CN103172669B - Monoalkyl/dialkyl phosphinate and preparation method thereof - Google Patents
Monoalkyl/dialkyl phosphinate and preparation method thereof Download PDFInfo
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- CN103172669B CN103172669B CN201310068662.8A CN201310068662A CN103172669B CN 103172669 B CN103172669 B CN 103172669B CN 201310068662 A CN201310068662 A CN 201310068662A CN 103172669 B CN103172669 B CN 103172669B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); Derivatives thereof
- C07F9/4808—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
Abstract
The invention discloses monoalkyl/dialkyl phosphinate and a preparation method thereof. The method comprises the steps that: an organic solvent is adopted as a reaction medium; under the effect of an initiator I, hypophosphite is subjected to a reaction with alkene I under a temperature of 70-90 DEG C, such that monoalkyl phosphinate is obtained; the temperature is increased to 90-110 DEG C by heating; the obtained monoalkyl phosphinate is subjected to a reaction with alkene II under the effect of an initiator II, such that dialkyl phosphinate is obtained; Or, an organic solvent is adopted as a reaction medium; under the effect of an initiator III, hypophosphite is subjected to a reaction with alkene III under a temperature of 70-120 DEG C, such that dialkyl phosphinate is obtained. The hypophosphite is hypophosphorous acid salt of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, or Sr. According to the invention, hypophosphite is directly adopted as a raw material, and the monoalkyl/dialkyl phosphinate is obtained with a one-step method. The reaction period is short, obtained monoalkyl/dialkyl phosphinate can be precisely controlled, a total yield is high, and process floe is simple. When the product is salified, the contents of other salts are low. The product is easy to wash.
Description
Technical field
The present invention relates to a kind of monoalkyl/dialkylphosphinic salts and preparation method thereof.
Background technology
Monoalkylphosphinic acid salt and dialkylphosphinic salts, be widely used as fire retardant, synthesizes by diverse ways.In the novel method of the research-phosphorus oxide acylation reaction-synthesis dialkyl phosphonic acids of organo phosphorous compounds 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 50wt% 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.
More than invent all with Hypophosporous Acid, 50 or Hypophosporous Acid, 50 an alkali metal salt, after being prepared into dialkyl phosphinic acid or dialkyl phosphinic acid an alkali metal salt, still need the throw out that could be prepared into dialkyl phosphinic acid alkaline earth salt or other salt after processing further in water.And the mixture being essentially dialkyl phosphinic acid hydrochlorate or monoalkylphosphinic acid salt and dialkylphosphinic salts of aforesaid method gained, is difficult to obtain the higher monoalkylphosphinic acid salt of comparatively content or Hypophosporous Acid, 50.
Summary of the invention
In order to the shortcoming overcoming prior art is with not enough, the object of the invention is to provide the preparation method of monoalkyl/dialkylphosphinic salts that a kind of technical process is simple, reaction time is short, overall yield is high.。
Another object of the present invention is to provide a kind of monoalkyl/dialkylphosphinic salts prepared by above-mentioned preparation method.
The present invention is achieved by the following technical solutions:
A preparation method for monoalkyl/dialkylphosphinic salts, comprises the steps:
Take organic solvent as reaction medium, hypophosphite is reacted with alkene I under initiator I effect at temperature is 70 ~ 90 DEG C, obtains monoalkylphosphinic acid salt;
Or be reaction medium with organic solvent, hypophosphite is reacted at temperature is 70 ~ 90 DEG C with alkene I under initiator I effect, obtain monoalkylphosphinic acid salt, be heated to 90 ~ 110 DEG C, the monoalkylphosphinic acid salt obtained is reacted with alkene II under initiator II effect, obtains dialkylphosphinic salts;
Or be reaction medium with organic solvent, hypophosphite is reacted with alkene III under initiator III effect at temperature is 70 ~ 120 DEG C, obtains dialkylphosphinic salts;
Wherein, described hypophosphite is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr salt of Hypophosporous Acid, 50.
Described organic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, benzene,toluene,xylene, acetone, ether, trichloromethane, tetrahydrofuran (THF), ritalin, vinyl acetic monomer and/or hexanaphthene.
Described organic solvent and the mass ratio of hypophosphite are 1:1 ~ 10:1, preferred 2:1 ~ 5:1.
Described initiator I, initiator II and initiator III are identical or different.
Described initiator I, initiator II, initiator III are azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator.
Described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organic peroxide evocating agent is perbenzoic acid, peroxylauric acid, ditertiary butyl peroxide, the special pentyl ester of peroxycarbonates, excessively oxalic acid, tert-butyl hydroperoxide isobutyrate, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester or peroxidation trimethylacetic acid; Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
The molar content of described initiator I is the 0.1mol% ~ 10mol% of hypophosphite; The molar content of described initiator II is the 0.1mol% ~ 10mol% of monoalkyl hypophosphite.
The molar content of described initiator III is the 0.1mol% ~ 10mol% of hypophosphite.
Described alkene I, alkene II and alkene III are identical or different, for naphthenic alkene or carbonatoms 2 ~ 20 ɑ-alkene or.
Described ɑ-alkene is selected from the mixture of one or more in ethene, propylene, butylene, iso-butylene or amylene; Described naphthenic alkene is cyclopentenes or tetrahydrobenzene.
The mol ratio of described hypophosphite and alkene I is less than 1:1, preferred 1:1.01 ~ 1.5; The mol ratio of described monoalkylphosphinic acid salt and alkene II is less than 1:1, preferred 1:1.01 ~ 1.5.
The mol ratio of described hypophosphite and alkene III is less than 1:2, preferred 1:2.01 ~ 2.5.
Described reaction pressure is 0.5MPa ~ 6MPa, preferred 0.6MPa ~ 2.5MPa.
Monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains is separated from mixture by filtration or centrifugal treating.
The invention also discloses a kind of monoalkyl/dialkylphosphinic salts prepared by above-mentioned preparation method, there is following structure formula I,
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is for both can not be H simultaneously;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr;
M is 2 ~ 4.
The invention also discloses the purposes that monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains is used as fire retardant.
The invention also discloses a kind of flame-proofed polymer material prepared by monoalkyl/dialkylphosphinic salts that above-mentioned preparation method obtains, comprise 5 ~ 20wt% monoalkyl/dialkylphosphinic salts, 50 ~ 70wt% polymkeric substance or its mixture, 0 ~ 30wt% glass fibre, other auxiliary agents of 0 ~ 5wt%; Wherein, monoalkyl/dialkylphosphinic salts has following structure formula I,
Wherein, R
1, R
2identical or different, be expressed as H, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group, condition is for both can not be H simultaneously; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr or Sr; M is 2 ~ 4.
Described 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 directly with target hypophosphite for raw material reacts, single stage method obtains corresponding monoalkylphosphinic acid salt and dialkylphosphinic salts flame retardant products.
2) reaction time of the present invention is extremely short, the shortlyest only needs within 3 ~ 5 hours, can obtain monoalkylphosphinic acid salt product, within the shortest 8 ~ 9 hours, obtains dialkylphosphinic salts product.
3) the present invention can comparatively accurately control to obtain monoalkylphosphinic acid salt, and productive rate is the highest close to 95wt%; Dialkylphosphinic salts productive rate is high, the highest close to 97wt% simultaneously.
4) present invention process flow process is simple; After product salify, other salts contgs are few, are easy to washing.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Wherein, in embodiment, products obtained therefrom productive rate all calculates by following formula:
Calculation of yield formula:
Wherein, w is productive rate, and m is product gained quality, and n is hypophosphite mole number, and M is molecular weight product
embodiment 1: the structure of ethylphosphinic acid aluminium and preparation thereof
By hypo-aluminum orthophosphate 444.0g(2mol), 1000mL toluene and 9.7g(0.04mol) dibenzoyl peroxide adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 4.8g(0.02mol with volume pump) solution that is mixed with of dibenzoyl peroxide and 50mL toluene, 1 hour is incubated again at 75 DEG C, cooling emptying, obtain ethylphosphinic acid aluminium-toluene mixed system 1538.8g, being equivalent to ethylene absorption amount was 171.0 (being equivalent to 101.8% of theoretical amount).
Gained mixed system filters, and wash 1 time with 1000mL hot ethanol, then use 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains ethylphosphinic acid aluminium in 5 hours: 588.9g, productive rate 96.23wt%, and wherein, the structural formula of ethylphosphinic acid aluminium is:
31p-NMR analyzes (in sample vitriolization):
Ethylphosphinic acid mol content: 95.1%
Diethyl phospho acid mol content: 3.8%
Other mol content: 1.1%
embodiment 2: the structure of aluminum diethylphosphinate and preparation thereof
By hypo-aluminum orthophosphate 444.2g(2mol), 800mL toluene and 9.7g(0.04mol) benzoyl peroxide adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4 hours, be evenly warming up to 75 DEG C and squeeze into 4.8g(0.02mol continuously with volume pump) solution that is mixed with of benzoyl peroxide and 30mL toluene; After 4.5 hours, be heated to 105 DEG C, in 4 hours, be evenly warming up to 115 DEG C and squeeze into 11.7g(0.06mol continuously with volume pump) solution that is mixed with of peroxidized t-butyl perbenzoate and 100mL toluene; At 110 DEG C, be incubated 1 hour again, cooling emptying, obtain aluminum diethylphosphinate-toluene mixed system 1621.2g, being equivalent to ethylene absorption amount is that 345.4g(is equivalent to 102.8% of theoretical amount).
Gained mixed system filters, and wash 1 time with 1000mL hot ethanol, with 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains aluminum diethylphosphinate in 5 hours: 749.8g, productive rate 96.12wt%, and wherein, the structural formula of aluminum diethylphosphinate is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 96.7%
Ethylphosphinic acid mol content: 2.6%
Ethyl-butyl Hypophosporous Acid, 50 mol content: 0.3%
Other mol content: 0.4%.
embodiment 3: the structure of aluminum diethylphosphinate and preparation thereof
By hypo-aluminum orthophosphate 444.0g(2.00mol), 1000mL benzene adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 105 DEG C, in 11 hours, even volume pump squeezes into 19.4g(0.10mol) solution that is mixed with of peroxidized t-butyl perbenzoate and 100mL benzene, and be evenly warming up to 115 DEG C, 1 hour is incubated again at 115 DEG C, cooling emptying, obtain aluminum diethylphosphinate-benzene mixed system 1623.3g, being equivalent to ethylene absorption amount is that 347.5g(is equivalent to 103.4% of theoretical amount).
Gained mixed system filters, and by 1000mL washing with alcohol 1 time, then use 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains aluminum diethylphosphinate in 5 hours: 747.8g, productive rate 95.87wt%, and wherein, the structural formula of aluminum diethylphosphinate is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 95.3%
Ethylphosphinic acid mol content: 0.4%
Ethyl-butyl Hypophosporous Acid, 50 mol content: 3.5%
Other mol content: 0.8%.
embodiment 4: the structure of ethyl-butyl phospho acid aluminium and preparation thereof
By hypo-aluminum orthophosphate 444.0g(2.00mol), 1000mL ethanol and 12.8g(0.04mol, 50%) tert-butyl hydroperoxide isobutyrate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 80 DEG C, in 4h, be evenly warming up to 85 DEG C and squeeze into 6.4g(0.02mol with volume pump, 50%) solution that is mixed with of tert-butyl hydroperoxide isobutyrate and 30mL ethanol, 1 hour is incubated again at 85 DEG C, cooling emptying, obtain ethylphosphinic acid aluminium-ethanol mixed system 1475.4g, being equivalent to ethylene absorption amount is that 171.7g(is equivalent to 102.2% of theoretical amount).
Gained ethylphosphinic acid aluminium-ethanol mixed system continues to be heated to 105 DEG C in autoclave, in high-pressure reactor, be filled with n-butene be about 350g, in 4h, even volume pump squeezes into 6.4g(0.02mol, 50%) solution that is mixed with of tert-butyl hydroperoxide isobutyrate and 30mL ethanol, after 110 DEG C insulation 2 hours, cooling emptying, the mixed system obtained is filtered, with 1000mL washing with alcohol once, with 1000mL water washing 2 times, the filter cake obtained vacuum-drying at 130 DEG C obtains ethyl-butyl phospho acid aluminium for 5 hours: 903.9g, productive rate 95.35wt%, wherein, the structural formula of ethyl-butyl phospho acid aluminium is:
31p-NMR analyzes (in sample vitriolization):
Ethyl-butyl phospho acid mol content: 95.1%
Diethyl phospho acid mol content: 3.2%
Ethylphosphinic acid mol content: 0.4%
Other mol content: 1.3%.
embodiment 5: the structure of butyl phospho acid iron and preparation thereof
By ferric hypophosphite 502.0g(2.00mol), 1200mL methyl alcohol and 12.8g(0.04mol, 50%) tert-butyl hydroperoxide isobutyrate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after n-butene be about 360g be filled with, be heated to 80 DEG C, in 4h, be evenly warming up to 85 DEG C and squeeze into 6.4g(0.04mol with volume pump, 50%) solution that is mixed with of tert-butyl hydroperoxide isobutyrate and 30mL methyl alcohol, 1 hour is incubated again at 85 DEG C, cooling emptying, by the mixed system Filtration Filtration obtained, by 1000mL washing with alcohol 1 time, with 1000mL water washing 2 times, the filter cake obtained vacuum-drying at 130 DEG C obtains butyl phospho acid iron for 5 hours: 760.9g, productive rate 90.16wt%, wherein, the structural formula of butyl phospho acid iron is:
31p-NMR analyzes (in sample vitriolization):
Butyl phospho acid mol content: 96.2%
Dibutyl phospho acid mol content: 2.7%
Other mol content: 1.1%.
embodiment 6: the structure of dibutyl phospho acid iron and preparation thereof
By ferric hypophosphite 502.0g(2.00mol), 1200mL methyl alcohol adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after butylene be about 700g be filled with, be heated to 105 DEG C, in 7 hours, even volume pump squeezes into 19.2g(0.06mol, 50%) solution that is mixed with of tert-butyl hydroperoxide isobutyrate and 100mL methyl alcohol, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, the mixed system obtained is filtered, with 1000mL washing with alcohol once, with 1000mL water washing 2 times, the filter cake obtained vacuum-drying at 130 DEG C obtains dibutyl phospho acid iron for 5 hours: 1046.3g, productive rate 88.7wt%, wherein, the structural formula of dibutyl phospho acid iron is:
31p-NMR analyzes (in sample vitriolization):
Dibutyl phospho acid mol content: 95.1%
Butyl phospho acid mol content: 3.7%
Other mol content: 1.2%.
embodiment 7: the structure of n-propyl phospho acid magnesium and preparation thereof
By magnesium hypophosphite 465.0g(3.00mol), 1000mL hexanaphthene and 12.8g(0.04mol, 50%) tert-butyl hydroperoxide isobutyrate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after propylene be adjusted to 1.5MPa by voltate regulator and be filled with, be heated to 80 DEG C, in 4h, be evenly warming up to 85 DEG C and squeeze into 6.4g(0.02mol with volume pump, 50%) solution that tert-butyl hydroperoxide isobutyrate and 30mL hexanaphthene are mixed with is crossed, 1 hour is incubated again at 85 DEG C, cooling emptying, obtain mixed system 1543.6g, be equivalent to that propylene absorbed dose is 256.0g(theoretical amount 101.6%).
Gained mixed system filters, and by 1000mL washing with alcohol 1 time, wash 2 times with water 1000mL, the vacuum-drying at 130 DEG C of gained filter cake obtains n-propyl phospho acid magnesium for 5 hours: 652.9g, productive rate 90.75wt%, and wherein, the structural formula of n-propyl phospho acid magnesium is:
31p-NMR analyzes (in sample vitriolization):
N-propyl phospho acid mol content: 94.9%
Dipropyl phospho acid mol content: 3.2%
Other mol content: 1.9%.
embodiment 8: the structure of dipropyl phospho acid magnesium and preparation thereof
Magnesium hypophosphite 465.0g (3.00mol), 1000mL ether are added in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after propylene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 105 DEG C, in 7 hours, even volume pump squeezes into 13.9g(0.08mol) solution that is configured to of ditertiary butyl peroxide and 100ml ether, and be evenly warming up to 115 DEG C, 1 hour is incubated again at 115 DEG C, cooling emptying, obtain mixed system 1776.8g, be equivalent to that propylene absorbed dose is 513.6g(theoretical amount 101.9%).
Gained mixed system filters, and by 1000mL washing with alcohol 1 time, with 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains dipropyl phospho acid magnesium for 5 hours: 890.7g, productive rate 91.64 wt%, and wherein the structural formula of dipropyl phospho acid magnesium is:
31p-NMR analyzes (in sample vitriolization):
Dipropyl phospho acid mol content: 92.8%
Propylphosphinic acid mol content: 5.5%
Other mol content: 1.7%.
embodiment 9: the structure of ethylphosphinic acid calcium and preparation thereof
By calcium propionate 510.0g(3.00mol), 1200mL tetrahydrofuran (THF) and 12.8g(0.04mol, 50%) tert-butyl hydroperoxide isobutyrate adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 80 DEG C, in 4h, be evenly warming up to 85 DEG C and squeeze into 6.4g(0.02mol with volume pump, 50%) solution that is mixed with of tert-butyl hydroperoxide isobutyrate and 100mL tetrahydrofuran (THF), 1 hour is incubated again at 85 DEG C, cooling emptying, obtain mixed system 1983.4g, being equivalent to ethylene absorption amount is that 173.7g(is equivalent to 103.4% of theoretical amount).
The mixed system of gained filters, and by 1000mL washing with alcohol 1 time, then use 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains ethylphosphinic acid calcium in 5 hours: 563.4g, productive rate 83.14 wt%, and wherein, the structural formula of ethylphosphinic acid calcium is:
31p-NMR analyzes (in sample vitriolization):
Ethylphosphinic acid mol content: 92.7%
Diethyl phospho acid mol content: 5.0%
Other mol content: 2.3%.
embodiment 10: the structure of diethyl phospho acid calcium and preparation thereof
By calcium propionate 510g(3mol), 1000mL ethanol adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 95 DEG C, in 7 hours, even volume pump squeezes into 19.2g(0.06mol, 50%) solution that is mixed with of tert-butyl hydroperoxide isobutyrate and 100mL ethanol, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, obtain mixed system 1775.2g, being equivalent to ethylene absorption amount is that 348.4g(is equivalent to 103.7% of theoretical amount).
The mixed system of gained filters, and by 1000mL washing with alcohol 1 time, then uses 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains diethyl phospho acid calcium for 5 hours: 703.9g, productive rate 83.21wt%, wherein, the structural formula of diethyl phospho acid calcium is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 96.8%
Ethylphosphinic acid mol content: 1.8%
Other mol content: 1.4%
embodiment 11: the structure of ethylphosphinic acid zinc and preparation thereof
By zinc hypophosphite 585g(3mol), 1000mL Virahol and 7.0g(0.04mol) the peroxidation trimethylacetic acid tert-butyl ester adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 72 DEG C, in 4h, be evenly warming up to 75 DEG C and squeeze into 3.5g(0.2mol with volume pump) solution that is mixed with of the peroxidation trimethylacetic acid tert-butyl ester and 30mL Virahol, 1 hour is incubated again at 75 DEG C, cooling emptying, obtain mixed system 1577.3g, being equivalent to ethylene absorption amount is that 171.9g(is equivalent to 102.3% of theoretical amount).
The mixed system of gained filters, and by 1000mL washing with alcohol 1 time, then use 1000mL water washing 2 times, the vacuum-drying at 130 DEG C of gained filter cake obtains ethylphosphinic acid zinc in 5 hours: 686.9g, productive rate 90.39wt%, and wherein, the structural formula of ethylphosphinic acid zinc is:
31p-NMR analyzes (in sample vitriolization):
Ethylphosphinic acid mol content: 95.2%
Diethyl phospho acid mol content: 3.3%
Other mol content: 1.5%.
embodiment 12: the structural formula of diethyl phospho acid zinc and preparation thereof
By zinc hypophosphite 585g(3mol), 1000mL Virahol adds in high-pressure reactor, airtight, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5MPa by voltate regulator and be filled with, be heated to 95 DEG C, in 7 hours, even volume pump squeezes into 13.9g(0.08mol) solution that is mixed with of the peroxidation trimethylacetic acid tert-butyl ester and 100mL Virahol, and be evenly warming up to 110 DEG C, 1 hour is incubated again at 110 DEG C, cooling emptying, obtain mixed system 1809.5g, being equivalent to ethylene absorption amount is that 345.7g(is equivalent to 102.9% of theoretical amount).
The mixed system of gained filters, and by 1000mL washing with alcohol 1 time, then uses 1000mL water washing 1 time, the vacuum-drying at 130 DEG C of gained filter cake obtains diethyl zinc hypophosphite in 5 hours: 830.9g, productive rate 90.22 wt%, wherein, the structural formula of diethyl phospho acid zinc is:
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 95.7%
Ethylphosphinic acid mol content: 2.9%
Other mol content: 1.4%.
comparative example 1
Get 360.6g50wt% Hypophosporous Acid, 50 (2.732mol) and 4.7g(0.027mol, 1.0%mol) the peroxidation trimethylacetic acid tert-butyl ester adds in autoclave together, enclosed high pressure still, nitrogen (0.5MPa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5Mpa by voltate regulator and be filled with, under agitation be heated to 72 DEG C, evenly 9.4g(0.054mol is added in 14h, 2.0%mol) the peroxidation trimethylacetic acid tert-butyl ester, and be evenly warming up to 85 DEG C, by this reactor cooling also emptying, obtain product water solution 508.9g;
31p-NMR analyzes diethyl phospho acid mol content: 74.1%
Ethylphosphinic acid mol content: 23.8%
Other mol content: 2.1 %
300g water and high density alkyl phosphinic acid 557.9g obtained above are added in reactor and stirs, obtain with 30% aqueous sodium hydroxide solution neutralization, post-heating to 95 DEG C, by 303.3g(0.455mol) Tai-Ace S 150 to be dissolved in the 700mL aqueous solution and to instill in 1 hour, being incubated 1 hour, being cooled to room temperature after dripping off at 90 ~ 95 DEG C, gained solid is leached, and with 700mL water washing three times, be dried to constant weight at 150 DEG C, obtain 295.7g alkyl phosphinic acid aluminium.
comparative example 2
Get 289.6g mono-hydration sodium hypophosphite (2.732mol), 500g acetic acid and 4.4g(0.027mol, 1.0%mol) Diisopropyl azodicarboxylate adds in autoclave together, enclosed high pressure still, nitrogen (0.5Mpa) is under agitation used to replace 5 times, after ethene be adjusted to 2.5Mpa by voltate regulator and be filled with, under agitation be heated to 75 DEG C, evenly 6.7(0.041mol is added in 10 hours, 1.5%mol) Diisopropyl azodicarboxylate, and be evenly warming up to 85 DEG C, by this reactor cooling also emptying, obtain solution 926.3g, 130 DEG C of underpressure distillation 2 hours, obtain 453.1g dope,
31p-NMR analyzes (in sample vitriolization):
Diethyl phospho acid mol content: 91.3%
Ethyl-butyl phospho acid mol content: 2.1%
Ethylphosphinic acid mol content: 3.1
Other mol content: 3.5 %
To be dissolved in the 750mL water of 80 DEG C with 453.1g dope obtained above and add in reactor, be heated with stirring to 95 DEG C, by 303.3g(0.455mol) Tai-Ace S 150 to be dissolved in the 700mL aqueous solution and to instill in 1 hour, at 90 ~ 95 DEG C, be incubated 1 hour after dripping off, be cooled to room temperature, gained solid is leached, and with 700mL water washing three times, be dried to constant weight at 150 DEG C, obtain 338.9g white powder, overall yield 95.41wt%.
Monoalkyl/the dialkylphosphinic salts of embodiment 1 ~ 12 and comparative example 1 ~ 2 gained is mixed by weight 10:60:25:5 with PBT, glass, auxiliary agent at 230 ~ 260 DEG C, extrude from Bitruder, obtained flame-proofed thermoplastic polymer in-mold moulding material, its combustionproperty and mechanical property are tested in sample preparation, record result and see table 1:
The moulding material combustionproperty that table 1 monoalkyl/dialkylphosphinic salts is obtained and mechanical property parameters table
Each performance test is undertaken by following standard:
Tensile strength: GB1040-1992 plastic tensile method for testing performance;
Flexural strength: GB9341-2000 Plastics-Oetermination of flexural properties method;
Amount of deflection: GB9341-2000 Plastics-Oetermination of flexural properties method;
Combustionproperty: UL94 Plastics Combustion performance test;
From upper table 1, the moulding material that monoalkyl/dialkylphosphinic salts prepared by preparation method of the present invention obtains stretches, bending and superior flame retardant property, is applicable to make polymer in-mold moulding material.
Claims (10)
1. a preparation method for monoalkyl/dialkylphosphinic salts, is characterized in that, comprises the steps:
Take organic solvent as reaction medium, hypophosphite is reacted with alkene I under initiator I effect at temperature is 70 ~ 90 DEG C, obtains monoalkylphosphinic acid salt;
Or be reaction medium with organic solvent, hypophosphite is reacted at temperature is 70 ~ 90 DEG C with alkene I under initiator I effect, obtain monoalkylphosphinic acid salt, be heated to 90 ~ 110 DEG C, the monoalkylphosphinic acid salt obtained is reacted with alkene II under initiator II effect, obtains dialkylphosphinic salts;
Or be reaction medium with organic solvent, hypophosphite is reacted with alkene III under initiator III effect at temperature is 70 ~ 120 DEG C, obtains dialkylphosphinic salts;
Wherein, described hypophosphite is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Sr salt of Hypophosporous Acid, 50;
Described organic solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, benzene,toluene,xylene, acetone, ether, trichloromethane, tetrahydrofuran (THF), ritalin, vinyl acetic monomer and/or hexanaphthene;
Described organic solvent and the mass ratio of hypophosphite are 1:1 ~ 10:1;
Described initiator I, initiator II, initiator III are azo-initiator, organic peroxide evocating agent or inorganic peroxide initiator;
The molar content of described initiator I is the 0.1mol% ~ 10mol% of hypophosphite; The molar content of described initiator II is the 0.1mol% ~ 10mol% of monoalkyl hypophosphite; The molar content of described initiator III is the 0.1mol% ~ 10mol% of hypophosphite;
Described alkene I, alkene II and alkene III are identical or different, are the ɑ-alkene of naphthenic alkene or carbonatoms 2 ~ 20;
The mol ratio of described hypophosphite and alkene I is less than 1:1; The mol ratio of described monoalkylphosphinic acid salt and alkene II is less than 1:1; The mol ratio of described hypophosphite and alkene III is less than 1:2;
Described reaction pressure is 0.5MPa ~ 6MPa.
2. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described organic solvent and the mass ratio of hypophosphite are 2:1 ~ 5:1.
3. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described initiator I, initiator II are identical with initiator III.
4. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described initiator I, initiator II are different with initiator III.
5. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, 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, the special pentyl ester of peroxycarbonates, excessively oxalic acid, tert-butyl hydroperoxide isobutyrate, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester or peroxidation trimethylacetic acid; Described inorganic peroxide initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
6. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described ɑ-alkene is selected from the mixture of one or more in ethene, propylene, butylene, iso-butylene or amylene; Described naphthenic alkene is cyclopentenes or tetrahydrobenzene.
7. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, mol ratio 1:1.01 ~ 1.5 of described hypophosphite and alkene I; Mol ratio 1:1.01 ~ 1.5 of described monoalkylphosphinic acid salt and alkene II.
8. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, mol ratio 1:2.01 ~ 2.5 of described hypophosphite and alkene III.
9. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, described reaction pressure is 0.6MPa ~ 2.5MPa.
10. the preparation method of monoalkyl/dialkylphosphinic salts according to claim 1, is characterized in that, the monoalkyl/dialkylphosphinic salts obtained is separated from mixture by filtration or centrifugal treating.
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| CN106243384B (en) * | 2016-07-30 | 2018-11-23 | 青岛科技大学 | The preparation method of dicyclohexenyl hypo-aluminum orthophosphate combustion inhibitor |
| DE102017212098A1 (en) * | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flame retardant polyamide compositions with high heat resistance and their use |
| KR20200062336A (en) | 2017-10-17 | 2020-06-03 | 셀라니즈 세일즈 저머니 게엠베하 | Flame retardant polyamide composition |
| CN108864182A (en) * | 2018-07-24 | 2018-11-23 | 济南泰星精细化工有限公司 | The synthetic method of alkyl phosphinic acid and its aluminium salt under a kind of normal pressure, temperate condition |
| CN110407869B (en) * | 2019-07-11 | 2020-11-17 | 兰州大学 | Preparation method and application of aluminum mono-trifluoropropylphosphinate flame retardant |
| CN110511242A (en) * | 2019-08-21 | 2019-11-29 | 贵州省材料产业技术研究院 | A kind of preparation method of high-purity monoalkylphosphinic acids |
| CN110726801A (en) * | 2019-10-31 | 2020-01-24 | 山东泰星新材料股份有限公司 | Method for monitoring reaction state of alkyl phosphinic acid |
| CN112794867A (en) * | 2020-11-28 | 2021-05-14 | 浙江万盛股份有限公司 | Synthesis method of aluminum diethylphosphinate |
| CN113480574B (en) * | 2020-12-10 | 2024-01-16 | 洪湖市一泰科技有限公司 | Recycling method of phosphorus-containing compound salt |
| CN117534702B (en) * | 2024-01-10 | 2024-04-05 | 太仓维龙化工有限公司 | Dialkyl-monoalkyl composite phosphinate and rapid preparation method thereof |
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| US20070213563A1 (en) * | 2006-03-07 | 2007-09-13 | Clariant International Ltd | Mixtures composed of monocarboxy-functionalized dialkylphosphinic acid salts, their use und a process for their preparation |
| CN101747368A (en) * | 2010-01-22 | 2010-06-23 | 华南理工大学 | Partially alkylated phosphinic acid nonalkali metal salt and preparing method and application thereof |
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| US20070213563A1 (en) * | 2006-03-07 | 2007-09-13 | Clariant International Ltd | Mixtures composed of monocarboxy-functionalized dialkylphosphinic acid salts, their use und a process for their preparation |
| CN101747368A (en) * | 2010-01-22 | 2010-06-23 | 华南理工大学 | Partially alkylated phosphinic acid nonalkali metal salt and preparing method and application thereof |
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