酰胺PA66，PA6，PPA，以及PBT中按照实施例11‐13的方式进行制样和测试，结果见表23和表24。
实施例41
将聚酰胺PA66、由实施例8制备过来的杂化盐、MPP以及复配抗氧剂按照82.6:12:5：0.4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 V‐0。
对比例1
将聚酰胺PA66、由实施例10制备过来的二乙基次膦酸铁、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2
将聚酰胺PA66、ADP、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、ADP、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。
对比例4
将聚酯PBT、ADP、复配抗氧剂按照84.6:15:0.4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UL94 V‐2。
对比例5
将聚酯PBT、二异丁基次膦酸铝(ABP)、复配抗氧剂按照84.6:15:0.4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UL94 V‐2。
对比例6
将聚酰胺PA66、二异丁基次膦酸铝(ABP)、复配抗氧剂按照87.1:12.5：0.4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 V‐1。
对比例结果见表25。
Figure PCTCN2021124204-appb-000049
Figure PCTCN2021124204-appb-000050
表25 对比例1‐对比例6的配方及测试结果
  对比例1 对比例2 对比例3 对比例4 对比例5 对比例6
PA66 79.6 79.6       87.1
PA6     79.6      
PBT       84.6 84.6  
阻燃剂制备 实施例10          
式(Ⅰ) 1.00/0/0/Fe          
阻燃剂份数 20          
ADP   20 20 15    
ABP         15 12.5
复配抗氧剂 0.4 0.4 0.4 0.4 0.4 0.4
UL‐94 NG NG NG V‐2 V‐2 V‐1
*：NG无等级
实施例11‐41说明含有本发明二烷基次膦酸杂化盐的阻燃剂对聚酰胺和聚酯都具有突出的阻燃效率。对比例1说明纯的二乙基次膦酸铁阻燃效率对聚酰胺和聚酯低。对比例2‐4说明纯的二乙基次膦酸铝阻燃效率对聚酰胺和聚酯低。对比例5说明纯的二异丁基次膦酸铝对聚酯阻燃效率低。对比例6说明在相同的添加量下，纯的二异丁基次膦酸铝对聚酰胺阻燃不如含有乙基异丁基次膦酸根的杂化盐，见实施例20，26，32和37。同时，在实施例中发现，对含有二异丁基次膦酸根的杂化盐，含量越多，阻燃样品的颜色越深，说明降解越多。由纯二异丁基次膦酸铝阻燃得到的高分子材料样品颜色最深。
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 (22)

  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 PCTCN2021124204-appb-100001
    其中，M为中心原子，二乙基次膦酸根离子、乙基异丁基次膦酸根离子、二异丁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M的价态；n选自2,3或4；
    0≤x≤0.95；0.05≤y≤0.8；0≤z≤0.5,且x+y+z＝1，x+z＞0。
  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，0.03≤x≤0.87；0.13≤y≤0.68；0≤z≤0.45。
  4. 根据权利要求3所述的二烷基次膦酸杂化盐，其特征在于，0.03≤x≤0.7；0.29≤y≤0.68；0.01≤z≤0.45。
  5. 权利要求1至4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、乙基异丁基次膦酸和/或其碱金属盐与二异丁基次膦酸和/或其碱金属盐。
  6. 根据权利要求5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0.1-20h。
  7. 根据权利要求5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异丁烯，反应II，得到所述混合物A。
  8. 根据权利要求7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自由基引发剂与所述次膦酸和/或其碱金属盐的总质量的10-99％。
  9. 根据权利要求7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。
  10. 根据权利要求7所述的制备方法，其特征在于，所述自由基引发剂与所述次膦酸和/或其碱金属盐总量的摩尔比为0.001-0.1：1。
  11. 根据权利要求7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异丁烯进行反应，待通入的异丁烯跟次膦酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入异丁烯，再继续通入乙烯反应，得到所述混合物A。
  12. 根据权利要求7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异丁烯和部分乙烯进行反应，乙烯跟次膦酸和/或其碱金属盐的总磷摩尔之比小于式(Ⅰ)中的(2x+y)/1，待通入的异丁烯跟次膦酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入异丁烯，再继续通入剩余部分乙烯反应，得到所述混合物A。
  13. 根据权利要求7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部分乙烯，所述部分乙烯跟次膦酸和/或其碱金属盐总磷的摩尔之比小于式(Ⅰ)中的(2x+y)/1，待所述部分乙烯反应完全后，再继续通入异丁烯进行反应，待通入的异丁烯跟次膦酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入异丁烯，继续通入剩余部分乙烯进行反应，得到所述混合物A。
  14. 根据权利要求5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。
  15. 一种阻燃剂，其特征在于，所述阻燃剂选自权利要求1至4任一项所述的二烷基次膦酸杂化盐。
  16. 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15所述的阻燃剂中的至少一种。
  17. 根据权利要求16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％。
  18. 根据权利要求16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。
  19. 根据权利要求18所述的阻燃材料，其特征在于，所述功能添加剂在所述阻燃材料中的质量含量为5-40％。
  20. 根据权利要求18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。
  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Q在所述阻燃材料中的质量含量为0.5-20％。
  22. 根据权利要求16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。
PCT/CN2021/124204 2021-10-15 2021-10-15 二烷基次膦酸杂化盐及其制备方法、应用 WO2023060590A1 (zh)

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US7807737B2 (en) 2004-06-22 2010-10-05 Icl-Ip America Inc. Phosphorus-containing flame retardant for thermoplastic polymers
CN104119377A (zh) * 2014-04-01 2014-10-29 中国科学院宁波材料技术与工程研究所 二烷基次膦酸盐的制备工艺及产品
CN106279268A (zh) * 2015-06-12 2017-01-04 中国科学院宁波材料技术与工程研究所 二烷基次膦酸类化合物的制备方法及其应用
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