CN103073576A - Preparation method of dialkyl phosphinic acid and salt thereof - Google Patents
Preparation method of dialkyl phosphinic acid and salt thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of dialkyl phosphinic acid and salts thereof. The method comprises steps of: reacting hypophosphorous acid with high concentration with olefin under the effect of an initiator by using an organic solvent as a solvent to obtain a dialkyl phosphinic acid-organic phase solution; removing the organic solvent by water extraction or vacuum distillation, and diluting with water to obtain a dialkyl phosphinic acid aqueous solution; neutralizing with an aqueous solution of an alkaline compound to obtain a dialkyl phosphinic acid alkali metal salt aqueous solution; and reacting the dialkyl phosphinic acid alkali metal salt aqueous solution with a metal compound aqueous solution to obtain dialkyl phosphinic acid salt. The method provided by the invention employs hypophosphorous acid with high concentration as a raw material and the organic solvent with low polarity as the solvent, has a short reaction cycle only requiring 4-6 h to complete a high pressure synthesis process, and has high total yield; the synthesized dialkyl phosphinic acid product has high concentration and high purity; the process is simple; and the salified product does not contain other harmful substance or need any post-treatment.
Description
Technical field
The present invention relates to the preparation method of a kind of dialkyl phosphinic acid and salt thereof.
Background technology
Dialkyl phosphinic acid and salt thereof are widely used as fire retardant, can synthesize by diverse ways.Yuan Cheng already waits the novel method of research at organic phosphine compound-phosphine oxide acylation reaction-synthetic dialkyl phosphonic acids and derivative thereof, and (Chinese science B collects; 1984; 12; 1088-1092) and Lin Qiang etc. by quantitatively synthetic phospho acid (the Central South University's journal (natural science edition) of dialkyl phosphine oxide; 1987; 18(6); 697.) in described the Grignard reagent method and generated the phosphonous acid diethyl ester by phosphorus trichloride and ethanol synthesis; phosphonous acid diethyl ester and the reaction of self-control Grignard reagent and hydrolysis obtain the dialkyl group phosphine oxide, can obtain dialkyl phosphinic acid after dialkyl group phosphine oxide and oxidant reaction and the acidifying.The product purity of this method is higher, but this method production technique is comparatively loaded down with trivial details, reaction time is long, and especially cost height and productive rate are low, thus to making it be difficult to realize suitability for industrialized production.
Patent DE4430932 disclose two replace metal phosphinates at polyester as fire retardant, two patents of DE19910232, US6248921 disclose a kind of two preparation methods that replace metal phosphinates.US Patent No. 6359171B1 discloses a kind of preparation method of dialkyl phosphinic acid aluminium, the method at first adopts yellow phosphorus to synthesize monoalkyl phosphonate, then utilize free radical to cause to be hydrolyzed behind the vinylation sour after and the aluminium reactant salt obtain dialkyl phosphinic acid aluminium fire retardant.
Chinese patent CN98811622.7, CN98811626.X, CN98811627.8 etc. disclose with a hydration sodium hypophosphite or the 50% Hypophosporous Acid, 50 aqueous solution in acetic acid medium, cause it and ɑ-olefine reaction prepares dialkyl phosphinic acid and metal-salt thereof by azo initiator or peroxide initiator.This method is reacted in acetic acid medium, its speed of response is very fast, but solvent acetic acid and a hydration the sodium hypophosphite particularly water in 50% Hypophosporous Acid, 50 make the aftertreatment very difficulty that becomes after miscible, and because the existence of water is arranged so that the easy cancellation inactivation of radical initiator, so that need to add more radical initiator reaction is finished, the side reaction of reaction process is increased.
Chinese patent CN200410104692.0 discloses and has adopted the free radical initiation in acidic aqueous solution of a hydration sodium hypophosphite or 50% Hypophosporous Acid, 50 solution to prepare dialkyl phosphinic acid and metal-salt thereof with ɑ-olefine reaction.This scheme is carried out in water, and aftertreatment is few, but so that the easy cancellation inactivation of radical initiator, reaction time is long.
Summary of the invention
For the shortcoming that overcomes prior art with not enough, the object of the invention is to provide a kind of technical process is simple, reaction time is extremely short, overall yield is high, product purity is high dialkyl phosphinic acid and the preparation method of salt thereof.
The present invention is achieved by the following technical solutions:
The preparation method of a kind of dialkyl phosphinic acid and salt thereof comprises the steps:
A) take organic solvent as solvent, with the high density Hypophosporous Acid, 50 under the initiator effect with olefine reaction, obtain dialkyl phosphinic acid-organic phase solution;
B) dialkyl phosphinic acid-organic phase solution water extraction or underpressure distillation steaming are obtained the dialkyl phosphinic acid aqueous solution except dilute with water behind the organic solvent;
C) will obtain the dialkyl phosphinic acid aqueous solution of alkali metal salt in the aqueous solution of the dialkyl phosphinic acid aqueous solution with basic cpd;
D) dialkyl phosphinic acid aqueous solution of alkali metal salt metallizing thing reactant aqueous solution is prepared dialkyl metal phosphinate;
Wherein, the mass concentration of described high density Hypophosporous Acid, 50 is 80% ~ 100%;
Described organic solvent comprises one or more in dimethylbenzene, dioxane, ether, chloroform, ethyl acetate, methylene dichloride, dithiocarbonic anhydride or the hexane;
Described basic cpd is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium acetate or potassium acetate, preferred sodium hydroxide;
Described metallic compound is the metallic compound of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr.
Described initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
The preferred Diisopropyl azodicarboxylate of described azo-initiator or 2,2'-Azobis(2,4-dimethylvaleronitrile); The preferred benzoyl peroxide formic acid of described organic peroxide evocating agent, peroxidation lauric acid, ditertiary butyl peroxide, peroxycarbonates, mistake oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester or the special pentyl ester of peroxidation; Described inorganic peroxide initiator initiator system of ammonium persulfate, Sodium Persulfate or Potassium Persulphate.
The mass ratio of described organic solvent and high density Hypophosporous Acid, 50 is 0.3 ~ 2:1, preferred 0.4 ~ 0.7:1.
Described alkene is ɑ-alkene or naphthenic alkene.The mixture of one or more in described ɑ-alkene optimal ethylene, propylene, butylene, iso-butylene or the amylene; Described naphthenic alkene cyclopentene or tetrahydrobenzene.
The mol ratio of described high density Hypophosporous Acid, 50 and alkene is greater than 2:1, preferred 2.1 ~ 2.5:1.
Temperature of reaction in the step a) is 50 ~ 100 ℃, preferred 70 ~ 80 ℃; Reaction pressure is 0.5MPa ~ 6MPa, preferred 0.6MPa ~ 2.5MPa.
The mass concentration of the described dialkyl phosphinic acid aqueous solution is 5% ~ 60%, preferred 10% ~ 40%.
The mol ratio of described basic cpd and dialkyl phosphinic acid is 0.9 ~ 1.1:1.
The mass concentration of the described basic cpd aqueous solution is 1% ~ 50%, preferred 10% ~ 30%.
Described metallic compound is metal oxide, metal hydroxides, metal nitrate, metal sulfate, metal chloride or metal acetate, is preferably Tai-Ace S 150, aluminum chloride, aluminium hydroxide, aluminum acetate, aluminum nitrate, aluminum oxide, ferric sulfate, Iron(III) chloride hexahydrate, ironic hydroxide, iron nitrate, ferric oxide, sal epsom, magnesium chloride, magnesium hydroxide, magnesium acetate, magnesium nitrate, calcium sulfate, calcium chloride, calcium hydroxide, zinc sulfate, zinc chloride, zinc hydroxide, zinc acetate, zinc nitrate, ferrous sulfate, iron protochloride, ferrous hydroxide or ferrous acetate.
Steps d) temperature of reaction is under 0 ℃ ~ 150 ℃, preferred 70 ℃ ~ 90 ℃.
Steps d) dialkyl metal phosphinate that obtains separates from mixture by filtration or centrifugal treating.
The preparation method of described high density Hypophosporous Acid, 50 comprises the steps:
A) the Hypophosporous Acid, 50 aqueous solution of 50% massfraction and organic solvent I being heated azeotropic distillation to massfraction in inert atmosphere is 80 ~ 95%, separates Hypophosporous Acid, 50 and the organic solvent I of 80 ~ 95% massfractions;
B) Hypophosporous Acid, 50 that step a) is obtained and organic solvent II heat azeotropic distillation in inert atmosphere, decompression steams organic solvent II, can obtain the Hypophosporous Acid, 50 of high density;
Wherein, described organic solvent I is benzene,toluene,xylene, chloroform or hexanaphthene; Described organic solvent II is methyl alcohol or ethanol.
The mass ratio of described organic solvent I and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferred 0.5 ~ 1.2:1; The mass ratio of organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferred 0.5 ~ 1.2:1.
Described high density Hypophosporous Acid, 50 can also prepare as follows:
A) the Hypophosporous Acid, 50 aqueous solution of 50% massfraction being evaporated to massfraction is 80 ~ 95%;
B) Hypophosporous Acid, 50 that step a) is obtained and organic solvent II heat azeotropic distillation in inert atmosphere, decompression steams organic solvent II, can obtain the Hypophosporous Acid, 50 of high density;
Described organic solvent II is methyl alcohol or ethanol.In this method, its operation stage a) in, described vacuum tightness is-0.090MPa ~-0.100MPa.
The mass ratio of described organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferred 0.5 ~ 1.2:1.
The reactor of using in rectifying described in above-mentioned two kinds of preparation methods is equipped with water-and-oil separator and condenser, and at operation stage b) in, drier system is housed in water-and-oil separator and condenser and is provided with the dismounting mouth that can dismantle at any time drier system, siccative uses calcium chloride, magnesium chloride, sal epsom, silica-gel drier, alumina gel siccative, molecular sieve desiccant, mineral agent or fiber desiccant etc. in the described solid drier system.
The invention also discloses a kind of flame-retardant polymer moulding material, comprise dialkyl phosphinic acid and salt thereof that the above-mentioned method of 5-20wt% is made, 50-70wt% polymkeric substance or its mixture, 15-30wt% glass fibre, other auxiliary agents of 1-5wt%.
Described polymkeric substance can be PBT, PET, PC, PA, PS etc.
The present invention compared with prior art has following beneficial effect:
1) to adopt the high density Hypophosporous Acid, 50 be raw material in the present invention, and take the lower organic solvent of polarity as solvent, reaction time is extremely short, only needs 4 ~ 6h can finish the high pressure building-up process;
2) utilize the overall yield of the dialkyl phosphinic acid that the method obtains high, near 90wt%; Side reaction is few, and the purity of product is high;
3) technical process of the present invention is simple; Without other objectionable impuritiess, do not need other aftertreatments behind the product salify yet;
4) organic solvent recoverable.
Embodiment
Further specify the present invention below by embodiment, following examples are the better embodiment of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.
Embodiment 1:The preparation of high density Hypophosporous Acid, 50
Getting the 400.1g massfraction is 50% Hypophosporous Acid, 50 and 250ml hexanaphthene, adds to be equipped with in the reaction flask of water-and-oil separator and condenser, fills it up with hexanaphthene in water-and-oil separator;
Heated and stirred is to the about 2h of azeotropic under nitrogen protection, and the water that separate the water-and-oil separator bottom is discharged in gradation midway; Solution in the reaction flask is added separating funnel separate to get the liquid 249.8g of lower floor, get acid content with the acid base titration titration and be: the 80%(massfraction).
Embodiment 2:The preparation of high density Hypophosporous Acid, 50
Getting the 400.1g massfraction is 50% Hypophosporous Acid, 50 and 250ml hexanaphthene, adds to be equipped with in the reaction flask of water-and-oil separator and condenser, fills it up with hexanaphthene in water-and-oil separator;
Heated and stirred is to the about 3h of azeotropic under nitrogen protection, and the water that separate the water-and-oil separator bottom is discharged in gradation midway; Solution in the reaction flask is added separating funnel separate to get the liquid 222.2g of lower floor, get acid content with the acid base titration titration and be: 90.35% (massfraction).
Embodiment 3:The preparation of high density Hypophosporous Acid, 50
Getting the 400.1g massfraction is 50% Hypophosporous Acid, 50 and 250ml hexanaphthene, adds to be equipped with in the reaction flask of water-and-oil separator and condenser, fills it up with hexanaphthene in water-and-oil separator;
Heated and stirred is to the about 4h of azeotropic under nitrogen protection, and the water that separate the water-and-oil separator bottom is discharged in gradation midway; Solution in the reaction flask is added separating funnel separate to get the liquid 212.4g of lower floor, get acid content with the acid base titration titration and be: 94.07% (massfraction).
Get Hypophosporous Acid, 50 200.2g and the 200ml methyl alcohol of 94.07% massfraction, add and be equipped with in the reaction flask of water-and-oil separator and condenser, fixing solid calcium chloride is housed in water-and-oil separator wherein and the condenser and fills it up with methyl alcohol in water-and-oil separator, heated and stirred is to azeotropic 4h under nitrogen protection; With the solution in the reaction flask on Rotary Evaporators 60 ℃, concentrating under reduced pressure 4h is cooled to room temperature under the-0.098KPa, and emptying obtains the 198.6g Hypophosporous Acid, 50.Drip to such an extent that acid content is 99.78% (massfraction) with acid base titration.Drip to such an extent that obtain Hypophosporous Acid, 50 content 99.49% (massfraction), phosphorous acid content with oxidation reduction process: 0.24% (massfraction).
Embodiment 4:
Being prepared into massfraction with embodiment 3 is 99.49% high density Hypophosporous Acid, 50, getting massfraction is 99.49% high density Hypophosporous Acid, 50 181.2g(2.732mol), dimethylbenzene 220ml and 2.4g(0.014mol, 0.5%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in the autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) displacement 5 times, after be filled with to 2.5MPa ethene saturated, under agitation be heated to 70 ℃, evenly add 4.7g(0.027mol in 4 hours, 1.0%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 20ml dimethylbenzene, in 5 hours, evenly be warming up to 80 ℃, with this reactor cooling and emptying, obtain diethyl phospho acid homogeneous phase solution 529.9g, acid content: 62.90% (massfraction);
31P-NMR analyzes diethyl phospho acid mol content: 97.3%
Ethyl-butyl phospho acid mol content: 2.2%
Other mol content: 0.5%
Diethyl phospho acid homogeneous phase solution 529.9g obtains diethyl phospho acid aqueous solution 1198.9g altogether with 300ml water extraction three times, and recording acid content is 24.91%, and sour mole number is 2.448mol, yield 89.6wt%;
Diethyl phospho acid aqueous solution 1198.9g is added in the reactor, be heated with stirring to 95 ℃, neutralizing with the sodium hydroxide of 30% massfraction obtains diethyl phospho acid sodium water solution;
With 271.8g(0.408mol) Tai-Ace S 150 is dissolved in the 600ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 600ml water washing three times, be dried to constant weight at 150 ℃, obtain 313.2g diethyl phospho acid aluminium, white powder, overall yield 88.18wt%.
Embodiment 5:
It is 80% high density Hypophosporous Acid, 50 that embodiment 1 is prepared into massfraction, getting massfraction is 80% high density Hypophosporous Acid, 50 500.2g(6.061mol), dimethylbenzene 725ml and 10.6g(0.061mol, 1.0%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in the autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) displacement 5 times, after be filled with to 2.5MPa ethene saturated, under agitation be heated to 70 ℃, evenly add 21.2g(0.061mol in 5 hours, 2.0%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 50ml dimethylbenzene, in 6 hours, evenly be warming up to 80 ℃, with this reactor cooling and emptying, obtain diethyl phospho acid homogeneous phase solution 1475.1g, acid content: 50.07% (massfraction);
31P-NMR analyzes diethyl phospho acid mol content: 94.3%
Ethyl-butyl phospho acid mol content: 4.6%
Other mol content: 1.1%
Diethyl phospho acid homogeneous phase solution 1475.1g obtains diethyl phospho acid aqueous solution 3658.9g altogether with 1000ml water extraction three times, and recording acid content is 18.0%, and sour mole number is 5.398mol, yield 89.1wt%;
Diethyl phospho acid aqueous solution 3658.9g is added in the reactor, be heated with stirring to 95 ℃, neutralizing with the sodium hydroxide of 30% massfraction obtains diethyl phospho acid sodium water solution;
With 599.2g(0.900mol) Tai-Ace S 150 is dissolved in the 1200ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 1200ml water washing three times, be dried to constant weight at 150 ℃, obtain 692.3g diethyl phospho acid aluminium, white powder, overall yield 87.87wt%.
Embodiment 6:
Being prepared into massfraction with embodiment 2 is 90.35% high density Hypophosporous Acid, 50, getting massfraction is 90.35% high density Hypophosporous Acid, 50 460.0g(6.273mol), dithiocarbonic anhydride 450ml, 7.6g(0.044mol, 0.7%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in the autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) displacement 5 times, after be filled with to 2.5MPa ethene saturated, under agitation be heated to 70 ℃, in 5.5 hours, add continuously 8.7g(0.050mol, 0.8%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 30ml dimethylbenzene, and in 7 hours, evenly be warming up to 80 ℃, with this reactor cooling and emptying, obtain diethyl phospho acid solution 1374.7g;
31P-NMR analyzes diethyl phospho acid mol content: 95.2%
Ethyl-butyl phospho acid mol content: 3.5%
Other mol content: 1.3%
Diethyl phospho acid homogeneous phase solution 1374.7g obtains diethyl phospho acid aqueous solution 3689.9g altogether with 1000ml water extraction three times, and recording acid content is 18.7%, and sour mole number is 5.656mol, yield 90.2wt%;
Diethyl phospho acid aqueous solution 3689.9g is added in the reactor, be heated with stirring to 95 ℃, neutralizing with the potassium hydroxide of 30% massfraction obtains diethyl phospho acid aqueous solutions of potassium;
With 627.8g(0.943mol) Tai-Ace S 150 is dissolved in the 1200ml aqueous solution and splashed into diethyl phospho acid aqueous solutions of potassium in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 1200ml water washing three times, be dried to constant weight at 150 ℃, obtain 725.1g diethyl phospho acid aluminium, white powder, overall yield 88.92wt%.
Embodiment 7:
Obtain diethyl phospho acid homogeneous phase solution 1475.1g with 1000ml water extraction three times with embodiment 5, obtain altogether diethyl phospho acid aqueous solution 3658.9g, recording acid content is 18.0%, and sour mole number is 5.398mol, yield 89.1wt%;
Get diethyl phospho acid 18.0% aqueous solution 1851.7g(2.732mol), be heated with stirring to 95 ℃, obtain diethyl phospho acid aqueous solutions of potassium with the neutralization of the potassium hydroxide of 30% massfraction;
Metal-salt adopts Iron(III) chloride hexahydrate, with 246.2g(0.911mol) Iron(III) chloride hexahydrate is dissolved in the 600ml aqueous solution and splashed into diethyl phospho acid aqueous solutions of potassium in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, obtain 305.3g diethyl phospho acid iron, white powder, salt manufacturing productive rate 80.01wt%.
IR：773CM-1,1045CM-1,1107CM-1,?2880CM-1,2939CM-1,2959CM-1。
340 ℃ of TG:1% weightless temperatures, 425 ℃ of 5% weightless temperatures.
Embodiment 8:
Obtain diethyl phospho acid homogeneous phase solution 1475.1g with 1000ml water extraction three times with embodiment 5, obtain altogether diethyl phospho acid aqueous solution 3658.9g, recording acid content is 18.0%, and sour mole number is 5.398mol, yield 89.1wt%;
Get diethyl phospho acid 18.0% aqueous solution 1851.7g(2.732mol), be heated with stirring to 95 ℃, obtain diethyl phospho acid sodium water solution with the neutralization of the sodium hydroxide of 30% massfraction;
Metal-salt adopts anhydrous magnesium sulfate, with 164.4g(1.367mol) anhydrous magnesium sulfate is dissolved in the 350ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, obtain 297.8g diethyl phospho acid magnesium, salt manufacturing yield 81.90wt%.
IR:?773CM-1,?1089CM-1,?1169CM-1,?2881CM-1,2939CM-1,2964CM-1。
330 ℃ of TG:1% weightless temperatures, 426 ℃ of 5% weightless temperatures.
Embodiment 9:
Obtain diethyl phospho acid homogeneous phase solution 1475.1g with 1000ml water extraction three times with embodiment 5, obtain altogether diethyl phospho acid aqueous solution 3658.9g, recording acid content is 18.0%, and sour mole number is 5.398mol, yield 89.1wt%;
Get diethyl phospho acid 18.0% aqueous solution 1851.7g(2.732mol), be heated with stirring to 95 ℃, obtain diethyl phospho acid sodium water solution with the neutralization of the sodium hydroxide of 30% massfraction;
Metal-salt adopts Calcium Chloride Powder Anhydrous, with 150.3g(1.367mol) Calcium Chloride Powder Anhydrous is dissolved in the 350ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, obtain 301.6g diethyl phospho acid calcium, yield 78.21wt%.
IR:?777CM-1,?1060CM-1,?1105CM-1,?2881CM-1,2939CM-1,2960CM-1。
332 ℃ of TG:1% weightless temperatures, 423 ℃ of 5% weightless temperatures.
Embodiment 10:
Obtain diethyl phospho acid homogeneous phase solution 1475.1g with 1000ml water extraction three times with embodiment 5, obtain altogether diethyl phospho acid aqueous solution 3658.9g, recording acid content is 18.0%, and sour mole number is 5.398mol, yield 89.1wt%.
Get diethyl phospho acid 18.0% aqueous solution 1851.7g(2.732mol), be heated with stirring to 95 ℃, obtain diethyl phospho acid sodium water solution with the neutralization of the sodium hydroxide of 30% massfraction;
Metal-salt adopts zinc sulfate, with 219.0g(1.367mol) zinc sulfate is dissolved in the 450ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, obtain 367.1g diethyl phospho acid zinc, yield 87.44wt%.
IR:?775CM-1,?1055CM-1,?1134CM-1,?2883CM-1,2941CM-1,2974CM-1。
315 ℃ of TG:1% weightless temperatures, 420 ℃ of 5% weightless temperatures.
Embodiment 11:
Obtain diethyl phospho acid homogeneous phase solution 1475.1g with 1000ml water extraction three times with embodiment 5, obtain altogether diethyl phospho acid aqueous solution 3658.9g, recording acid content is 18.0%, and sour mole number is 5.398mol, yield 89.1wt%;
Get diethyl phospho acid 18.0% aqueous solution 1851.7g(2.732mol), be heated with stirring to 95 ℃, obtain diethyl phospho acid sodium water solution with the neutralization of the sodium hydroxide of 30% massfraction;
Metal-salt adopts ferrous sulfate, with 379.7g(1.367mol) ferrous sulfate is dissolved in the 450ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, it is ferrous to obtain 300.5 g diethyl phospho acid, yield 73.63wt%.
IR:?773CM-1,?1043CM-1,?1105CM-1,?2880CM-1,2939CM-1,2958CM-1。316 ℃ of TG:1% weightless temperatures, 418 ℃ of 5% weightless temperatures.
Comparative Examples 1
Getting the 360.6g massfraction is 50% Hypophosporous Acid, 50 (2.732mol) and 4.7g(0.027mol, 1.0%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in the autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) displacement 5 times, after be filled with to 2.5MPa ethene saturated, under agitation be heated to 72 ℃, in 14h, evenly add 9.4g(0.054mol, 2.0%mol) the peroxidation trimethylacetic acid tert-butyl ester, and evenly be warming up to 85 ℃, with this reactor cooling and emptying, obtain product water solution 557.9g, acid content: 30.75% (massfraction);
31P-NMR analyzes diethyl phospho acid mol content: 57.4%
Ethyl-butyl phospho acid mol content: 32.2%
Other mol content: 10.4 %
300g water and high density diethyl phospho acid 557.9g obtained above are added in the reactor, are heated with stirring to 95 ℃,
Sodium hydroxide neutralization with 30% massfraction obtains diethyl phospho acid sodium water solution;
With 303.3g(0.455mol) Tai-Ace S 150 is dissolved in the 700ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, obtain the 295.7g white powder, overall yield 83.26wt%.
Comparative Examples 2
Get 289.6g one hydration sodium hypophosphite (2.732mol), 500g acetic acid and 7.0g(0.027mol, 1.0%mol) Diisopropyl azodicarboxylate adds in the autoclave together, the enclosed high pressure still, under agitation use nitrogen (0.5MPa) displacement 5 times, after be filled with to 2.5MPa ethene saturated, under agitation be heated to 72 ℃, in 8h, evenly add 10.5g(0.041mol, 1.5%mol) Diisopropyl azodicarboxylate, and evenly be warming up to 85 ℃, with this reactor cooling and emptying, obtain solution 946.1g, 130 ℃ of underpressure distillation 2 hours obtain the 453.1g dope;
31P-NMR analyzes diethyl phospho acid mol content: 91.3%
Ethyl-butyl phospho acid mol content: 5.1%
Other mol content: 3.6 %
To be dissolved in the 750ml water with 453.1g dope obtained above and add in the reactor, be heated with stirring to 95 ℃, obtain diethyl phospho acid sodium water solution with the sodium hydroxide neutralization of 30% massfraction; With 303.3g(0.455mol) Tai-Ace S 150 is dissolved in the 700ml aqueous solution and splashed into diethyl phospho acid sodium water solution in 1 hour, under 90 ~ 95 ℃, be incubated 1 hour after dripping off, be cooled to room temperature, the gained solid is leached, and with 700ml water washing three times, be dried to constant weight at 150 ℃, obtain the 326.9g white powder, overall yield 92.03wt%.
The dialkylphosphinic salts of embodiment 4 ~ 11 and Comparative Examples 1-2 gained is mixed by weight 10:60:25:5 with PBT, glass, auxiliary agent at 230-260 ℃, from Bitruder, extrude, make flame-proofed thermoplastic or thermosetting polymer moulding material, its combustionproperty and mechanical property are tested in sample preparation, record the result and see table 1:
The moulding material combustionproperty that table 1, dialkylphosphinic salts make 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 as can be known, moulding material stretching, bending and flame retardant properties that the dialkylphosphinic salts of preparation method's preparation of the present invention makes are superior, are applicable to make the polymer in-mold moulding material.
Claims (22)
1. the preparation method of a dialkyl phosphinic acid and salt thereof is characterized in that, comprises the steps:
A) take organic solvent as solvent, with the high density Hypophosporous Acid, 50 under the initiator effect with olefine reaction, obtain dialkyl phosphinic acid-organic phase solution;
B) dialkyl phosphinic acid-organic phase solution water extraction or underpressure distillation steaming are obtained the dialkyl phosphinic acid aqueous solution except dilute with water behind the organic solvent;
C) the dialkyl phosphinic acid aqueous solution is obtained the dialkyl phosphinic acid aqueous solution of alkali metal salt with the neutralization of the aqueous solution of basic cpd;
D) dialkyl phosphinic acid aqueous solution of alkali metal salt metallizing thing reactant aqueous solution is prepared dialkyl metal phosphinate;
Wherein, the mass concentration of described high density Hypophosporous Acid, 50 is 80% ~ 100%;
Described organic solvent comprises one or more in dimethylbenzene, dioxane, ether, chloroform, ethyl acetate, methylene dichloride, dithiocarbonic anhydride or the hexane;
Described basic cpd is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium acetate or potassium acetate, preferred sodium hydroxide;
Described metallic compound is the metallic compound of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr.
2. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, described initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
3. the preparation method of dialkyl phosphinic acid according to claim 2 and salt thereof is characterized in that, described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organic peroxide evocating agent is benzoyl peroxide formic acid, peroxidation lauric acid, ditertiary butyl peroxide, peroxycarbonates, mistake oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester or the special pentyl ester of peroxidation; Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
4. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the mass ratio of described organic solvent and high density Hypophosporous Acid, 50 is 0.3 ~ 2:1, preferred 0.4 ~ 0.7:1.
5. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, described alkene is ɑ-alkene or naphthenic alkene.
6. the preparation method of dialkyl phosphinic acid according to claim 5 and salt thereof is characterized in that, described ɑ-alkene comprises one or more the mixture in ethene, propylene, butylene, iso-butylene or the amylene; Described naphthenic alkene is cyclopentenes or tetrahydrobenzene.
7. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the mol ratio of described high density Hypophosporous Acid, 50 and alkene is greater than 2:1, preferred 2.1 ~ 2.5:1.
8. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the temperature of reaction in the step a) is 50 ~ 100 ℃, preferred 70 ~ 80 ℃; Reaction pressure is 0.5MPa ~ 6MPa, preferred 0.6MPa ~ 2.5MPa.
9. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the mass concentration of the described dialkyl phosphinic acid aqueous solution is 5% ~ 60%, preferred 10% ~ 40%.
10. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the mol ratio of described basic cpd and dialkyl phosphinic acid is 0.9 ~ 1.1:1; The mass concentration of the described basic cpd aqueous solution is 1% ~ 50%, preferred 10% ~ 30%.
11. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, described metallic compound is metal oxide, metal hydroxides, metal nitrate, metal sulfate, metal chloride or metal acetate.
12. the preparation method of dialkyl phosphinic acid according to claim 11 and salt thereof, it is characterized in that described metallic compound is Tai-Ace S 150, aluminum chloride, aluminium hydroxide, aluminum acetate, aluminum nitrate, aluminum oxide, ferric sulfate, Iron(III) chloride hexahydrate, ironic hydroxide, iron nitrate, ferric oxide, sal epsom, magnesium chloride, magnesium hydroxide, magnesium acetate, magnesium nitrate, calcium sulfate, calcium chloride, calcium hydroxide, zinc sulfate, zinc chloride, zinc hydroxide, zinc acetate, zinc nitrate, ferrous sulfate, iron protochloride, ferrous hydroxide or ferrous acetate.
13. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, steps d) temperature of reaction be under 0 ℃ ~ 150 ℃, preferred 70 ℃ ~ 90 ℃.
14. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, steps d) dialkyl metal phosphinate that obtains is by filtering or centrifugal treating is separated from mixture.
15. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the preparation method of described high density Hypophosporous Acid, 50 comprises the steps:
A) the Hypophosporous Acid, 50 aqueous solution of 50% massfraction and organic solvent I being heated azeotropic distillation to massfraction in inert atmosphere is 80 ~ 95%, separates Hypophosporous Acid, 50 and the organic solvent I of 80 ~ 95% massfractions;
B) Hypophosporous Acid, 50 that step a) is obtained and organic solvent II heat azeotropic distillation in inert atmosphere, decompression steams organic solvent II, can obtain the Hypophosporous Acid, 50 of high density;
Wherein, described organic solvent I is benzene,toluene,xylene, chloroform or hexanaphthene; Described organic solvent II is methyl alcohol or ethanol.
16. the preparation method of dialkyl phosphinic acid according to claim 15 and salt thereof is characterized in that, the mass ratio of described organic solvent I and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferred 0.5 ~ 1.2:1; The mass ratio of organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferred 0.5 ~ 1.2:1.
17. the preparation method of dialkyl phosphinic acid according to claim 1 and salt thereof is characterized in that, the preparation method of described high density Hypophosporous Acid, 50 comprises the steps:
A) the Hypophosporous Acid, 50 aqueous solution of 50% massfraction being evaporated to massfraction is 90 ~ 95%;
B) Hypophosporous Acid, 50 that step a) is obtained and organic solvent II heat azeotropic distillation in inert atmosphere, decompression steams organic solvent II, can obtain the Hypophosporous Acid, 50 of high density;
Described organic solvent II is methyl alcohol or ethanol, and the mass ratio of organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferred 0.5 ~ 1.2:1.
18. the preparation method of dialkyl phosphinic acid according to claim 17 and salt thereof is characterized in that, its operation stage a) in, described vacuum tightness is-0.090MPa ~-0.100MPa.
19. according to claim 15 or the preparation method of 17 described dialkyl phosphinic acids and salt thereof, it is characterized in that the reactor that described rectifying is used is equipped with water-and-oil separator and condenser.
20. according to claim 15 or the preparation method of 17 described dialkyl phosphinic acids and salt thereof, it is characterized in that, its operation stage b) in, the reactor that described rectifying is used is equipped with water-and-oil separator and condenser, drier system is housed in water-and-oil separator and condenser and is provided with the dismounting mouth that can dismantle at any time drier system.
21. the preparation method of dialkyl phosphinic acid according to claim 20 and salt thereof, it is characterized in that the siccative in the described drier system is calcium chloride, magnesium chloride, sal epsom, silica-gel drier, alumina gel siccative, molecular sieve desiccant, mineral agent or fiber desiccant.
22. one kind comprises dialkyl phosphinic acid that each described method of claim 1-21 makes or the flame-retardant polymer moulding material of its salt, it is characterized in that, comprise 5-20wt% dialkyl phosphinic acid or its salt, 50-70wt% polymkeric substance or its mixture, the 15-30wt% glass fibre, other auxiliary agents of 1-5wt%.
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