CN103087098A - Dialkylhypophosphite and preparation method thereof - Google Patents
Dialkylhypophosphite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a dialkylhypophosphite disclosed as a structural formula (I), wherein R1 and R2 are identical or different and are respectively a C2-6 alkyl group; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr; m=1-4; and the telomer content is 0.1-10 mol%. The preparation method comprises the following steps: by using cyclohexane and/or cyclohexene as a solvent, reacting high-concentration hypophosphorous acid with alkene under the action of an initiator to obtain dialkylhypophosphorous acid-organic phase solution; extracting with water, or carrying out vacuum distillation to remove the organic solvent and diluting with water, thereby obtaining a dialkylhypophosphorous acid water solution; neutralizing with an alkaline compound water solution to obtain a dialkylhypophosphorous acid alkali metal salt water solution; and reacting the dialkylhypophosphorous acid alkali metal salt water solution with the metal compound water solution to obtain the dialkylhypophosphite. The high-concentration hypophosphorous acid is used as the raw material, and the cyclohexane and/or cyclohexene is used as the solvent to obtain the product containing part of telomer; and thus, the invention has the advantages of very short reaction period (the synthesis can be completed only by 4-6 hours) and high overall yield. The technical process is simple, and the organic solvent can be recycled.
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, can synthesize by diverse ways.(Chinese science B collects Yuan Chengye etc. in the novel method of the research of organic phosphine compound-phosphine oxide acylation reaction-synthetic dialkyl phosphonic acids and derivative thereof, 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 self-control Grignard reagent react and are hydrolyzed and obtain the dialkyl group phosphine oxide, can obtain dialkyl phosphinic acid after dialkyl group phosphine oxide and oxidant reaction and 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 disclose two replace metal phosphinates at polyester as fire retardant, DE19910232, two patents of 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, at first the method adopts yellow phosphorus to synthesize monoalkyl phosphonate, then utilize free radical to cause to be hydrolyzed after 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 there is the existence of water to make the easy cancellation inactivation of radical initiator, make and to add more radical initiator reaction is completed, 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 makes the easy cancellation inactivation of radical initiator, and reaction time is long.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, the object of the invention is to provide a kind of dialkylphosphinic salts that contains 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, be the alkyl of 2-6 for carbonatoms;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 1-4;
Wherein telomer is ethyl-butyl phospho acid, ethyl (cyclohexyl ethylidene) phosphinates and/or butyl (cyclohexyl ethylidene) phosphinates of 0.1-10mol content.
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) take hexanaphthene and/or tetrahydrobenzene 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 after organic solvent;
C) the dialkyl phosphinic acid aqueous solution is obtained the dialkyl hypophosphorous 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 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 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 hexanaphthene and/or tetrahydrobenzene and high density Hypophosporous Acid, 50 is 0.2 ~ 3:1, preferred 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, preferred 2.1 ~ 2.5:1.
Temperature of reaction in 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, in described solid drier system, siccative is calcium chloride, magnesium chloride, sal epsom, silica-gel drier, alumina gel siccative, molecular sieve desiccant, mineral agent or fiber desiccant.
The invention also discloses above-mentioned dialkylphosphinic salts as the purposes of 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) to adopt the high density Hypophosporous Acid, 50 be raw material in the present invention, take hexanaphthene and/or tetrahydrobenzene as solvent, can obtain containing the product of part telomer, and reaction time is extremely short, only needs 4 ~ 6h can complete the high pressure building-up process;
2) utilize the overall yield of the dialkylphosphinic salts that the method obtains high, near 90wt%;
3) technical process of the present invention is simple, the organic solvent recoverable.
Embodiment
Further illustrate 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 in the reaction flask that water-and-oil separator and condenser are housed, and 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; Add separating funnel to separate to get the liquid 223.1g of lower floor the solution in reaction flask, get acid content with the acid base titration titration and be: 90.31% 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 in the reaction flask that water-and-oil separator and condenser are housed, and 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; Add separating funnel to separate to get the liquid 212.0g of lower floor the solution in reaction flask, get acid content with the acid base titration titration and be: 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, fixing solid silicone siccative is housed in water-and-oil separator wherein and 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 reaction flask on Rotary Evaporators 60 ℃, under-0.098KPa, concentrating under reduced pressure 4h, be cooled to room temperature, and emptying obtains the 198.5g Hypophosporous Acid, 50.Drip to such an extent that acid content is the 99.75%(massfraction with acid base titration).Drip to such an extent that obtain Hypophosporous Acid, 50 content 99.43%(massfraction with oxidation reduction process), phosphorous acid content: the 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, 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 hexanaphthene, evenly be warming up to 80 ℃ in 5 hours, cooling and the emptying with this reactor, obtain containing the diethyl phospho acid homogeneous phase solution 474.1g of telomer, acid content: the 72.01%(massfraction),
Diethyl phospho acid homogeneous phase solution 474.1g with 300ml water extraction three times, obtains the diethyl phospho acid aqueous solution altogether
1197.3g recording acid content is the 24.23%(massfraction), sour mole number is 2.383mol, yield 87.2wt%;
Diethyl phospho acid aqueous solution 1197.3g is added in reactor, be heated with stirring to 95 ℃, obtain the diethyl sodium hypophosphite aqueous solution with the neutralization of the sodium hydroxide of 30% massfraction;
With 264.5g(0.397mol) Patent alum is dissolved in the 550ml aqueous solution and splashed into the diethyl sodium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, be cooled to room temperature, the gained solid is leached, and with 550ml water washing three times, be dried to constant weight at 150 ℃, obtain the diethyl phospho acid aluminium that 304.3g contains telomer, white powder, overall yield 85.68wt%.To contain in the diethyl phospho acid aluminium sample vitriolization of telomer,
31P-NMR analyzes.
31P-NMR analyzes
Diethyl phospho acid mol content: 93.3%
Ethyl-butyl phospho acid mol content: 3.0%
Ethyl phospho 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:
be prepared into the high density Hypophosporous Acid, 50 of 99.43% massfraction with 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, 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 ℃, added continuously 8.7g(0.050mol 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 evenly be warming up to 80 ℃ in 7 hours, cooling and the emptying with this reactor, obtain containing the diethyl phospho acid solution 1167.1g of telomer,
Diethyl phospho acid homogeneous phase solution 1167.1g with 800ml water extraction three times, obtains diethyl phospho acid aqueous solution 3087.8g altogether, and recording acid content is the 22.20%(massfraction), sour mole number is 5.621mol, yield 89.6wt%;
Diethyl phospho acid aqueous solution 3087.8g is added in reactor, be heated with stirring to 95 ℃, obtain the diethyl sodium hypophosphite aqueous solution with the neutralization of the sodium hydroxide of 30% massfraction;
With 623.9g(0.937mol) Patent alum is dissolved in the 1200ml aqueous solution and splashed into the diethyl sodium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, 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 the diethyl phospho acid aluminium that 720.0g contains telomer, white powder, overall yield 88.2wt%.To contain in the diethyl phospho acid aluminium sample vitriolization of telomer,
31P-NMR analyzes.
31P-NMR analyzes
Diethyl phospho acid mol content: 94.1%
Ethyl-butyl phospho acid mol content: 1.3%
Ethyl phospho 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, 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 5 hours, 1.0%mol) the solution that is configured to of the peroxidation trimethylacetic acid tert-butyl ester and 20ml tetrahydrobenzene, evenly be warming up to 80 ℃ in 6 hours, cooling and the emptying with this reactor, obtain containing the diethyl phospho acid homogeneous phase solution 473.8g of telomer, acid content: the 72.31%(massfraction),
Diethyl phospho acid homogeneous phase solution 473.8g with 300ml water extraction three times, obtains the diethyl phospho acid aqueous solution altogether
1193.9g recording acid content is the 24.03%(massfraction), sour mole number is 2.359mol, yield 86.3wt%;
Diethyl phospho acid aqueous solution 1197.3g is added in reactor, be heated with stirring to 95 ℃, obtain the diethyl sodium hypophosphite aqueous solution with the neutralization of the sodium hydroxide of 30% massfraction;
With 261.8g(0.393mol) Patent alum is dissolved in the 550ml aqueous solution and splashed into the diethyl sodium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, be cooled to room temperature, the gained solid is leached, and with 550ml water washing three times, be dried to constant weight at 150 ℃, obtain the diethyl phospho acid aluminium that 302.6g contains telomer, white powder, overall yield 85.24wt%.To contain in the diethyl phospho acid aluminium sample vitriolization of telomer,
31P-NMR analyzes.
31P-NMR analyzes diethyl phospho acid mol content: 93.5%
Ethyl-butyl phospho acid mol content: 1.8%
Ethyl phospho 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:
Get diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, with 800ml water extraction three times, obtain altogether diethyl phospho acid aqueous solution 3081.1g, recording acid content is the 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 ℃, obtain the diethyl sodium hypophosphite aqueous solution with the neutralization of the sodium 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 the diethyl sodium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, 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 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。
353 ℃ of TG:1% weightless temperatures, 5% 427 ℃ of weightless temperatures.
Embodiment 7:
Get diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, with 800ml water extraction three times, obtain altogether diethyl phospho acid aqueous solution 3081.1g, recording acid content is the 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 ℃, obtain the diethyl potassium hypophosphite aqueous solution with the neutralization of the potassium 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 the diethyl potassium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, 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 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。
335 ℃ of TG:1% weightless temperatures, 5% 428 ℃ of weightless temperatures.
Embodiment 8:
Get diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, with 800ml water extraction three times, obtain altogether diethyl phospho acid aqueous solution 3081.1g, recording acid content is the 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 ℃, obtain the diethyl potassium hypophosphite aqueous solution with the neutralization of the potassium 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 the diethyl potassium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, 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 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。
332 ℃ of TG:1% weightless temperatures, 5% 423 ℃ of weightless temperatures.
Embodiment 9:
Get diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, with 800ml water extraction three times, obtain altogether diethyl phospho acid aqueous solution 3081.1g, recording acid content is the 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 ℃, obtain the diethyl sodium hypophosphite aqueous 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 the diethyl sodium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, 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 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。
329 ℃ of TG:1% weightless temperatures, 5% 432 ℃ of weightless temperatures.
Embodiment 10:
Get diethyl phospho acid homogeneous phase solution 1185.3g with embodiment 3, with 800ml water extraction three times, obtain altogether diethyl phospho acid aqueous solution 3081.1g, recording acid content is the 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 ℃, obtain the diethyl sodium hypophosphite aqueous 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 the diethyl sodium hypophosphite aqueous solution in 1 hour, be incubated 1 hour after dripping off under 90 ~ 95 ℃, 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 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。
316 ℃ of TG:1% weightless temperatures, 5% 418 ℃ of weightless temperatures.
The dialkylphosphinic salts of embodiment 3 ~ 10 gained is mixed by weight 10:60:25:5 with PBT, glass, auxiliary agent at 230-260 ℃, extrude from Bitruder, make flame-proofed thermoplastic or thermosetting polymer 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, 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 (23)
1. a dialkylphosphinic salts, have following structure formula I,
Wherein, R
1, R
2Identical or different, be the alkyl of 2-6 for carbonatoms;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 1-4;
Wherein telomer is ethyl-butyl phospho acid, ethyl (cyclohexyl ethylidene) phosphinates and/or butyl (cyclohexyl ethylidene) phosphinates of 0.1-10mol% content.
2. 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.
3. the preparation method of dialkylphosphinic salts as claimed in claim 1, is characterized in that, comprises the steps: (be the independent claim of method, theme should be the preparation method) here
A) take hexanaphthene and/or tetrahydrobenzene 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 after organic solvent;
C) will obtain the dialkyl hypophosphorous 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 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.
4. the preparation method of dialkylphosphinic salts according to claim 3, 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 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.
6. the preparation method of dialkylphosphinic salts according to claim 3, is characterized in that, the mass ratio of described hexanaphthene and/or tetrahydrobenzene and high density Hypophosporous Acid, 50 is 0.2 ~ 3:1, preferred 0.3 ~ 0.7:1.
7. the preparation method of dialkylphosphinic salts according to claim 3, is characterized in that, described alkene is ɑ-alkene, the mixture of one or more in optimal ethylene, propylene, butylene, iso-butylene or amylene.
8. the preparation method of dialkylphosphinic salts according to claim 3, 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.
9. the preparation method of dialkylphosphinic salts according to claim 3, is characterized in that, the temperature of reaction in step a) is 50 ~ 100 ℃, preferred 70 ~ 80 ℃; Reaction pressure is 0.5MPa ~ 6MPa, preferred 0.6MPa ~ 2.5MPa.
10. the preparation method of dialkylphosphinic salts according to claim 3, is characterized in that, the mass concentration of the described dialkyl phosphinic acid aqueous solution is 5% ~ 60%, preferred 10% ~ 40%.
11. the preparation method of dialkylphosphinic salts according to claim 3 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%.
12. the preparation method of dialkylphosphinic salts according to claim 3, 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 dialkylphosphinic salts according to claim 3 is characterized in that, steps d) temperature of reaction be under 0 ℃ ~ 150 ℃, preferred 70 ℃ ~ 90 ℃.
14. the preparation method of dialkylphosphinic salts according to claim 3 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 dialkylphosphinic salts according to claim 3 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 and the organic solvent II that step a) are obtained 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.
16. the preparation method of dialkylphosphinic salts according to claim 15 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 dialkylphosphinic salts according to claim 3 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 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, 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 dialkylphosphinic salts according to claim 17 is characterized in that, its operation stage a) in, described vacuum tightness is-0.090MPa ~-0.100MPa.
19. the preparation method of according to claim 15 or 17 described dialkylphosphinic salts is characterized in that, the reactor that described rectifying is used is equipped with water-and-oil separator and condenser.
20. the preparation method of according to claim 15 or 17 described dialkylphosphinic salts, 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 dialkylphosphinic salts according to claim 20, it is characterized in that, in described drier system, siccative is calcium chloride, magnesium chloride, sal epsom, silica-gel drier, alumina gel siccative, molecular sieve desiccant, mineral agent or fiber desiccant.
22. dialkylphosphinic salts as claimed in claim 1 is as the purposes of fire retardant.
23. a flame-retardant polymer moulding material that comprises dialkylphosphinic salts claimed in claim 1 is characterized in that, comprises the 5-20wt% dialkylphosphinic salts, 50-70wt% polymkeric substance or its mixture, 15-30wt% glass fibre, other auxiliary agents of 1-5wt%.
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| CN104478923A (en) * | 2014-12-19 | 2015-04-01 | 西华大学 | Preparation method of diethyl phosphinic acid without monoethyl phosphinic acid group and salt thereof |
| JP2019527687A (en) * | 2016-07-20 | 2019-10-03 | クラリアント・プラスティクス・アンド・コーティングス・リミテッド | Diorganylphosphinate, process for its production and use thereof |
| 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 |
| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104478923A (en) * | 2014-12-19 | 2015-04-01 | 西华大学 | Preparation method of diethyl phosphinic acid without monoethyl phosphinic acid group and salt thereof |
| JP2019527687A (en) * | 2016-07-20 | 2019-10-03 | クラリアント・プラスティクス・アンド・コーティングス・リミテッド | Diorganylphosphinate, process for its production and use thereof |
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| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | 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 |
| WO2023138015A1 (en) * | 2022-01-22 | 2023-07-27 | 兰州瑞朴科技有限公司 | Aluminum diethylphosphinate flame retardant and preparation method therefor |
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