Summary of the invention
In order to the shortcoming overcoming prior art is with not enough, the object of the invention is to provide the preparation method of monoalkyl/dialkylphosphinic salts that a kind of technical process is simple, reaction time is short, overall yield is high, product purity is high.
The present invention is achieved by the following technical solutions:
A preparation method for monoalkyl/dialkylphosphinic salts, comprises the steps:
Take water as reaction medium, hypophosphite is reacted with alkene I under initiator I effect at temperature is 70 ~ 90 DEG C, obtains monoalkylphosphinic acid salt;
Or, take water as reaction medium, hypophosphite is reacted at temperature is 70 ~ 90 DEG C with alkene I under initiator I effect, obtain monoalkylphosphinic acid salt, be heated to 90 ~ 110 DEG C, the monoalkylphosphinic acid salt obtained is reacted with alkene II under initiator II effect, obtains dialkylphosphinic salts;
Or, take water as reaction medium, hypophosphite is reacted with alkene III under initiator III effect at 70 ~ 120 DEG C, obtains dialkylphosphinic salts;
Wherein, described hypophosphite is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr salt of Hypophosporous Acid, 50.
The mass ratio of described hypophosphite and water is 1:1 ~ 50, is preferably 1:2 ~ 10, is more preferably 1:2.5 ~ 5;
Described initiator I, initiator II are identical with initiator III;
Described initiator I, initiator II are different with initiator III;
Described initiator I, initiator II and initiator III are the 0.1mol% ~ 10mol% of hypophosphite.
Described initiator I, initiator II and initiator III are azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
Described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described organic peroxide evocating agent is perbenzoic acid, peroxylauric acid, ditertiary butyl peroxide, the special pentyl ester of peroxycarbonates, excessively oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester or peroxidation;
Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
Described alkene I, alkene II and alkene III are identical or different, are the ɑ-alkene of naphthenic alkene or carbonatoms 2 ~ 20.
Described ɑ-alkene is selected from the mixture of one or more in ethene, propylene, butylene, iso-butylene or amylene.
Described naphthenic alkene is cyclopentenes or tetrahydrobenzene.
The mol ratio of described hypophosphite and alkene I is less than 1:1, is preferably 1:1.01 ~ 1.5;
The mol ratio of described hypophosphite and alkene II is less than 1:1, is preferably 1:1.01 ~ 1.5;
The mol ratio of described hypophosphite and alkene III is less than 1:2, is preferably 1:2.01 ~ 2.5.
Described reaction pressure is 0.5MPa ~ 6MPa, is preferably 0.6MPa ~ 2.5MPa.
Monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains is separated from mixture by filtration or centrifugal treating.
The invention also discloses a kind of monoalkyl/dialkylphosphinic salts prepared by above-mentioned preparation method, there is following structure formula I,
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is for both can not be H simultaneously;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 2 ~ 4.
The invention also discloses the purposes that monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains is used as fire retardant.
The invention also discloses a kind of flame-proofed polymer material prepared by monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains, comprise 5 ~ 20wt% monoalkyl/dialkylphosphinic salts, 50 ~ 70wt% polymkeric substance or its mixture, 0 ~ 30wt% glass fibre, other auxiliary agents of 0 ~ 5wt%; Wherein, monoalkyl/dialkylphosphinic salts has following structure formula I,
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is for both can not be H simultaneously;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 2 ~ 4; Described polymer materials can be PBT, PET, PC, PA, PS etc.
The present invention compared with prior art, has following beneficial effect:
1) the present invention directly with target hypophosphite for raw material reacts, single stage method obtains corresponding monoalkylphosphinic acid salt and dialkylphosphinic salts flame retardant products.
2) reaction time of the present invention is extremely short, the shortlyest can obtain monoalkylphosphinic acid salt product at 3 ~ 5 hours, the shortlyest can obtain dialkylphosphinic salts product at 8 ~ 9 hours.
3) the present invention prepares the monoalkylphosphinic acid salt of gained, and productive rate is the highest can close to 95%; Simultaneously dialkylphosphinic salts productive rate is high, the highest can close to 97%.
4) present invention process flow process is simple; Organic solvent-free or other solvents, without any need for aftertreatment; After product salify, other salts contgs are few, are easy to washing.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Wherein, in embodiment, products obtained therefrom productive rate all calculates by following formula:
Calculation of yield formula:
Wherein, w is productive rate, and m is product gained quality, and n is hypophosphite mole number, and M is molecular weight product.
embodiment 1: the structure of ethylphosphinic acid aluminium and preparation thereof
By hypo-aluminum orthophosphate 444.0g(2mol), 1500mL water and 10.0g(0.044mol) ammonium persulphate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 5.0g(0.022mol with volume pump) solution that is mixed with of ammonium persulphate and 25mL water, 1 hour is incubated again at 75 DEG C, cooling emptying, by the ethylphosphinic acid aluminium-water mixed system 2156.2g obtained, being equivalent to ethylene absorption amount is that 172.2g(is equivalent to 102.5% of theoretical amount),
Gained ethylphosphinic acid aluminium-water mixed system is heated to 95 DEG C of filtrations, washs 1 time with 95 DEG C of hot water 1000mL, and solid vacuum-drying at 130 DEG C obtains ethylphosphinic acid aluminium in 5 hours: 576.4g, productive rate 94.18%, and wherein, the structural formula of ethylphosphinic acid aluminium is:
31p-NMR analyzes (in sample vitriolization):
Ethylphosphinic acid mol content: 96.3%
Diethyl phospho acid mol content: 2.5%
Other mol content: 1.2%.
embodiment 2: the structure of aluminum diethylphosphinate and preparation thereof
By hypo-aluminum orthophosphate 444g(2mol), 1500mL water and 10.0g(0.044mol) ammonium persulphate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4 hours, be evenly warming up to 75 DEG C and squeeze into 5.0g(0.022mol continuously with volume pump) solution that is mixed with of ammonium persulphate and 25mL water; After 4.5 hours, be heated to 95 DEG C, in 4 hours, be evenly warming up to 110 DEG C and squeeze into volume pump the solution that 15.0g ammonium persulphate and 75mL water is mixed with continuously, 1 hour is incubated again at 110 DEG C, cooling emptying, the aluminum diethylphosphinate obtained-water mixed system 2416g, be equivalent to that ethylene absorption amount is 342.0g(theoretical amount 101.8%).
Gained aluminum diethylphosphinate-water mixed system filters, and with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains aluminum diethylphosphinate in 5 hours: 752.8g, productive rate 96.51%, and wherein, the structural formula of aluminum diethylphosphinate is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 97.3%
Ethylphosphinic acid mol content: 2.0%
Ethyl-butyl Hypophosporous Acid, 50 mol content: 0.3%
Other mol content: 0.4%.
embodiment 3: the structure of aluminum diethylphosphinate and preparation thereof
By hypo-aluminum orthophosphate 444.0g(2.00mol), 1500mL water adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 95 DEG C, in 11 hours, even volume pump squeezes into 20.0g(0.088mol ammonium persulphate) solution that is mixed with 100mL water, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, the aluminum diethylphosphinate obtained-water mixed system 2417.2g, be equivalent to that ethylene absorption amount is 343.2g(theoretical amount 102.1%),
Gained aluminum diethylphosphinate-water mixed system filters, and with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains aluminum diethylphosphinate in 5 hours: 756.1g, productive rate 96.93%, and wherein, the structural formula of aluminum diethylphosphinate is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 94.1%
Ethylphosphinic acid mol content: 0.4%
Ethyl-butyl Hypophosporous Acid, 50 mol content: 5.0%
Other mol content: 0.5%.
embodiment 4: the structure of ethyl-butyl phospho acid aluminium and preparation thereof
By hypo-aluminum orthophosphate 444.0g(2.00mol), 1500mL water and 10.0g(0.044mol) ammonium persulphate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 5.0g(0.022mol with volume pump) solution that is mixed with of ammonium persulphate and 25mL water, 1 hour is incubated again at 75 DEG C, cooling emptying, namely ethylphosphinic acid aluminium-water mixed system 2156.4g is obtained, be equivalent to that ethylene absorption amount is 172.4g(theoretical amount 102.6%),
Be heated to 105 DEG C, in high-pressure reactor, be filled with n-butene be about 350g, in 4h, even volume pump squeezes into 10g(0.044mol) solution that is mixed with of ammonium persulphate and 50mL water, after 110 DEG C insulation 2 hours, be cooled to 50 DEG C of emptying, the mixed system 2555.3g obtained, be equivalent to that n-butene absorbed dose is 338.9g(theoretical amount 100.9%);
Gained mixed system filters, and with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains ethyl-butyl phospho acid aluminium for 5 hours: 918.9g, productive rate 96.93%, and wherein, the structural formula of ethyl-butyl phospho acid aluminium is:
31p-NMR analyzes (in sample vitriolization):
Ethyl-butyl phospho acid mol content: 96.2%
Diethyl phospho acid mol content: 2.3%
Ethylphosphinic acid mol content: 0.7%
Other mol content: 0.8%.
embodiment 5: the structure of butyl phospho acid iron and preparation thereof
By ferric hypophosphite 502.0g(2.00mol), 1500mL water and 10g(0.041mol) dibenzoyl peroxide adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after n-butene 360g is filled with, by nitrogen pressurization to 2.5MPa, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 5g(0.021mol with volume pump) solution that is mixed with of dibenzoyl peroxide and 30mL toluene, 1 hour is incubated again at 75 DEG C, cooling emptying, the mixed system obtained is heated to 95 DEG C of filtrations, 1 time is washed with 95 DEG C of hot water 1000mL, solid vacuum-drying at 130 DEG C obtains butyl phospho acid iron for 5 hours: 757.8g, productive rate 89.79%, wherein, the structural formula of butyl phospho acid iron is:
31p-NMR analyzes (in sample vitriolization):
Butyl phospho acid mol content: 95.6%
Dibutyl phospho acid mol content: 4.1%
Other mol content: 1.3%.
embodiment 6: the structure of dibutyl phospho acid iron and preparation thereof
By ferric hypophosphite 502.0g(2.00mol), 1500mL water adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after n-butene 700g is filled with, by nitrogen pressurization to 2.5MPa, be heated to 95 DEG C, in 7 hours, even volume pump squeezes into 20.0g(0.85mol) solution that is mixed with of Sodium Persulfate and 100mL water, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, the mixed system obtained is filtered, with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains dibutyl phospho acid iron for 5 hours: 1072.3g, productive rate 90.87%, wherein, the structural formula of dibutyl phospho acid iron is:
31p-NMR analyzes (in sample vitriolization):
Dibutyl phospho acid mol content: 97.4%
Butyl phospho acid mol content: 1.6%
Other mol content: 1.0%.
embodiment 7: the structure of n-propyl phospho acid magnesium and preparation thereof
By magnesium hypophosphite 465.0g(3.00mol), 1500mL water and 12.0g(0.044mol) Potassium Persulphate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after propylene be adjusted to 1.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 5.0g(0.022mol with volume pump) solution that is mixed with of Potassium Persulphate and 25mL water, 1 hour is incubated again at 75 DEG C, cooling emptying, the mixed system 2261.3g obtained, being equivalent to absorb propylene amount is 100.9% of 254.3g(theoretical amount);
Gained mixed system is heated to 95 DEG C of filtrations, washs 1 time with 95 DEG C of hot water 1000mL, and solid vacuum-drying at 130 DEG C obtains n-propyl phospho acid magnesium for 5 hours: 571.0g, productive rate 79.37%, and wherein, the structural formula of n-propyl phospho acid magnesium is:
31p-NMR analyzes (in sample vitriolization):
N-propyl phospho acid mol content: 95.7%
Dipropyl phospho acid mol content: 2.4%
Other mol content: 1.9%.
embodiment 8: the structure of dipropyl phospho acid magnesium and preparation thereof
Magnesium hypophosphite 465.0g (3.00mol), 1500mL water are added in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after propylene be adjusted to 1.5MPa by voltate regulator and be filled with, be heated to 95 DEG C, in 7 hours, even volume pump squeezes into 13.0g(0.089mol) ditertiary butyl peroxide, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, obtain mixed system 2490.3g, being equivalent to absorb propylene amount is 101.6% of 512.3g(theoretical amount);
Gained mixed system filters, and with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains dipropyl phospho acid magnesium for 5 hours: 894.2g, productive rate 92.00%, and wherein the structural formula of dipropyl phospho acid magnesium is:
31p-NMR analyzes (in sample vitriolization):
Dipropyl phospho acid mol content: 94.9%
Propylphosphinic acid mol content: 3.5%
Other mol content: 1.6%.
embodiment 9: the structure of ethylphosphinic acid calcium and preparation thereof
By calcium propionate 510.0g(3.00mol), 1500mL water and 10.0g, 0.044mol ammonium persulphate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 5.0g with volume pump, the solution that 0.022mol ammonium persulphate and 25mL water are mixed with, 1 hour is incubated again at 75 DEG C, cooling emptying, obtains mixed system 2222.0g, and the amount being equivalent to absorb ethene is 102.4% of 172.0(theoretical amount);
Gained mixed system is heated to 95 DEG C of filtrations, washs 1 time with 95 DEG C of hot water 1000mL, and solid vacuum-drying at 130 DEG C obtains ethylphosphinic acid calcium in 5 hours: 430.0g, productive rate 63.42%, and wherein, the structural formula of ethylphosphinic acid calcium is:
31p-NMR analyzes (in sample vitriolization):
Ethylphosphinic acid mol content: 91.5%
Diethyl phospho acid mol content: 6.2%
Other mol content: 2.3%.
embodiment 10: the structure of diethyl phospho acid calcium and preparation thereof
By calcium propionate 510g(3mol), 1500mL water adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 95 DEG C, in 7 hours, even volume pump squeezes into 20.0g, the solution that 0.088mol ammonium persulphate and 100mL water are mixed with, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, obtains mixed system 2473.4g, and be equivalent to that ethylene absorption amount is 343.4g(theoretical amount 102.2%);
Gained mixed system filters, and with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains diethyl phospho acid calcium for 5 hours: 650.5g, productive rate 76.89%, and wherein, the structural formula of diethyl phospho acid calcium is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 97.4%
Ethylphosphinic acid mol content: 1.4%
Other mol content: 1.2%
embodiment 11: the structure of ethylphosphinic acid zinc and preparation thereof
By zinc hypophosphite 585g(3mol), 1500mL water and 7.7g, the 0.044mol peroxidation trimethylacetic acid tert-butyl ester adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into volume pump the solution that the 3.8g peroxidation trimethylacetic acid tert-butyl ester and 25mL ethanol is mixed with, 1 hour is incubated again at 75 DEG C, cooling emptying, obtain mixed system 2291.6, be equivalent to that ethylene absorption amount is 175.1g(theoretical amount 104.2%);
Gained mixed system is heated to 95 DEG C of filtrations, washs 1 time with 95 DEG C of hot water 1000mL, and solid vacuum-drying at 130 DEG C obtains ethylphosphinic acid zinc in 5 hours: 689.3g, productive rate 90.70%, and wherein, the structural formula of ethylphosphinic acid zinc is:
31p-NMR analyzes (in sample vitriolization):
Ethylphosphinic acid mol content: 96.5%
Diethyl phospho acid mol content: 2.3%
Other mol content: 1.2%.
embodiment 12: the structural formula of diethyl phospho acid zinc and preparation thereof
By zinc hypophosphite 585g(3mol), 1500mL water adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 95 DEG C, in 7 hours, even volume pump squeezes into 15.3g, the solution that the 0.088mol peroxidation trimethylacetic acid tert-butyl ester and 100mL ethanol are mixed with, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, obtains mixed system 2448.4g, and be equivalent to that ethylene absorption amount is 348.1g(theoretical amount 103.6%);
Filter, with 1000mL water washing 1 time, solid vacuum-drying at 130 DEG C obtains diethyl zinc hypophosphite in 5 hours: 848.4g, productive rate 92.12%, and wherein, the structural formula of diethyl phospho acid zinc is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 97.2%
Ethylphosphinic acid mol content: 1.5%
Other mol content: 1.3%.
comparative example 1
Get 360.6g50wt% Hypophosporous Acid, 50 (2.732mol) and 4.7g(0.027mol, 1.0%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in autoclave together, enclosed high pressure still, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, under agitation be heated to 72 DEG C, evenly 9.4g(0.054mol is added in 14h, 2.0%mol) the peroxidation trimethylacetic acid tert-butyl ester, and be evenly warming up to 85 DEG C, by this reactor cooling also emptying, obtain product water solution 508.9g;
31p-NMR analyzes
Diethyl phospho acid mol content: 74.1%
Ethylphosphinic acid mol content: 23.8%
Other mol content: 2.1%
300g water and high density alkyl phosphinic acid 557.9g obtained above are added in reactor and stirs, obtain with the neutralization of 30%wt aqueous sodium hydroxide solution, post-heating to 95 DEG C, by 303.3g(0.455mol) Tai-Ace S 150 to be dissolved in the 700mL aqueous solution and to instill in 1 hour, being incubated 1 hour, being cooled to room temperature after dripping off at 90 ~ 95 DEG C, gained solid is leached, and with 700mL water washing three times, be dried to constant weight at 150 DEG C, obtain 295.7g alkyl phosphinic acid aluminium.
comparative example 2
Get 289.6g mono-hydration sodium hypophosphite (2.732mol), 500g acetic acid and 4.4g(0.027mol, 1.0%mol) Diisopropyl azodicarboxylate adds in autoclave together, enclosed high pressure still, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, under agitation be heated to 75 DEG C, evenly 6.7(0.041mol is added in 10 hours, 1.5%mol) Diisopropyl azodicarboxylate, and be evenly warming up to 85 DEG C, by this reactor cooling also emptying, obtain solution 926.3g, 130 DEG C of underpressure distillation 2 hours, obtain 453.1g dope,
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 91.3%
Ethyl-butyl phospho acid mol content: 2.1%
Ethylphosphinic acid mol content: 3.1%
Other mol content: 3.5%
To be dissolved in the 750mL water of 80 DEG C with 453.1g dope obtained above and add in reactor, be heated with stirring to 95 DEG C, by 303.3g(0.455mol) Tai-Ace S 150 to be dissolved in the 700mL aqueous solution and to instill in 1 hour, at 90 ~ 95 DEG C, be incubated 1 hour after dripping off, be cooled to room temperature, gained solid is leached, and with 700mL water washing three times, be dried to constant weight at 150 DEG C, obtain 338.9g white powder, overall yield 95.41%.
Monoalkyl/the dialkylphosphinic salts of embodiment 1 ~ 12 and comparative example 1 ~ 2 gained is mixed by weight 10:60:25:5 with PBT, glass, auxiliary agent at 230 ~ 260 DEG C, extrude from Bitruder, obtained flame-proofed thermoplastic polymer in-mold moulding material, its combustionproperty and mechanical property are tested in sample preparation, record result and see table 1:
The moulding material combustionproperty that table 1 monoalkyl/dialkylphosphinic salts is obtained and mechanical property parameters table
Each performance test is undertaken by following standard:
Tensile strength: GB1040-1992 plastic tensile method for testing performance;
Flexural strength: GB9341-2000 Plastics-Oetermination of flexural properties method;
Amount of deflection: GB9341-2000 Plastics-Oetermination of flexural properties method;
Combustionproperty: UL94 Plastics Combustion performance test;
From upper table 1, the moulding material that monoalkyl/dialkylphosphinic salts prepared by preparation method of the present invention obtains stretches, bending and superior flame retardant property, is applicable to make polymer in-mold moulding material.