WO2023201541A1 - 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 PDFInfo
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- WO2023201541A1 WO2023201541A1 PCT/CN2022/087756 CN2022087756W WO2023201541A1 WO 2023201541 A1 WO2023201541 A1 WO 2023201541A1 CN 2022087756 W CN2022087756 W CN 2022087756W WO 2023201541 A1 WO2023201541 A1 WO 2023201541A1
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- WIPO (PCT)
- Prior art keywords
- flame retardant
- acid
- salt
- propylene
- reaction
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- 238000000034 method Methods 0.000 title claims abstract description 8
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WAAOFXJSLMXEIQ-UHFFFAOYSA-N ethyl(propan-2-yl)phosphinic acid Chemical compound CCP(O)(=O)C(C)C WAAOFXJSLMXEIQ-UHFFFAOYSA-N 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ZZQOYTDRIVRGAP-UHFFFAOYSA-N propan-2-yl(propyl)phosphinic acid Chemical compound CCCP(O)(=O)C(C)C ZZQOYTDRIVRGAP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- 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.
- Dialkyl phosphinate especially aluminum diethyl phosphinate, has been widely used as a halogen-free flame retardant for polymer materials.
- the density of dialkyl phosphinate flame retardant products is low, and the amount of flame retardant is low. Smaller, good mechanical properties, but the flame retardant efficiency of existing dialkyl phosphinates as flame retardants is limited.
- dialkyl phosphinates can be used as flame retardants for non-glass fiber reinforced nylon, flame retardant The efficiency is low, and when used, it will have a greater adverse impact on the physical properties of flame-retardant polymer materials.
- Aluminum dipropylphosphinate has high flame retardant efficiency, but its thermal stability is low and it begins to degrade and volatilize in large quantities at 300°C. , which is detrimental to engineering plastics that require high-temperature processing, such as nylon 66.
- dialkyl phosphinate when dialkyl phosphinate is used as a flame retardant, in addition to its flame retardant properties, it is desired that the flame retardant has a large particle size and density during preparation and use to reduce filtration time and dust. And when mixed with polymer materials, the free flow speed of the two in the feeding barrel will not be inconsistent due to too large a density difference, resulting in poor uniformity of the distribution of the flame retardant in the flame retardant material.
- the dialkylphosphinic acid hybrid salt has a dialkylphosphinic acid hybrid salt composed of formula (I). Phosphonic acid hybrid salt.
- This hybrid salt has a small amount of addition. It has high flame retardant efficiency for various polymer materials and good thermal stability. It can meet the processing requirements of engineering plastics that require high temperatures. It has large particles and low dust.
- 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, R 1 and R 2 are independently selected from any one of n-propyl and isopropyl; diethylphosphinate ion, ethylpropylphosphinate ion, di Propylphosphinate ions are all ligands; and at least two acid ions among diethylphosphinate ion, ethylpropylphosphinate ion and dipropylphosphinate ion are paired with the same metal atom, and among them One ligand must be an ethylpropylphosphinate ion;
- 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 metal M; n is selected from 2, 3 or 4;
- the propyl group in the ethylpropylphosphinate ion and dipropylphosphinate ion is n-propyl or isopropyl.
- the lower limit of x is independently selected from 0, 0.03, 0.05, 0.10, 0.15; the upper limit is independently selected from 0.80, 0.75, 0.70, 0.65, 0.55, 0.50, 0.45, 0.40, 0.35, 0.30.
- 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 0.70, 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, 0.05, 0.08; the upper limit is independently selected from 0.95, 0.9, 0.85, 0.80, 0.75, 0.7, 0.65, 0.60, 0.55, 0.50, 0.45, 0.40, 0.35, 0.3, 0.25, 0.2, 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 IV A 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.
- it is not a simple mixture of aluminum diethylphosphinate and aluminum ethylpropylphosphinate.
- the mixture is composed of at least two ions of diethylphosphinate ion, ethylpropylphosphinate ion, and dipropylphosphinate ion coordinated with the same aluminum atom.
- a hybrid salt, and one of the ligands in the hybrid salt is an ethylpropylphosphinate ion.
- the X-ray diffraction (XRD) patterns 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 interplanar spacing displayed by the maximum peak is also different from that of aluminum diethylphosphinate and aluminum dipropylphosphinate.
- the value is basically between the above two.
- the physical mixed salt obtained by simply mixing aluminum diethylphosphinate and aluminum dipropylphosphinate shows two completely independent peaks in the XRD pattern, and their d values are close to diethylphosphinate respectively.
- the d value of aluminum phosphate and aluminum dipropylphosphinate shows two completely independent peaks in the XRD pattern, and their d values are close to diethylphosphinate respectively.
- dialkylphosphinic acid hybrid salt having formula (I) after simple physical mixing of the dialkylphosphinic acid hybrid salt having formula (I) and aluminum diethylphosphinate or aluminum dipropylphosphinate, their XRD patterns Two independent peaks also appear in the strongest absorption peak area. These results strongly indicate that the dialkylphosphinic acid hybrid salt having formula (I) obtained in the present invention is not simply aluminum diethylphosphinate, aluminum ethylpropylphosphinate, or dipropylphosphinate.
- It is a mixture of aluminum phosphates, but contains a structure in which at least two acid ions of diethylphosphinate, ethylpropylphosphinate, and dipropylphosphinate are paired with the same aluminum atom.
- pure aluminum dipropylphosphinate has good flame retardant effect, its thermal stability is low, making it difficult to meet the requirements of polymer materials that require high-temperature processing.
- pure aluminum dipropylphosphinate is dusty and difficult to operate.
- the particles of pure aluminum dipropylphosphinate are fine, when mixed with polymer materials, it is easy to cause local delamination and poor mixing uniformity.
- the dialkylphosphinic acid hybrid salt with formula (I) has high thermal stability, large particles, no dust, and has a flow rate similar to that of polymer particles in the feeding barrel, and has good mixing uniformity. .
- the flame retardant effect of pure diethylphosphinate is not good, and is far inferior to the flame retardant effect of the dialkylphosphinic acid hybrid salt composed of formula (I) good.
- 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 diethylphosphinic acid and/or its alkali metal salt, ethylpropylphosphinic acid and/or its alkali metal salt, and dipropylphosphinic acid and/or its alkali metal salt.
- 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.
- hybrid salts with high solubility diethylphosphinic acid and/or its alkali metal salts, ethylpropylphosphinic acid and/or its alkali metal salts, dipropylphosphinic acid and/or its bases are included in the solution.
- the values of x, y, and z in the 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 theoretical calculated value.
- the actual values of x, y, z and q can be determined by phosphorus NMR.
- the mixture A includes diethylphosphinic acid and/or its alkali metal salt, ethylpropylphosphinic acid and/or its alkali metal salt and dipropylphosphinic acid and/or its alkali metal salt.
- the molar ratio of the salt is the same or substantially the same as the x, y, z ratio in formula (I).
- the conditions of the reaction I are: temperature is 0-250°C; pressure is 0.1MPa-10MPa; time is 0.1-20h.
- obtaining the mixture A includes the following steps:
- Ethylene and propylene are passed into an aqueous solution containing phosphinic acid and/or its alkali metal salt and a free radical initiator to perform reaction II to obtain the mixture A.
- the molar ratio of the phosphinic acid and/or its alkali metal salt, ethylene, and propylene is 1:0.05-1.8:0.2-1.95.
- reaction II the order of adding ethylene and propylene can be interchanged, they can be added at the same time, or some of them can be added first.
- hypophosphorous acid and/or its alkali metal salt reacts with propylene first, and then reacts with ethylene substantially completely or completely after obtaining the corresponding y and z values.
- Roughly complete means that the total phosphorus contained in ethylphosphinate, propylphosphinate and phosphinate in the reaction mixture is less than 5 mol% of the total phosphorus in the reaction liquid.
- 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.
- reaction II temperature is 0-250°C; time is 0.01-50h; pressure is 0-3MPa.
- 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 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'-Azodipropylamidine One or more hydrochlorides.
- the peroxide initiator is preferably an inorganic peroxide and an organic peroxide free radical initiator, particularly preferably hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, and sodium percarbonate. , benzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, or one or more of peracetic acid.
- the free radical initiator is a peroxide.
- 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.
- obtaining the mixture A includes the following steps:
- Propylene is passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salts and a free radical initiator to carry out the reaction.
- the ratio of propylene to be introduced to the total phosphorus molar ratio of hypophosphorous acid and/or its alkali metal salts reaches the formula (I ) in (y+2z)/1, stop feeding propylene, and then continue to feed ethylene for reaction to obtain the mixture A.
- obtaining the mixture A includes the following steps:
- Propylene is passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator. After the propylene reaction is complete or nearly complete, the ethylene reaction is continued to be introduced to obtain the mixture A.
- hypophosphorous acid and/or its alkali metal salt reacts with propylene first to obtain monopropylphosphinic acid or its alkali metal salt with a y value or substantially close to it, and control z to be less than or equal to 0.95, and then stop adding Propylene is added to ethylene instead, and the reaction continues in the presence of an initiator, and then reacts with the required metal salt to obtain a flame retardant of formula (I).
- obtaining the mixture A includes the following steps:
- Propylene and part of ethylene are passed into an aqueous solution containing hypophosphorous acid and/or its alkali metal salt and a free radical initiator for reaction.
- the total phosphorus molar ratio between ethylene and hypophosphorous acid and/or its alkali metal salt is less than the formula (I) (2x+y)/1 in formula (I), stop feeding after the total phosphorus molar ratio of propylene and hypophosphorous acid and/or its alkali metal salt reaches (y+2z)/1 in formula (I) propylene, and then continue to feed the remaining part of ethylene for reaction to obtain the mixture A.
- obtaining the mixture A includes the following steps:
- the molar ratio of the total amount of ethylene to the propylene is 0.026-9:1.
- 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 feed propylene for reaction, the ratio of the propylene to be fed to the total phosphorus molar ratio of the starting hypophosphorous acid and/or its alkali metal salt After reaching (y+2z)/1 in formula (I), the flow of propylene is stopped, and the remaining part of ethylene is continued to be fed for reaction to obtain the mixture A.
- obtaining the mixture A includes the following steps:
- the molar ratio of the total amount of ethylene to the propylene is 0.026-9:1.
- 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.
- hypophosphinic acid and/or its alkali metal salts are simultaneously reacted with propylene and part of ethylene in the presence of a free radical initiator, controlling the amounts of propylene and ethylene, and propylphosphinic acid or its alkali metal salts in the reaction system
- a free radical initiator controlling the amounts of propylene and ethylene, and propylphosphinic acid or its alkali metal salts in the reaction system
- 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), the flow of ethylene is stopped, propylene is continued to be added, and the reaction is continued to completion in the presence of the initiator to obtain the mixture A.
- reaction II After the completion of reaction II, there is no need to separate diethylphosphinic acid, ethylpropylphosphinic acid, dipropylphosphinic acid or their alkali metal mixtures, and the next reaction can be carried out directly.
- a flame retardant is also provided, and the flame retardant includes at least one of the above-mentioned dialkylphosphinic acid hybrid salts.
- the flame retardant also contains at least one selected from the group consisting of phosphate ions, phosphite ions, alkylphosphonate ions, and alkylphosphinate ions.
- phosphorus-containing acid ions are 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-mentioned dialkylphosphinic acid hybrid salts and the above-mentioned 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 materials refer to plastics that have 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 reinforcing agents, anti-drip agents, stabilizers, pigments, dyes, carbon-forming catalysts, dispersants, nucleating agents, inorganic fillers, and antioxidants.
- 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 mass content of the functional additive in the flame retardant material is 5-40%.
- the flame retardant material also includes flame retardant Q;
- the flame retardant Q is selected from at least one of nitrogen-based flame retardants and boron-based flame retardants.
- 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 semi-aromatic polyamide is made from an aliphatic diamine and an aromatic dicarboxylic acid; optionally, an aliphatic dicarboxylic acid can also be added, and the mole of the 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 the group consisting of polyhexamethylene terephthalamide (abbreviated as PA6T), polyhexamethylene isophthalamide (abbreviated as PA6I), terephthalic acid/hexamethylene diamine/ Caprolactam copolymer (abbreviated as PA6T/6), terephthalic acid/hexamethylenediamine/adipic acid copolymer (abbreviated as PA6T/66), terephthalic acid/hexamethylenediamine/adipic acid/isophthalic acid Formic acid copolymer (abbreviated as PA6T/6I/66), polynonanediamine terephthalamide (abbreviated as PA9T), polydecanediamine terephthalamide (abbreviated as PA10T), polyterephthalamide Dodecanediamine (abbreviated as PA12T), terephthalic acid/hexamethylenediamine/laurolactam copolymer (abbreviated
- 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
- the flame retardant having the composition of formula (I) may contain trace amounts of other phosphorus-containing ions. Due to impurities contained in raw materials or impurities generated by the synthesis process, some trace amounts of phosphate ions, phosphite ions, alkylphosphonate ions, and alkylphosphinate ions may be present in flame retardants.
- Some oligomer products derived from the polymerization of ethylene and or propylene, such as ethyl n-butylphosphinate ion, ethylhexylphosphinate ion, butylbutylphosphinate ion, butylhexylphosphinate ion , propylhexylphosphinate ions will also exist as impurities in flame retardants composed of formula (I). However, as long as the total amount of these other phosphorus-containing acid ions does not exceed 5 mol% of the total phosphorus, 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 n-propyl phosphinate, ethyl isopropyl phosphinate, di-n-propyl phosphinate and n-propyl isopropyl phosphinate have different chemical shifts of 31 P , there are five independent peaks in the 31 P-NMR spectrum, and the peak areas of these five peaks respectively correspond to the molar concentrations of the five dialkylphosphinate ions.
- long-chain dialkylphosphinate ions are present, which are present in small amounts and with chemical shifts close to the corresponding dialkylphosphinate ions, and therefore, when integrated, are incorporated into the corresponding dialkylphosphinate ions.
- Phosphinate ion From this, the values of x, y and z can be easily calculated through the ratio of peak areas. For example, the molar concentration of diethylphosphinate corresponds to x, ethyl n-propylphosphinate and ethylisopropylphosphinate.
- the sum of the molar concentrations of acid radicals corresponds to y
- the sum of the molar concentrations of di-n-propylphosphinate and n-propylisopropylphosphinate corresponds to z
- the ratio of the three is the value of x, y and z.
- the dialkylphosphinic acid hybrid salt with the formula (I) provided by the present invention has a small amount of addition, easy filtration of large particle size products, less dust, high thermal stability, and high flame retardant efficiency for polymer materials. , good economy. It not only overcomes the shortcomings of diethylphosphinate's low flame retardant efficiency for polymer materials, but also overcomes the shortcomings of dipropylphosphinate's low thermal stability and large dust, and can be widely used in applications requiring high-temperature processing. Flame retardancy of polymer materials;
- This application provides a method for preparing hybrid salts of dialkylphosphinic acids, which avoids the disadvantage of needing to prepare different dialkylphosphinic acids independently, uses water as the reaction solvent, and is environmentally friendly. The raw materials are easy to obtain and the economy is high.
- Figure 1 shows the thermal weight loss curves of dialkylphosphinic acid hybrid salts with different x, y, z values, as well as aluminum diethylphosphinate and aluminum dipropylphosphinate;
- Figures 2a and 2b show the XRD curves of dialkylphosphinic acid hybrid salts, diethylphosphinic acid aluminum and dipropylphosphinic acid aluminum with different x, y, z values.
- Figure 2b is the most accurate representation of Figure 2a. Partial enlargement of strong absorption peak;
- Figure 3 is the 31 P-NMR spectrum after alkaline hydrolysis of the dialkylphosphinic acid hybrid salt in Example 7.
- 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;
- Antioxidant 1010 Pentaerythritol tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Shanghai McLean Biochemical Technology Co., Ltd.
- Antioxidant 168 Tris[2,4-di-tert-butylphenyl]phosphite, Strem Company of the United States.
- Antioxidant 1010 tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenylpropionate]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.
- the instrument model used for X-ray diffraction (XRD) testing D8 ADVANCE DAVINCI, Bruker Company, Germany.
- Particle size D50 German Sympatek laser particle size analyzer Heloise-oasis HELOS (H3938), dry test.
- R, R 1 and R 2 are all selected from n-propyl and isopropyl, and two different propyl groups can fall into the same unit structure represented by y or z. That is to say, in the same unit structure represented by y, R has both n-propyl and isopropyl groups.
- the specific R value cannot be defined in detail in the specific embodiments because it is not the only value. There is no need to define the required content of n-propyl and isopropyl in each unit structure shown by y or z, as long as the total amount meets the standard.
- Double addition product a product in which two P-H bonds on hypophosphite are added to an alkene double bond
- single addition product a product in which one P-H bond on hypophosphite is added to an alkene double bond.
- 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 characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- diethylphosphinate ions are 3.3 mol%
- the sum of dipropylphosphinate ions is 35.7mol%
- ethylpropylphosphinate ions are 3.3 mol%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- diethylphosphinate ions are 8.1 mol%
- the sum of dipropylphosphinate ions is 22.2 mol%
- ethylpropylphosphinate ions are 22.2 mol%.
- the total amount of ions is 68.5 mol%
- the total amount of other phosphorus-containing impurities such as monopropylphosphinate ions and propylphosphonate ions is 1.3 mol%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- diethylphosphinate ions are 25.1 mol%
- the sum of dipropylphosphinate ions is 10.2mol%
- ethylpropylphosphinate ions are 10.2 mol%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- diethylphosphinate ions are 25.7 mol%
- the sum of dipropylphosphinate ions is 9.1mol%
- ethylpropylphosphinate ions are 9.1 mol%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- the hybrid salt obtained in this example was alkali hydrolyzed and measured for nuclear magnetic resonance.
- the 31 P-NMR (nuclear magnetic) spectrum is shown in Figure 3.
- the peak areas of these six peaks respectively correspond to the molar concentrations of the six phosphinic acid radicals. Therefore, Through the ratio of peak areas, the values of x, y and z can be easily calculated.
- the peak areas of long-chain dialkylphosphinate ions and ethylpropylphosphinate ions are combined.
- diethylphosphinate ions are 54.4 mol%
- the sum of dipropylphosphinate ions is 2.0 mol%
- ethylpropylphosphinate ions are 2.0 mol%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- diethylphosphinate ions are 62.7 mol%
- the sum of dipropylphosphinate ions is 1.7mol%
- ethylpropylphosphinate ions are 1.7 mol%.
- the total ions are 34.9 mol%
- propylphosphonate ions are 0.4%
- other phosphorus-containing compounds are 0.3%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- diethylphosphinate ions are 76.4 mol%
- the sum of dipropylphosphinate ions is 0.5mol%
- ethylpropylphosphinate ions are 0.5 mol%.
- 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%).
- diethylphosphinate ions are 96.3 mol%, the sum of dipropylphosphinate ions is 0 mol%, and ethylpropyl
- the total amount of phosphinate ions was 3.1 mol%, and the total amount of propylphosphonate ions was 0.6 mol%.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- FIG. 1 is a graph with different x, y, z values.
- Figure 2a is an XRD pattern of the dialkylphosphinic acid hybrid salt, aluminum dipropylphosphinate, ADP and the physical mixed salt of aluminum dipropylphosphinate and ADP obtained in Examples 1-12.
- the simple physical mixed salt has two independent peaks in the XRD spectrum in the strongest absorption peak area, and their d values are close to aluminum diethylphosphinate and dipropyl phosphinate respectively.
- the d value of aluminum phosphinate, the hybrid salt composed of formula (I) has only one peak or overlapping peaks, and the d value is basically between the d values of aluminum diethylphosphinate and aluminum dipropylphosphinate. between.
- dialkylphosphinic acid hybrid salt having the formula (I) of the present invention is not simply aluminum diethylphosphinate, aluminum ethylpropylphosphinate, or aluminum dipropylphosphinate.
- the mixture is a hybrid salt containing a structure in which at least two acid ions of diethylphosphinate, ethylpropylphosphinate, and dipropylphosphinate are paired with the same aluminum atom.
- Polyamide PA6 the hybrid salt prepared in Example 1 and the compound antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm according to the weight ratio of 79.6:20:0.4, 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 UL94 V-1.
- the hybrid salts prepared in Examples 1-10 were prepared and tested in polyamide PA66 and PA6 according to the methods of Examples 13 and 14 respectively. The results are shown in Table 14, Table 15 and Table 16.
- the characteristic peak with the highest relative intensity measured by the obtained XRD corresponds to the layer spacing: (100%).
- Polyamide PA66, the aluminum dipropylphosphinate prepared in Comparative Example 1, and the compound antioxidant were mixed according to the weight ratio of 84.6:15:0.4 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 V-0.
- Polyamide PA66, the aluminum dipropylphosphinate prepared in Comparative Example 1, and the compound antioxidant were mixed according to the weight ratio of 87.1:12.5:0.4 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 V-0.
- Polyamide PA66, the aluminum dipropylphosphinate prepared in Comparative Example 1, and the compound antioxidant were mixed according to the weight ratio of 89.6:10:0.4 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 V-1.
- Polyamide PA6, the aluminum dipropylphosphinate prepared in Comparative Example 1, and the compound antioxidant were mixed according to the weight ratio of 84.6:15:0.4 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 rating of the 1.6mm sample is UL-94 V-1.
- Polyamide PA66, the aluminum diethylphosphinate prepared in Comparative Example 2, and the compound antioxidant were mixed according to the weight ratio of 84.6:15:0.4 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 diethylphosphinate prepared in Comparative Example 2, and the compound antioxidant were mixed according to the weight ratio of 84.6:15:0.4 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 rating of the 1.6mm sample is UL-94 Unrated.
- Polyamide PA66, the hybrid salt prepared in Example 11, and the compound antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm according to the weight ratio of 84.6:15:0.4.
- the set temperature was 280°C, 5 After a few minutes, take it out to 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 hybrid salt prepared in Example 11, and the compound antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm according to the weight ratio of 84.6:15:0.4.
- the set temperature was 260°C, 5 After a few 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 rating of the 1.6mm sample is UL-94 Unrated.
- Polyamide PA66, the hybrid salt prepared in Example 12, and the compound antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm according to the weight ratio of 84.6:15:0.4.
- the set temperature was 280°C, 5 After a few minutes, take it out to 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 hybrid salt prepared in Example 12, and the compound antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm according to the weight ratio of 84.6:15:0.4.
- the set temperature was 260°C, 5 After a few 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 rating of the 1.6mm sample is UL-94 Unrated.
- Examples 15-51 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.
- the comparative example shows that under the same conditions, the particle sizes of the obtained aluminum dipropylphosphinate and aluminum diethylphosphinate are smaller than those of the hybrid salts, and the large particle sizes of the hybrid salts are unexpected. .
- Comparative Examples 3-6 show that dipropylphosphinate has certain flame retardancy, but its flame retardant efficiency for polyamide is not as good as the hybrid salt with formula (I) structure described in the present invention, see Example 17, 21, 22, 27, 30, 31, 34, 35, 40, 44 and 47. And when preparing flame-retardant polyamide, it was observed that dipropylphosphinate dust was large, resulting in a poor operating environment. In addition, it can be seen from Figure 1 that its thermal stability is too low and the prepared flame-retardant PA66 is highly brittle, indicating serious degradation. Comparative Examples 7-10 illustrate that pure aluminum diethylphosphinate has low flame retardant efficiency for polyamide. Comparative Examples 11-14 illustrate that when the proportion of diethylphosphinate in the hybrid salt with the structure of formula (I) is too high, that is, when x>0.8, the flame retardant efficiency of the hybrid salt for polyamide is reduced. .
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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，并且克服了二丙基次膦酸盐热稳定性低，粉尘大的缺点，可以广泛应用于需要高温加工的高分子材料的阻燃。
Description
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。
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。还有报道使用二丙基次膦酸铝用于尼龙6的阻燃，二丙基次膦酸铝阻燃效率较高，但它的热稳定性较低，在300℃下就开始大量降解挥发，对需要高温加工的工程塑料譬如尼龙66不利。
另外，当二烷基次膦酸盐作为阻燃剂使用时，除了阻燃性能之外，在制备和使用的时候，希望阻燃剂粒径大以及密度大，以减少过滤时间以及减少粉尘，并在跟高分子材料混合时不会因为密度差异过大而导致两者在加料桶里自由流动速度不一致，从而引起阻燃剂在阻燃材料中分布均匀性差。
因此，获得阻燃性好，热稳定性高，加工性好的阻燃剂是业界的一大挑战。现在，令人惊讶的是，具有特定组成的二烷基次膦酸杂化盐能很好地满足上述要求。
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具有式(Ⅰ)组成的二烷基次膦酸杂化盐，该杂化盐添加量少，对各类高分子材料阻燃效率高，热稳定性好，能满足需要高温的工程塑料的加工要求，颗粒大，粉尘低。
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：
其中，M为中心原子；R、R
1、R
2均独立地选自正丙基、异丙基中的任一种；二乙基次膦酸根离子、乙基丙基次膦酸根离子、二丙基次膦酸根离子均为配体；并且二乙基次膦酸根离子、乙基丙基次膦酸根离子、二丙次膦酸根离子中至少二个酸根离子跟同一个金属原子配对，并且其中一个配体必须是乙基丙基次膦酸根离子；
M选自金属元素；所述金属元素选自第Ⅱ A、Ⅲ A、Ⅳ A、Ⅴ A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≤0.80；0.05≤y≤0.7；0≤z≤0.95,且x+y+z＝1。
具体地，所述乙基丙基次膦酸根离子、二丙基次膦酸根离子中的丙基为正丙基或异丙基。
本申请实施例中，在式(Ⅰ)中，x若大于0.80，阻燃性能不佳。z若大于0.95，制备时候颗粒小，过滤慢，在使用时粉尘大，同时热稳定性下降，对阻燃高分子材料制备和物理性能不利。y大于0.7，制备成本高，经济性差，对阻燃高分子材料的制备和物理性能不利。
可选地，x的下限独立地选自0、0.03、0.05、0.10、0.15；上限独立地选自0.80、0.75、0.70、0.65、0.55、0.50、0.45、0.40、0.35、0.30。
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0.70、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、0.05、0.08；上限独立地选自0.95、0.9、0.85、0.80、0.75、0.7、0.65、0.60、0.55、0.50、0.45、0.40、0.35、0.3、0.25、0.2、0.15、0.10。
可选地，所述第Ⅱ A族金属元素选自Be、Mg、Ca、Sr、Ba中的至少一种；
所述第Ⅲ A族金属元素为Al；
所述第Ⅳ A族金属元素为Sn；
所述第Ⅴ A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≤0.80；0.05≤y≤0.70；0.005≤z≤0.92。
可选地，0≤x≤0.66；0.30≤y≤0.70；0.01≤z≤0.60。
可选地，0≤x≤0.30；0.35≤y<0.70；0.05≤z≤0.60。
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丙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、乙基丙基次膦酸根离子、二丙基次膦酸根离子中的至少2种离子组成的杂化盐，并且该杂化盐中的一个配体是乙基丙基次膦酸根离子。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。并且最大峰显示的晶面间距也与二乙基次膦酸铝和二丙基次膦酸铝的不同。二乙基次膦酸铝的最大峰显示晶面间距d＝9.663，二丙基次膦酸铝的d＝11.079，而具有式(Ⅰ)二烷基次膦酸杂化盐的晶面间距d值基本介于上述两者之间。但由二乙基次膦酸铝和二丙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丙基次膦酸铝的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或者二丙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、乙基丙基次膦酸铝、二丙基次膦酸铝的混合物，而是包含了二乙基次膦酸根、乙基丙基次膦酸根、二丙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。
本申请实施例中，在相同的用量下，纯的二丙基次膦酸铝虽然阻燃效果好，但热稳定性低，难以满足需要高温加工的高分子材料的要求。并且纯的二丙基次膦酸铝粉尘大，操作困难。又由于纯的二丙基次膦酸铝颗粒细，跟高分子材料混合时，容易引起局部分层，混合均匀性差。相比之下，具有式(Ⅰ)组成的二烷基次膦酸杂化盐则热稳定性高，颗粒大，无粉尘，而且跟高分子粒子在加料桶里流动速度相近，混合均匀性好。
本申请实施例中，在相同的用量下，纯的二乙基次膦酸盐阻燃效果不佳，远远不如具有式(Ⅰ)组成的二烷基次膦酸杂化盐的阻燃效果好。
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、乙基丙基次膦酸和/或其碱金属盐与二丙基次膦酸和/或其碱金属盐。
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、乙基丙基次膦酸和/或其碱金属盐、二丙基次膦酸和/或其碱金属盐与金属元素M源的摩尔比接近为x:y:z:q，所述丙基选自正丙基、异丙基，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、乙基丙基次膦酸和/或其碱金属盐、二丙基次膦酸和/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、乙基丙基次膦酸和/或其碱金属盐与二丙基次膦酸和/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丙烯，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、丙烯的摩尔比为1：0.05-1.8：0.2-1.95。
实际反应中，由于一些副反应的存在，譬如乙烯和/或丙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、丙烯的摩尔比和式(Ⅰ)中x,y,z值相同或接近。由于在次磷酸或其碱金属盐跟乙烯 或丙烯反应过程中，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/或二丙基次膦酸或者它们的盐，对经济性不利。
具体地，在反应II中，乙烯和丙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/或其碱金属盐先与丙烯反应，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、丙基次膦酸根、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，在所述水溶液中，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水溶液总质量的20‐95％。
可选地，在所述水溶液中，所述水的质量为所述水溶液总质量的45‐92％。
可选地，在所述水溶液中，所述水的质量为所述水溶液总质量的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：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入丙烯进行反应，待通入的丙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入丙烯，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：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入丙烯，待所述丙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，次磷酸和/或其碱金属盐与丙烯先反应来获得具有或大体上接近y值的单丙基次膦酸或其碱金属盐，并且控制z小于等于0.95，然后再停止加入丙烯，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：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入丙烯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，待通入的丙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入丙烯，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：
向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入丙烯和部分乙烯，待所述丙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丙烯的摩尔比为0.026‐9:1。
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，再继续通入丙烯进行反应，待通入的丙烯跟起始次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入丙烯，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，再继续通入丙烯进行反应，待所述丙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丙烯的摩尔比为0.026‐9:1。
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丙烯和部分乙烯在自由基引发剂存在下进行反应，控制丙烯和乙烯的量，待反应体系中丙基次膦酸或其碱金属盐摩尔百分比接近y值，且二丙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0.95，停止加入丙烯，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。
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，继续加入丙烯，在引发剂存在下继续反应至结束，得到所述混合物A。
具体地，在反应II结束后，无需分离出二乙基次膦酸、乙基丙基次膦酸、二丙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。
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％，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。
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。
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。一些由乙烯和或者丙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、丙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5％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、乙基正丙基次膦酸根、乙基异丙基次膦酸根、二正丙基次膦酸根、正丙基异丙基次膦酸根具有不同的
31P的化学位移，在
31P‐NMR谱中呈现独立地五个峰，这五个峰的峰面积分别对应五个二烷基次膦酸根离子的摩尔浓度。在一些情况下，存在长链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，将其并入相应的二烷基次膦酸根离子。由此通过峰面积的比例，可以很方便地计算出x，y和z的值，例如二乙基次膦酸根摩尔浓度对应x，乙基正丙基次膦酸根和乙基异丙基次膦酸根摩尔浓度之和(简称为乙基丙基次膦酸根的摩尔浓度)对应y，二正丙基次膦酸根和正丙基异丙基次膦酸根摩尔浓度之和(简称为二丙基次膦酸根的摩尔浓度)对应z，三者之比就是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，大粒径产物过滤容易，粉尘少，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对高分子材料阻燃效率低的缺点，并且克服了二丙基次膦酸盐热稳定性低，粉尘大的缺点，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。
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丙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盐、二乙基次膦酸铝和二丙基次膦酸铝的XRD曲线，其中图2b是图2a最强吸收峰的局部放大图；
图3为实施例7中的二烷基次膦酸杂化盐碱解后的
31P‐NMR谱图。
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 70G35 HSL 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；
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：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，乙基丙基次膦酸根，二丙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：D8 ADVANCE 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。
粒径D50:德国新帕泰克激光粒度仪Heloise‐oasis HELOS(H3938)，干法测试。
本申请中，R、R
1、R
2均选自正丙基、异丙基中的任一种，2个不同的丙基可以落在同一个y或者z所示的单元结构中。也就是说同一个y所示的单元结构中，R同时存在正丙基和异丙基的情况，但是具体实施例中无法详尽定义具体R值，因为它不是唯一值。在每一个y或z所示的单元结构中不需要定义正丙基和异丙基的含量各自需要多少，只需要总量达到标准即可。申请人在表1中示例性地给出了具体说明：譬如双混结构式下标对应的是y，它包含了双混1(R＝异丙基)，和双混2(R＝正丙基)。
实施例1
具有式(Ⅰ)组成的杂化盐的制备，其中x＝0,y＝0.086,z＝0.914,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.75MPa，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丙烯，通过气体流量表来计量烯烃的通入量。9小时后，停止通丙烯，开始通入乙烯。16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。
反应中间过程取样，做核磁，
31P‐NMR结果如表1所示：
表1
注：双加成产物：次磷酸根上的2个P‐H键加成到烯烃双键上的产物；单加成产物：次磷酸根上的1个P‐H键加成到烯烃双键上的产物；双混1：乙基异丙基次膦酸根离子(R＝异丙基)；双混2：乙基正丙基次膦酸根离子(R＝正丙基)；双乙：二乙基次膦酸根离子；双丙：正丙基异丙基次膦酸根离子(R
1≠R
2，分别是正丙基和异丙基)加二正丙基次膦酸根(R
1＝R
2＝正丙基)离子的总和；单乙：单乙基次膦酸根离子；单丙1：单异丙基次膦酸根离子；单丙2：单正丙基次膦酸根离子；单氧化：乙基膦酸根离子加丙基膦酸根离子的总和。下同。
将上述部分溶液551.94克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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93克白色固体。将样品溶解于氢氧化钠的水溶液中，做磷核磁,得到乙基丙基次膦酸根离子总和8.6mol％，二丙基次膦酸根离子总和91.0mol％，丙基膦酸根离子0.4％。归一化后得到x＝0,y＝0.086,z＝0.914。
对样品进行粒径测试，D
50＝53.71μm。
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
(100％)。
实施例2具有式(Ⅰ)组成的杂化盐的制备，其中x＝0,y＝0.192,z＝0.808,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.75MPa，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丙烯，通过气体流量表来计量烯烃的通入量。8.5小时后，停止通丙烯，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。
反应中间过程取样，做核磁，
31P‐NMR结果如表2所示：
表2
将上述部分溶液559.8克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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90克白色固体，收率98.4％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中可以得到：二丙基次膦酸根离子总和为80.8mol％，乙基丙基次膦酸根离子总和为19.2mol％。因此x＝0,y＝0.192,z＝0.808。
对样品进行粒径测试，D
50＝24.66μm。
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
(100％)。
实施例3具有式(Ⅰ)组成的杂化盐的制备，其中x＝0,y＝0.412,z＝0.588,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。6小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。17.5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。
反应中间过程取样，做核磁，
31P‐NMR结果如表3所示：
表3
将上述部分溶液559.94克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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87.3克白色固体，收率98％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中可以得到：二丙基次膦酸根离子总和为58.3mol％，乙基丙基次膦酸根离子总和为40.9mol％，剩余0.8mol％为其它一些含磷杂质，含磷杂质包括单丙基次膦酸根离子、丙基膦酸根离子等。归一化后得到x＝0,y＝0.412,z＝0.588。
对样品进行粒径测试，D
50＝27.69μm。
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
(100％)。
实施例4具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.033,y＝0.610,z＝0.357,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。5.5小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。16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。
反应中间过程取样，做核磁，
31P‐NMR结果如表4所示：
表4
将上述部分溶液536.33克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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86.1克白色固体，收率98％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子3.3mol％，二丙基次膦酸根离子总和为35.7mol％，乙基丙基次膦酸根离子总和为61.0mol％，得到x＝0.033,y＝0.610,z＝0.357。
对样品进行粒径测试，D
50＝29.98μm。
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
(100％)。
实施例5具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.082,y＝0.694,z＝0.224,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。5小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。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。
反应中间过程取样，做核磁，
31P‐NMR结果如表5所示：
表5
将上述部分溶液548.44克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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84克白色固体，收率99％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子8.1mol％，二丙基次膦酸根离子总和为22.2mol％，乙基丙基次膦酸根离子总和为68.5mol％，其它含磷杂质如单丙基次膦酸根离子、丙基膦酸根离子总和为1.3mol％。归一化之后得到x＝0.082,y＝0.694,z＝0.224。
对样品进行粒径测试，D
50＝49.26μm。
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
(100％)。
实施例6具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.251,y＝0.647,z＝0.102,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。4.5小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。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。
反应中间过程取样，做核磁，
31P‐NMR结果如表6所示：
表6
将上述部分溶液544.38克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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80.4克白色固体，收率96％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子25.1mol％，二丙基次膦酸根离子总和为10.2mol％，乙基丙基次膦酸根离子总和为64.7mol％，得到x＝0.251,y＝0.647,z＝0.102。
对样品进行粒径测试，D
50＝49.85μm。
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
(100％)。
实施例7具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.257,y＝0.652,z＝0.091,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。5小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。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。
反应中间过程取样，做核磁，
31P‐NMR结果如表7所示：
表7
将上述部分溶液471.95克(含磷0.54摩尔)，慢慢跟10％质量浓度的含59.98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72克白色固体，收率96％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子25.7mol％， 二丙基次膦酸根离子总和为9.1mol％，乙基丙基次膦酸根离子加长链烷二基次膦酸根离子总和为65.2mol％，得到x＝0.257,y＝0.652,z＝0.091。
对样品进行粒径测试，D
50＝62.31μm。
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
(100％)。
将本实施例中得到的杂化盐碱解后测核磁，
31P‐NMR(核磁)图谱如图3所示，这六个峰的峰面积分别对应六种次膦酸根的摩尔浓度，因此，通过峰面积的比值，可以很方便地计算出x,，y和z的值，计算时将长链二烷基次膦酸根离子与乙基丙基次膦酸根离子的峰面积合并。
实施例8具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.544,y＝0.436,z＝0.020,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。5小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。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。
反应中间过程取样，做核磁，
31P‐NMR结果如表8所示：
表8
将上述部分溶液458.58克(含磷0.54摩尔)，慢慢跟10％质量浓度的含59.98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56.3克白色固体，收率93％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子54.4mol％，二丙基次膦酸根离子总和为2.0mol％，乙基丙基次膦酸根离子总和为43.6mol％，得到x＝0.544,y＝0.436,z＝0.020。
对样品进行粒径测试，D
50＝70.79μm。
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
(100％)。
实施例9具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.631,y＝0.351,z＝0.018,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.70MPa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丙烯，通过气体流量表来计量烯烃的通入量。3小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。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。
反应中间过程取样，做核磁，
31P‐NMR结果如表9所示：
表9
将上述部分溶液376.79克(含磷0.45摩尔)，慢慢跟10％质量浓度的含49.98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56.3克白色固体，收率94％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子62.7mol％，二丙基次膦酸根离子总和为1.7mol％，乙基丙基次膦酸根离子总和为34.9mol％，丙基膦酸根离子0.4％，其它含磷化合物0.3％。归一化之后得到x＝0.631,y＝351,z＝0.018。
对样品进行粒径测试，D
50＝79.96μm。
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
(100％)。
实施例10具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.764,y＝0.231,z＝0.005,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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.50MPa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丙烯，通过气体流量表来计量烯烃的通入量。3小时后，停止通丙烯，开始通入乙烯，保持压力为0.8MPa。13.5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。
反应中间过程取样，做核磁，
31P‐NMR结果如表10所示：
表10
将上述部分溶液449.42克(含磷0.54摩尔)，慢慢跟10％质量浓度的含59.98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68.1克白色固体，收率96％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子76.4mol％，二丙基次膦酸根离子总和为0.5mol％，乙基丙基次膦酸根离子总和为23.1mol％，得到x＝0.764,y＝0.231,z＝0.005。
对样品进行粒径测试，D
50＝69.99μm。
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
(100％)。
实施例11(对比例)具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.902,y＝0.096,z＝0.002,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，充乙烯至压0.8MPa。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乙烯，通过气体流量表来计量烯烃的通入量。4.5小时后，停止通乙烯，开始通入丙烯，保持压力为0.8MPa左右。10.5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。
反应中间过程取样，做核磁，
31P‐NMR结果如表11所示：
表11
将上述部分溶液759.4克(含磷0.93摩尔)，慢慢跟10％质量浓度的含103.29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116.6克白色固体，收率97％。将样品溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子90.2mol％，二丙基次膦酸根离子总和为0.2mol％，乙基丙基次膦酸根离子总和为9.6mol％，得到x＝0.902,y＝0.096,z＝0.002。
对样品进行粒径测试，D
50＝80.56μm。
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
(100％)。
实施例12(对比例)具有式(Ⅰ)组成的杂化盐的制备，其中x＝0.969,y＝0.031,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，充乙烯至压0.8MPa。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乙烯，通过气体流量表来计量烯烃的通入量。6.5小时后，停止通乙烯，开始通入丙烯，保持压力为0.8MPa左右。9.5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。
反应中间过程取样，做核磁，
31P‐NMR结果如表12所示：
表12
将上述部分溶液751.4克(含磷0.93摩尔)，慢慢跟10％质量浓度的含103.29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115.2克白色固体，收率97％。取一小部分白色固体溶解于氢氧化钠水溶液中，做核磁，从磷谱中得到：二乙基次膦酸根离子96.3mol％，二丙基次膦酸根离子总和为0mol％，乙基丙基次膦酸根离子总和为3.1mol％，丙基膦酸根离子0.6mol％。归一化之后得到x＝0.969,y＝0.031,z＝0。
对样品进行粒径测试，D
50＝76.33μm。
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
(100％)。
对实施例1‐12中得到的二烷基次膦酸杂化盐，二丙基次磷酸铝和ADP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ADP和二丙基次膦酸铝的热失重曲线图(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是实施例1‐12得到的二烷基次膦酸杂化盐，二丙基次磷酸铝，ADP及二丙基次磷酸铝和ADP物理混合盐的XRD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丙基次膦酸铝的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丙基次膦酸铝的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、乙基丙基次膦酸铝、二丙基次膦酸铝的混合物，而是包含了二乙基次膦酸根、乙基丙基次膦酸根、二丙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13
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14
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UL94 V‐1。
实施例15‐51
将实施例1‐10制备的杂化盐分别在聚酰胺PA66，PA6中按照实施例13、14的方式进行制样和测试，结果见表14、表15和表16。
对比例1二丙基次膦酸铝
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，充丙烯至压力不再上升。对反应液加热至90℃左右，此时压力表显示为0.8MPa，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丙烯，通过气体流量表来计量丙烯的通入量。15.5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。
反应中间过程取样，做核磁，
31P‐NMR结果如表13所示：
表13
将上述部分溶液525克(含磷0.6摩尔)，慢慢跟10％质量浓度的含66.64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92.8克白色固体，收率98％。
对样品进行粒径测试，D
50＝5.21μm。
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
(100％)。
对比例2二乙基次膦酸铝
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，充乙烯至0.8MPa。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乙烯，通过气体流量表来计量乙烯的通入量。8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。反应结束取样，做核磁，
31P‐NMR结果显示：
将上述部分溶液190克(含磷0.24摩尔)，慢慢跟10％质量浓度的含26.66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29.8克白色固体，收率95.4％。
对样品进行粒径测试，D
50＝29.5μm。
对比例3
将聚酰胺PA66、对比例1制备的二丙基次膦酸铝、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4
将聚酰胺PA66、对比例1制备的二丙基次膦酸铝、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‐0。
对比例5
将聚酰胺PA66、对比例1制备的二丙基次膦酸铝、复配抗氧剂按照89.6:10:0.4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6
将聚酰胺PA6、对比例1制备的二丙基次膦酸铝、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UL‐94 V‐1。
对比例7
将聚酰胺PA66、对比例2制备的二乙基次膦酸铝、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8
将聚酰胺PA6、对比例2制备的二乙基次膦酸铝、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UL‐94无等级。
对比例9
将聚酰胺PA66、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10
将聚酰胺PA6、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UL‐94无等级。
对比例11
将聚酰胺PA66、实施例11制备的杂化盐、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12
将聚酰胺PA6、实施例11制备的杂化盐、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UL‐94无等级。
对比例13
将聚酰胺PA66、实施例12制备的杂化盐、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14
将聚酰胺PA6、实施例12制备的杂化盐、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UL‐94无等级。
对比例3‐14测试结果见表17。
实施例15-51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。在制备阻燃聚酰胺时候，操作无明显粉尘。所制备的阻燃PA66样条韧性好，无明显降解。对比例说明在相同条件下，所获得的二丙基次膦酸铝和二乙基次膦酸铝的粒径相比于杂化盐的要小，杂化盐的大粒径是意想不到的。对比例3-6显示二丙基次膦酸盐具有一定的阻燃性，但其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，见实施例17、21、22、27、30、31、34、35、40、44和47。并且在制备阻燃聚酰胺时候，观察到二丙基次膦酸盐粉尘大，带来操作环境差。另外从图1中可知，其热稳定性过低，所制备的阻燃PA66脆性大，说明降解严重。对比例7-10说明纯的二乙基次膦酸铝对聚酰胺阻燃效率低。对比例11-14说明，当具有式(Ⅰ)结构杂化盐中，二乙基次膦酸根所占比例过高，即x>0.8时，所述杂化盐对聚酰胺的阻燃效率降低。
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 (13)
- 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：
其中，M为中心原子；R、R 1、R 2均独立地选自正丙基、异丙基中的任一种；二乙基次膦酸根离子、乙基丙基次膦酸根离子、二丙基次膦酸根离子均为配体；并且二乙基次膦酸根离子、乙基丙基次膦酸根离子、二丙次膦酸根离子中至少二个酸根离子跟同一个金属原子配对，并且其中一个配体必须是乙基丙基次膦酸根离子；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≤0.80；0.05≤y≤0.7；0≤z≤0.95,且x+y+z＝1。 - 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。
- 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≤0.80；0.05≤y≤0.70；0.005≤z≤0.92；优选地，0≤x≤0.66；0.30≤y≤0.70；0.01≤z≤0.60；优选地，0≤x≤0.30；0.35≤y<0.70；0.05≤z≤0.60。
- 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。
- 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、乙基丙基次膦酸和/或其碱金属盐与二丙基次膦酸和/或其碱金属盐。
- 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：向含有次磷酸和/或其碱金属盐、自由基引发剂的水溶液中通入乙烯和丙烯，反应II，得到所述混合物A；优选地，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％；优选地，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；优选地，所述自由基引发剂与所述次磷酸和/或其碱金属盐总量的摩尔比为0.001-0.1：1；优选地，所述次磷酸和/或其碱金属盐、乙烯、丙烯的摩尔比为1：0.05-1.8：0.2-1.95；优选地，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丙烯进行反应，待通入的丙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入丙烯，再继续通入乙烯反应，得到所述混合物A；优选地，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丙烯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，待通入的丙烯跟次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入丙烯，再继续通入剩余部分乙烯反应，得到所述混合物A；优选地，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，再继续通入丙烯进行反应，待通入的丙烯跟起始次磷酸和/或其碱金属盐的总磷摩尔之比达到式(Ⅰ)中的(y+2z)/1之后，停止通入丙烯，继续通入剩余部分乙烯进行反应，得到所述混合物A；优选地，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。
- 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、根据权利要求5或6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。
- 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7所述的阻燃剂中的至少一种。
- 根据权利要求8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％。
- 根据权利要求8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％。
- 根据权利要求10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。
- 根据权利要求11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％。
- 根据权利要求8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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