CN103087098B - A kind of dialkylphosphinic salts and preparation method thereof - Google Patents
A kind of dialkylphosphinic salts and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of dialkylphosphinic salts, there is structure formula I,
r
1, R
2identical or different, for carbonatoms is the alkyl of 2-6; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr; M=1-4; Wherein telomer content is 0.1-10mol%.Preparation method: with hexanaphthene and/or tetrahydrobenzene for solvent, high density Hypophosporous Acid, 50 under initiator effect with olefine reaction, obtain dialkyl phosphinic acid-organic phase solution; After removing organic solvent with water extraction or underpressure distillation steaming, dilute with water obtains the dialkyl hypophosphorous acid aqueous solution; Dialkyl hypophosphorous acid aqueous solution of alkali metal salt is obtained with the aqueous solution neutralization of basic cpd; Dialkyl phosphinic acid aqueous solution of alkali metal salt metallizing thing reactant aqueous solution and get final product.The present invention is with high density Hypophosporous Acid, 50 for raw material, and with hexanaphthene and/or tetrahydrobenzene for solvent, obtain the product containing part telomer, reaction time is extremely short, and only need 4 ~ 6h to complete synthesis, overall yield is high; Technical process is simple, the recyclable process of organic solvent.
Description
Technical field
The present invention relates to a kind of dialkylphosphinic salts and preparation method thereof.
Background technology
Dialkylphosphinic salts, is widely used as fire retardant, synthesizes by diverse ways.In the novel method of the research-phosphine oxide acylation reaction-synthesis dialkyl phosphonic acids of organic phosphine compound and derivative thereof, (Chinese science B collects Yuan Chengye etc., 1984, 12, 1088-1092) and Lin Qiang etc. quantitatively synthesized phospho acid (Central South University's journal (natural science edition) by dialkyl phosphine oxide, 1987, 18(6), 697.) describe Grignard reagent method in and generate phosphonous acid diethyl ester by phosphorus trichloride and ethanol synthesis, phosphonous acid diethyl ester and self-control Grignard reagent react and are hydrolyzed and obtain dialkyl group phosphine oxide, dialkyl group phosphine oxide and oxidant reaction also can obtain dialkyl phosphinic acid after 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 is high and productive rate is low, thus to making it be difficult to realize suitability for industrialized production.
Patent DE4430932 discloses two replacement metal phosphinates and is used as fire retardant at polyester, DE19910232, US6248921 two patents, discloses the preparation method that a kind of two replace metal phosphinate.US Patent No. 6359171B1 discloses a kind of preparation method of dialkyl phosphinic acid aluminium, first the method adopts yellow phosphorus to synthesize monoalkyl phosphonate, then utilize free radical to cause to be hydrolyzed after vinylation sour after and 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 50% aqueous hypophosphorous acid 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 make aftertreatment become very difficulty after solvent acetic acid and the hydration sodium hypophosphite water particularly in 50% Hypophosporous Acid, 50 is miscible, and because there is the existence of water to make the easy cancellation inactivation of radical initiator, making to need to add more radical initiator just can make reaction complete, and while increasing cost, the side reaction of reaction process is increased.
Chinese patent CN200410104692.0 discloses employing one hydration sodium hypophosphite or 50% Hypophosporous Acid, 50 solution free radical in acidic aqueous solution causes and ɑ-olefine reaction prepares dialkyl phosphinic acid and metal-salt thereof.The program is carried out in water, and aftertreatment is few, but makes the easy cancellation inactivation of radical initiator, and reaction time is long.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the invention is to provide a kind of dialkylphosphinic salts containing telomer.
Another object of the present invention is to provide the preparation method of the dialkylphosphinic salts that a kind of technical process is simple, reaction time is extremely short, overall yield is high, product purity is high.
The present invention is achieved by the following technical solutions:
A kind of dialkylphosphinic salts, has following structure formula I,
Wherein, R
1, R
2identical or different, for carbonatoms is the alkyl of 2-6;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 1-4;
Wherein telomer is the ethyl-butyl phospho acid of 0.1-10mol content, ethyl (cyclohexyl ethylidene) phosphinates and/or butyl (cyclohexyl ethylidene) phosphinates.
Preferably, R
1, R
2identical or different, be ethyl, propyl group, butyl, isobutyl-and/or amyl group.
The preparation method of above-mentioned dialkylphosphinic salts, comprises the steps:
A) with hexanaphthene and/or tetrahydrobenzene for solvent, by high density Hypophosporous Acid, 50 under initiator effect with olefine reaction, obtain dialkyl phosphinic acid-organic phase solution;
B) after dialkyl phosphinic acid-organic phase solution water extraction or underpressure distillation steaming being removed organic solvent, dilute with water obtains the dialkyl phosphinic acid aqueous solution;
C) neutralization of the aqueous solution of dialkyl phosphinic acid aqueous solution basic cpd is obtained dialkyl hypophosphorous acid aqueous solution of alkali metal salt;
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 90% ~ 100%;
Described basic cpd is sodium hydroxide, potassium hydroxide, sodium carbonate, 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 special pentyl ester of the preferred perbenzoic acid of described organic peroxide evocating agent, peroxylauric acid, ditertiary butyl peroxide, peroxycarbonates, excessively oxalic acid, tert-butyl hydroperoxide isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester or peroxidation; Described inorganic peroxide initiator initiator system of ammonium persulfate, Sodium Persulfate or Potassium Persulphate.
The mass ratio of described hexanaphthene and/or tetrahydrobenzene and high density Hypophosporous Acid, 50 is 0.2 ~ 3:1, preferably 0.3 ~ 0.7:1.
Described alkene is ɑ-alkene.
The mixture of one or more in described ɑ-alkene optimal ethylene, propylene, butylene, iso-butylene or amylene.
The mol ratio of described high density Hypophosporous Acid, 50 and alkene is greater than 2:1, preferably 2.1 ~ 2.5:1.
Temperature of reaction in step a) is 50 ~ 100 DEG C, preferably 70 ~ 80 DEG C; 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%, preferably 10% ~ 40%.
Described basic cpd and the mol ratio of dialkyl phosphinic acid are 0.9 ~ 1.1:1.
The mass concentration of the described basic cpd aqueous solution is 1% ~ 50%, preferably 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, magnesium sulfate, 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 be at 0 DEG C ~ 150 DEG C, preferably 70 DEG C ~ 90 DEG C.
Steps d) dialkyl metal phosphinate that obtains is by filter or centrifugal treating is separated from mixture.
The preparation method of described high density Hypophosporous Acid, 50 comprises the steps:
A) aqueous hypophosphorous acid of 50% massfraction and organic solvent I being heated azeotropic distillation to massfraction is in an inert atmosphere 80 ~ 95%, is separated Hypophosporous Acid, 50 and the organic solvent I of 80 ~ 95% massfractions;
B) Hypophosporous Acid, 50 step a) obtained and organic solvent II heat azeotropic distillation in an inert atmosphere, and 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, preferably 0.5 ~ 1.2:1; The mass ratio of organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 2:1, preferably 0.5 ~ 1.2:1.
Described high density Hypophosporous Acid, 50 can also be prepared as follows:
A) aqueous hypophosphorous acid of 50% massfraction being evaporated to massfraction is 80 ~ 95%;
B) Hypophosporous Acid, 50 step a) obtained and organic solvent II heat azeotropic distillation in an inert atmosphere, and 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, preferably 0.5 ~ 1.2:1.
Described in above-mentioned two kinds of preparation methods, the reactor of rectifying is equipped with water-and-oil separator and condenser, and at operation stage b) in, in water-and-oil separator and condenser, drier system be housed and be provided with the dismounting mouth can dismantling drier system at any time, in described solid drier system, siccative is calcium chloride, magnesium chloride, magnesium sulfate, silica-gel drier, alumina gel siccative, molecular sieve desiccant, mineral agent or fiber desiccant.
The invention also discloses the purposes that above-mentioned dialkylphosphinic salts is used as fire retardant.
The invention also discloses a kind of flame-retardant polymer moulding material, comprise the above-mentioned dialkylphosphinic salts of 5-20wt%, 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) the present invention adopts high density Hypophosporous Acid, 50 to be raw material, and with hexanaphthene and/or tetrahydrobenzene for solvent, can obtain the product containing part telomer, reaction time is extremely short, only needs 4 ~ 6h can complete high-pressure synthesis process;
2) overall yield of the dialkylphosphinic salts utilizing the method to obtain is high, close to 90wt%;
3) present invention process flow process is simple, organic solvent recoverable.
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.
embodiment 1:the preparation of high density Hypophosporous Acid, 50
Getting 400.1g massfraction is 50% Hypophosporous Acid, 50 and 250ml hexanaphthene, adds in the reaction flask that water-and-oil separator and condenser are housed, in water-and-oil separator, fills it up with hexanaphthene;
Heated and stirred is about 3h to azeotropic under nitrogen protection, midway gradation discharge water-and-oil separator bottom part from water; Solution in reaction flask is added separating funnel and be separated to obtain lower floor liquid 223.1g, obtaining acid content with acid base titration titration is: 90.31% massfraction.
embodiment 2:the preparation of high density Hypophosporous Acid, 50
Getting 400.1g massfraction is 50% Hypophosporous Acid, 50 and 250ml hexanaphthene, adds in the reaction flask that water-and-oil separator and condenser are housed, in water-and-oil separator, fills it up with hexanaphthene;
Heated and stirred is about 4h to azeotropic under nitrogen protection, midway gradation discharge water-and-oil separator bottom part from water; Solution in reaction flask is added separating funnel and be separated to obtain lower floor liquid 212.0g, obtaining acid content with acid base titration titration is: 94.09% massfraction.
Get Hypophosporous Acid, 50 200.2g and the 200ml methyl alcohol of 94.09% massfraction, add in the reaction flask that water-and-oil separator and condenser are housed, in water-and-oil separator wherein and condenser, fixing solid silicone siccative is housed and fills it up with methyl alcohol in water-and-oil separator, heated and stirred is to azeotropic 4h under nitrogen protection; By the solution in reaction flask 60 DEG C on a rotary evaporator, under-0.098KPa, concentrating under reduced pressure 4h, is cooled to room temperature, and emptying obtains 198.5g Hypophosporous Acid, 50.Drip acid content is 99.75%(massfraction by acid base titration).Drip obtain Hypophosporous Acid, 50 content 99.43%(massfraction by oxidation reduction process), phosphorous acid content: 0.28%(massfraction).
embodiment 3:
Be prepared into the high density Hypophosporous Acid, 50 of 99.43% massfraction with embodiment 2, get the high density time phosphorus of 99.43% massfraction
181.6g(2.733mol), hexanaphthene 150ml and 2.4g(0.014mol, 0.5%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 is filled with to 2.5MPa saturated, under agitation be heated to 70 DEG C, evenly 4.7g(0.027mol is added in 4 hours, 1.0%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 20ml hexanaphthene, 80 DEG C are evenly warming up in 5 hours, by this reactor cooling also emptying, obtain the diethyl phospho acid homogeneous phase solution 474.1g containing telomer, acid content: 72.01%(massfraction),
Diethyl phospho acid homogeneous phase solution 474.1g, extracts three times with 300ml water, obtains the diethyl phospho acid aqueous solution altogether
1197.3g, recording acid content is 24.23%(massfraction), sour mole number is 2.383mol, yield 87.2wt%;
Diethyl phospho acid aqueous solution 1197.3g is added in reactor, is heated with stirring to 95 DEG C, obtain the diethyl sodium hypophosphite aqueous solution with the sodium hydroxide neutralization of 30% massfraction;
By 264.5g(0.397mol) Patent alum to be dissolved in the 550ml aqueous solution and in 1 hour, to instill the diethyl sodium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 550ml water washing three times, be dried to constant weight at 150 DEG C, obtain the aluminum diethylphosphinate that 304.3g contains telomer, white powder, overall yield 85.68wt%.By in the aluminum diethylphosphinate sample vitriolization containing telomer,
31p-NMR analyzes.
31p-NMR analyzes
Diethyl phospho acid mol content: 93.3%
Ethyl-butyl phospho acid mol content: 3.0%
Ethylphosphinic acid mol content 0.2%
Ethyl (cyclohexyl ethylidene) phosphinates mol content 2.7%
Butyl (cyclohexyl ethylidene) phosphinates mol content 0.2%
Other mol content: 0.6%.
embodiment 4:
The high density Hypophosporous Acid, 50 of 99.43% massfraction is prepared into embodiment 2, get the high density Hypophosporous Acid, 50 460.0g(6.279mol of 99.43% massfraction), hexanaphthene 420ml, 7.6g(0.044mol, 0.7%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 is filled with to 2.5MPa saturated, under agitation be heated to 70 DEG C, 8.7g(0.050mol is added continuously in 5.5 hours, 0.8%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 20ml hexanaphthene, and 80 DEG C were evenly warming up in 7 hours, by this reactor cooling also emptying, obtain the diethyl phospho acid solution 1167.1g containing telomer,
Diethyl phospho acid homogeneous phase solution 1167.1g, extracts three times with 800ml water, obtains diethyl phospho acid aqueous solution 3087.8g altogether, and recording acid content is 22.20%(massfraction), sour mole number is 5.621mol, yield 89.6wt%;
Diethyl phospho acid aqueous solution 3087.8g is added in reactor, is heated with stirring to 95 DEG C, obtain the diethyl sodium hypophosphite aqueous solution with the sodium hydroxide neutralization of 30% massfraction;
By 623.9g(0.937mol) Patent alum to be dissolved in the 1200ml aqueous solution and in 1 hour, to instill the diethyl sodium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 1200ml water washing three times, be dried to constant weight at 150 DEG C, obtain the aluminum diethylphosphinate that 720.0g contains telomer, white powder, overall yield 88.2wt%.By in the aluminum diethylphosphinate sample vitriolization containing telomer,
31p-NMR analyzes.
31p-NMR analyzes
Diethyl phospho acid mol content: 94.1%
Ethyl-butyl phospho acid mol content: 1.3%
Ethylphosphinic acid mol content 2.2%
Ethyl (cyclohexyl ethylidene) phosphinates mol content 1.6%
Butyl (cyclohexyl ethylidene) phosphinates mol content 0.2%
Other mol content: 0.6%.
embodiment 5:
Be prepared into the high density Hypophosporous Acid, 50 of 99.43% massfraction with embodiment 2, get the high density Hypophosporous Acid, 50 of 99.43% massfraction
181.5g(2.734mol), tetrahydrobenzene 150ml and 2.4g(0.014mol, 0.5%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 is filled with to 2.5MPa saturated, under agitation be heated to 70 DEG C, evenly 4.7g(0.027mol is added in 5 hours, 1.0%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 20ml tetrahydrobenzene, 80 DEG C are evenly warming up in 6 hours, by this reactor cooling also emptying, obtain the diethyl phospho acid homogeneous phase solution 473.8g containing telomer, acid content: 72.31%(massfraction),
Diethyl phospho acid homogeneous phase solution 473.8g, extracts three times with 300ml water, obtains the diethyl phospho acid aqueous solution altogether
1193.9g, recording acid content is 24.03%(massfraction), sour mole number is 2.359mol, yield 86.3wt%;
Diethyl phospho acid aqueous solution 1197.3g is added in reactor, is heated with stirring to 95 DEG C, obtain the diethyl sodium hypophosphite aqueous solution with the sodium hydroxide neutralization of 30% massfraction;
By 261.8g(0.393mol) Patent alum to be dissolved in the 550ml aqueous solution and in 1 hour, to instill the diethyl sodium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 550ml water washing three times, be dried to constant weight at 150 DEG C, obtain the aluminum diethylphosphinate that 302.6g contains telomer, white powder, overall yield 85.24wt%.By in the aluminum diethylphosphinate sample vitriolization containing telomer,
31p-NMR analyzes.
31p-NMR analyzes diethyl phospho acid mol content: 93.5%
Ethyl-butyl phospho acid mol content: 1.8%
Ethylphosphinic acid mol content 0.2%
Ethyl (cyclohexyl ethylidene) phosphinates mol content 3.6%
Butyl (cyclohexyl ethylidene) phosphinates mol content 0.3%
Other mol content: 0.6%.
embodiment 6:
Obtain diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, extract three times with 800ml water, obtain diethyl phospho acid aqueous solution 3081.1g altogether, recording acid content is 22.07%(massfraction), sour mole number is 5.574mol, yield 88.9wt%;
Get diethyl phospho acid 22.07%(massfraction) aqueous solution 1510.2g(2.732mol), be heated with stirring to 95 DEG C, obtain the diethyl sodium hypophosphite aqueous solution with the sodium hydroxide neutralization of 30% massfraction;
Metal-salt adopts Iron(III) chloride hexahydrate, by 246.2g(0.911mol) Iron(III) chloride hexahydrate to be dissolved in the 600ml aqueous solution and in 1 hour, to instill the diethyl sodium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 700ml water washing three times, constant weight is dried at 150 DEG C, obtain the diethyl phospho acid iron that 307.3g contains telomer, white powder, salt manufacturing productive rate 80.05wt%.
IR：773CM-1,1045CM-1,1107CM-1,2880CM-1,2939CM-1,2959CM-1。
TG:1% weightless temperature 353 DEG C, 5% weightless temperature 427 DEG C.
embodiment 7:
Obtain diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, extract three times with 800ml water, obtain diethyl phospho acid aqueous solution 3081.1g altogether, recording acid content is 22.07%(massfraction), sour mole number is 5.574mol, yield 88.9wt%;
Get diethyl phospho acid 22.07%(massfraction) aqueous solution 1510.2g(2.732mol), be heated with stirring to 95 DEG C, obtain the diethyl potassium hypophosphite aqueous solution with the potassium hydroxide neutralization of 30% massfraction;
Metal-salt adopts anhydrous magnesium sulfate, by 164.4g(1.367mol) anhydrous magnesium sulfate to be dissolved in the 350ml aqueous solution and in 1 hour, to instill the diethyl potassium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 700ml water washing three times, is dried to constant weight at 150 DEG C, obtain the diethyl phospho acid magnesium that 299.8g contains telomer, salt manufacturing yield 82.50wt%.
IR:773CM-1,1089CM-1,1169CM-1,2881CM-1,2939CM-1,2964CM-1。
TG:1% weightless temperature 335 DEG C, 5% weightless temperature 428 DEG C.
embodiment 8:
Obtain diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, extract three times with 800ml water, obtain diethyl phospho acid aqueous solution 3081.1g altogether, recording acid content is 22.07%(massfraction), sour mole number is 5.574mol, yield 88.9wt%;
Get diethyl phospho acid 22.07%(massfraction) aqueous solution 1510.2g(2.732mol), be heated with stirring to 95 DEG C, obtain the diethyl potassium hypophosphite aqueous solution with the potassium hydroxide neutralization of 30% massfraction;
Metal-salt adopts Calcium Chloride Powder Anhydrous, by 150.3g(1.367mol) Calcium Chloride Powder Anhydrous to be dissolved in the 350ml aqueous solution and in 1 hour, to instill the diethyl potassium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 700ml water washing three times, is dried to constant weight at 150 DEG C, obtain the diethyl phospho acid calcium that 307.9g contains telomer, salt manufacturing yield 79.93wt%.
IR:777CM-1,1060CM-1,1105CM-1,2881CM-1,2939CM-1,2960CM-1。
TG:1% weightless temperature 332 DEG C, 5% weightless temperature 423 DEG C.
embodiment 9:
Obtain diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, extract three times with 800ml water, obtain diethyl phospho acid aqueous solution 3081.1g altogether, recording acid content is 22.07%(massfraction), sour mole number is 5.574mol, yield 88.9wt%;
Get diethyl phospho acid 22.07%(massfraction) aqueous solution 1510.2g(2.732mol), be heated with stirring to 95 DEG C, obtain the diethyl sodium hypophosphite aqueous solution with the sodium hydroxide neutralization of 30% massfraction;
Metal-salt adopts zinc sulfate, by 219.0g(1.367mol) zinc sulfate to be dissolved in the 450ml aqueous solution and in 1 hour, to instill the diethyl sodium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 700ml water washing three times, is dried to constant weight at 150 DEG C, obtain the diethyl phospho acid zinc that 374.8g contains telomer, salt manufacturing yield 89.37wt%.
IR:775CM-1,1055CM-1,1134CM-1,2883CM-1,2941CM-1,2974CM-1。
TG:1% weightless temperature 329 DEG C, 5% weightless temperature 432 DEG C.
embodiment 10:
Obtain diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, extract three times with 800ml water, obtain diethyl phospho acid aqueous solution 3081.1g altogether, recording acid content is 22.07%(massfraction), sour mole number is 5.574mol, yield 88.9wt%;
Get diethyl phospho acid 22.07%(massfraction) aqueous solution 1510.2g(2.732mol), be heated with stirring to 95 DEG C, obtain the diethyl sodium hypophosphite aqueous solution with the sodium hydroxide neutralization of 30% massfraction;
Metal-salt adopts ferrous sulfate, by 379.7g(1.367mol) ferrous sulfate to be dissolved in the 450ml aqueous solution and in 1 hour, to instill the diethyl sodium hypophosphite aqueous solution, at 90 ~ 95 DEG C, 1 hour is incubated after dripping off, be cooled to room temperature, gained solid is leached, and with 700ml water washing three times, is dried to constant weight at 150 DEG C, obtain the diethyl phospho acid ferrous iron that 300.7g contains telomer, yield 73.86wt%.
IR:773CM-1,1043CM-1,1105CM-1,2880CM-1,2939CM-1,2958CM-1。
TG:1% weightless temperature 316 DEG C, 5% weightless temperature 418 DEG C.
The dialkylphosphinic salts of embodiment 3 ~ 10 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 or thermosetting polymer moulding material, its combustionproperty and mechanical property are tested in sample preparation, record result and see table 1:
Table 1, the moulding material combustionproperty that 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 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.
Claims (28)
1. a preparation method for dialkylphosphinic salts, described dialkylphosphinic salts has following structure formula I,
Wherein, R
1, R
2identical or different, for carbonatoms is the alkyl of 2-6;
M is Mg, Ca, Al, Zn or Fe;
M is 1-4, and m is not 1 or 4;
Wherein telomer is the ethyl-butyl phospho acid of 0.1-10mol% content, ethyl (cyclohexyl ethylidene) phosphinates and/or butyl (cyclohexyl ethylidene) phosphinates;
It is characterized in that, comprise the steps:
A) with hexanaphthene and/or tetrahydrobenzene for solvent, by high density Hypophosporous Acid, 50 under initiator effect with olefine reaction, obtain dialkyl phosphinic acid-organic phase solution;
B) after dialkyl phosphinic acid-organic phase solution water extraction or underpressure distillation steaming being removed organic solvent, dilute with water obtains the dialkyl phosphinic acid aqueous solution;
C) neutralization of the aqueous solution of dialkyl phosphinic acid aqueous solution basic cpd is obtained dialkyl hypophosphorous acid aqueous solution of alkali metal salt;
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 90% ~ 100%;
Described basic cpd is sodium hydroxide or potassium hydroxide;
Described metallic compound is Tai-Ace S 150, aluminum chloride, aluminum nitrate, ferric sulfate, Iron(III) chloride hexahydrate, iron nitrate, magnesium sulfate, magnesium chloride, magnesium acetate, magnesium nitrate, calcium sulfate, calcium chloride, zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, ferrous sulfate, iron protochloride or ferrous acetate;
The mol ratio of described high density Hypophosporous Acid, 50 and alkene is greater than 2:1.
2. the preparation method of dialkylphosphinic salts according to claim 1, is characterized in that, described basic cpd is sodium hydroxide.
3. the preparation method of dialkylphosphinic salts according to claim 1, is characterized in that, R
1, R
2identical or different, be ethyl, propyl group, butyl, isobutyl-and/or amyl group.
4. the preparation method of dialkylphosphinic salts according to claim 1, is characterized in that, described initiator is azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
5. the preparation method of dialkylphosphinic salts according to claim 4, is characterized in that, 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, peroxycarbonates, excessively oxalic acid, tert-butyl hydroperoxide isobutyrate or the peroxidation trimethylacetic acid tert-butyl ester; Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
6. the preparation method of dialkylphosphinic salts according to claim 1, is characterized in that, the mass ratio of described hexanaphthene and/or tetrahydrobenzene and high density Hypophosporous Acid, 50 is 0.2 ~ 3:1.
7. the preparation method of dialkylphosphinic salts according to claim 6, is characterized in that, the mass ratio of described hexanaphthene and/or tetrahydrobenzene and high density Hypophosporous Acid, 50 is 0.3 ~ 0.7:1.
8. the preparation method of dialkylphosphinic salts according to claim 1, is characterized in that, described alkene is ɑ-alkene.
9. the preparation method of dialkylphosphinic salts according to claim 8, is characterized in that, described alkene is the mixture of one or more in ethene, propylene, butylene, iso-butylene or amylene.
10. the preparation method of dialkylphosphinic salts according to claim 1, is characterized in that, the mol ratio of described high density Hypophosporous Acid, 50 and alkene is 2.1 ~ 2.5:1.
The preparation method of 11. dialkylphosphinic salts according to claim 1, is characterized in that, the temperature of reaction in step a) is 50 ~ 100 DEG C; Reaction pressure is 0.5MPa ~ 6MPa.
The preparation method of 12. dialkylphosphinic salts according to claim 11, is characterized in that, the temperature of reaction in step a) is 70 ~ 80 DEG C; Reaction pressure is 0.6MPa ~ 2.5MPa.
The preparation method of 13. dialkylphosphinic salts according to claim 1, is characterized in that, the mass concentration of the described dialkyl phosphinic acid aqueous solution is 5% ~ 60%.
The preparation method of 14. dialkylphosphinic salts according to claim 13, is characterized in that, the mass concentration of the described dialkyl phosphinic acid aqueous solution is 10% ~ 40%.
The preparation method of 15. dialkylphosphinic salts according to claim 1, is characterized in that, described basic cpd and the mol ratio of dialkyl phosphinic acid are 0.9 ~ 1.1:1; The mass concentration of the described basic cpd aqueous solution is 1% ~ 50%.
The preparation method of 16. dialkylphosphinic salts according to claim 15, is characterized in that, the mass concentration of the described basic cpd aqueous solution is 10% ~ 30%.
The preparation method of 17. dialkylphosphinic salts according to claim 1, is characterized in that, steps d) temperature of reaction be at 0 DEG C ~ 150 DEG C.
The preparation method of 18. dialkylphosphinic salts according to claim 17, is characterized in that, steps d) temperature of reaction be 70 DEG C ~ 90 DEG C.
The preparation method of 19. dialkylphosphinic salts according to claim 1, is characterized in that, steps d) dialkyl metal phosphinate that obtains is by filter or centrifugal treating is separated from mixture.
The preparation method of 20. dialkylphosphinic salts according to claim 1, is characterized in that, the preparation method of described high density Hypophosporous Acid, 50 comprises the steps:
A) aqueous hypophosphorous acid of 50% massfraction and organic solvent I being heated azeotropic distillation to massfraction is in an inert atmosphere 80 ~ 95%, is separated Hypophosporous Acid, 50 and the organic solvent I of 80 ~ 95% massfractions;
B) Hypophosporous Acid, 50 step a) obtained and organic solvent II heat azeotropic distillation at inert atmosphere, and 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 preparation method of 21. dialkylphosphinic salts according to claim 20, is characterized in that, the mass ratio of described organic solvent I and Hypophosporous Acid, 50 is 0.5 ~ 2:1; The mass ratio of organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 2:1.
The preparation method of 22. dialkylphosphinic salts according to claim 21, is characterized in that, the mass ratio of described organic solvent I and Hypophosporous Acid, 50 is 0.5 ~ 1.2:1; The mass ratio of organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 1.2:1.
The preparation method of 23. dialkylphosphinic salts according to claim 1, is characterized in that, the preparation method of described high density Hypophosporous Acid, 50 comprises the steps:
A) aqueous hypophosphorous acid of 50% massfraction being evaporated to massfraction is 80 ~ 95%;
B) Hypophosporous Acid, 50 step a) obtained and organic solvent II heat azeotropic distillation in an inert atmosphere, and 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.
The preparation method of 24. dialkylphosphinic salts according to claim 23, is characterized in that, the mass ratio of described organic solvent II and Hypophosporous Acid, 50 is 0.5 ~ 1.2:1.
The preparation method of 25. dialkylphosphinic salts according to claim 23, is characterized in that, its operation stage a) in, described vacuum tightness is-0.090MPa ~-0.100MPa.
The preparation method of 26. dialkylphosphinic salts according to claim 20 or 23, it is characterized in that, the reactor of described rectifying is equipped with water-and-oil separator and condenser.
27. the preparation method of the dialkylphosphinic salts according to claim 20 or 23, it is characterized in that, its operation stage b) in, the reactor of described rectifying is equipped with water-and-oil separator and condenser, in water-and-oil separator and condenser, drier system is housed and is provided with the dismounting mouth can dismantling drier system at any time.
The preparation method of 28. dialkylphosphinic salts according to claim 27, it is characterized in that, in described drier system, siccative is calcium chloride, magnesium chloride, magnesium sulfate, silica-gel drier, alumina gel siccative, molecular sieve desiccant, mineral agent or fiber desiccant.
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| DE102016213280B4 (en) | 2016-07-20 | 2024-03-07 | Clariant International Ltd | Diorganylphosphinic acid salts, a process for their preparation and their use |
| KR20200062336A (en) | 2017-10-17 | 2020-06-03 | 셀라니즈 세일즈 저머니 게엠베하 | Flame retardant polyamide composition |
| CN112661789A (en) * | 2019-10-15 | 2021-04-16 | 中国科学院上海有机化学研究所 | Method for preparing dialkyl phosphinic acid or salt thereof |
| CN112794867A (en) * | 2020-11-28 | 2021-05-14 | 浙江万盛股份有限公司 | Synthesis method of aluminum diethylphosphinate |
| CN114478624A (en) * | 2022-01-22 | 2022-05-13 | 兰州瑞朴科技有限公司 | Telomer of aluminum diethylphosphinate and preparation method thereof |
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| WO2012034680A2 (en) * | 2010-09-14 | 2012-03-22 | Clariant International Ltd | Phosphorus-containing mixtures, processes for preparing them and use thereof |
| CN102617638A (en) * | 2012-03-02 | 2012-08-01 | 山东兄弟科技股份有限公司 | Normal pressure two-phase phase-transfer catalysis synthesizing process of dialkyl phosphinate |
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| WO2012034680A2 (en) * | 2010-09-14 | 2012-03-22 | Clariant International Ltd | Phosphorus-containing mixtures, processes for preparing them and use thereof |
| CN102617638A (en) * | 2012-03-02 | 2012-08-01 | 山东兄弟科技股份有限公司 | Normal pressure two-phase phase-transfer catalysis synthesizing process of dialkyl phosphinate |
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