CN101830926A - Dialkyl metal phosphinate and synthesis process of fire retardant thereof - Google Patents
Dialkyl metal phosphinate and synthesis process of fire retardant thereof Download PDFInfo
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- CN101830926A CN101830926A CN201010168431A CN201010168431A CN101830926A CN 101830926 A CN101830926 A CN 101830926A CN 201010168431 A CN201010168431 A CN 201010168431A CN 201010168431 A CN201010168431 A CN 201010168431A CN 101830926 A CN101830926 A CN 101830926A
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Abstract
The invention relates to a preparation method of a fire retardant, in particular to a dialkyl metal phosphinate and a synthesis process of a fire retardant thereof. The dialkyl metal phosphinate has a structural formula described in the specification, wherein R1 represents alkyl, M represents metal ions, n represents an integer from 1 to 3, and R2 represents olefin of aliphatic series. The preparation method comprises the steps of: reacting alkylphosphonous dichloride with alcohol to obtain monoalkyl phosphate; carrying out radical reaction on the monoalkyl phosphate with olefin to obtain dialkyl ester phosphinate; and reacting the dialkyl ester phosphinate with lewis acid to obtain the dialkyl metal phosphinate fire retardant. The invention has mild reaction condition; the prepared product has good thermal stability and high yield, wherein the yield can reach 87.6 percent by the count of methyl butyl ester phosphate; and the preparation method is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, the synthesis technique of specifically a kind of dialkyl metal phosphinate and fire retardant thereof.
Background technology
Dialkylphosphinic salts can be used as fire retardant, dialkylphosphinic salts class flame retardant products density is lower, the fire retardant consumption is less, better mechanical property, color and luster is preferable, and smoke density is lower, CTI (phase ratio creepage tracking index) value higher (can reach 600V), in electric industry, have very much an application prospect, and be specially adapted to thin-walled electronic devices and components, transparent film-making and film.In addition, from toxicology and environmental angle research metal phosphinates, find that it is without any retroaction.Dialkyl hypophosphorous acid salt structural formula is as follows:
As far back as beginning of the eighties late 1970s, U.S. Pennwalt company tests with regard to the character to various dialkylphosphinic salts.U.S. Ticona company successively studied phospho acid zinc aluminium calcium do the performance of fire retardant in PA and PBT.German in recent years Clariant company is devoted to the research and development of this novel phosphorus flame retardant.And set up pilot production line in 2004, developed the fire retardant of two kinds of metal phosphinates interpolation nitrogen synergists, board Exolit OP 1311 by name and Exolit OP 1312, these two kinds of fire retardants are mainly used in the fire-retardant of PA6 and PA66, have realized overall equilbrium preferably on processibility, mechanical property, flame retardant resistance, living cigarette, electric property, color and luster and cost.This fire retardant does not reduce the electric leakage track index CTI value of GRPA66, this be other fire retardants can not compare.In addition, compare with fire retardant material not with the common mechanical performance of the fire-retardant GRPA66 of Exolit OP 1312M1, drop-out value is 20%～30%, and this also is an acceptable.This fire-retardant GRPA66 is specially adapted to make injection moulding high-pressure electronic components and parts
[13]
Chinese scholars is for the existing a lot of researchs of the synthetic method of dialkylphosphinic salts class.Use the Grignard reagent method the earliest, productivity ratio is lower, washs isolating operation more complicated, and technical process and raw material are equipped with complicated.The metal coordination catalysis additive process generally only is applied to the synthetic aspect of monoalkyl phospho acid or its salt, and the reaction times is longer, the technical process complexity.Foreign patent had been reported in a large number with yellow phosphorus and methyl chloride and had been reacted under the phase-transfer catalyst effect in recent years, obtain the methyl hypophosphite, and then by introducing second alkyl with alkene generation free radical reaction, but this process recovery ratio is lower, should not be applied to the industrial production of alkyl phosphinic acid or its salt of scale.
Summary of the invention
The objective of the invention is is exactly defective at existing dialkyl metal phosphinate preparation method, the synthesis technique of dialkyl metal phosphinate fire retardant is provided, it by methyl dichloro phosphorus as initial feed, this synthesis technique can carry out under the purification step that does not have complexity smoothly, thereby make dialkylphosphinic salts in a kind of easy mode, the by product that generates in the reaction process can be recycled, environmentally safe.Be suitable for suitability for industrialized production.
Technical scheme of the present invention is achieved in that the structural formula of dialkyl metal phosphinate is as follows:
R wherein
1The expression alkyl, M represents metal ion, n represents the integer of 1-3, R
2Expression aliphatics alkene.
R wherein
1Preferable methyl, ethyl or propyl group; The preferred iron ion of M, aluminum ion, zine ion or stannous ion.
R wherein
2Expression vinyl, positive propenyl, pseudoallyl, n-butene base, isobutenyl, positive pentenyl, isopentene group, n-hexylene base, dissident's thiazolinyl, positive octenyl, isooctene base, 1-decene base, 1,2-cyclooctadiene base, 1,3 cyclopentadienyl, dicyclopentadiene base, cyclohexenyl, cyclopentenyl, cycloheptenyl or styryl.
The present invention's technical scheme preferably is: R
1Expression methyl, M represent aluminum ion, R
2Expression styryl or cyclohexenyl.
A kind of synthesis technique of dialkyl metal phosphinate fire retardant, it may further comprise the steps:
(1), with alkyl dichloro phosphine and alcohol reaction, obtain the monoalkyl-phosphonic acid ester;
(2), with the monoalkyl-phosphonic acid ester under action of evocating with alkene generation free radical reaction, obtain the dialkyl phosphinic acid ester;
(3), with the reaction of dialkyl hypophosphorous acid ester and Lewis acid, obtain the dialkyl metal phosphinate fire retardant.
Wherein said Lewis acid is iron trichloride, aluminum chloride, zinc chloride or tin protochloride; Described alcohol is methyl alcohol, ethanol, butanols, n-dodecanol, Virahol or isooctyl alcohol; Described alkene is ethene, positive propylene, different propylene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene, dissident's alkene, positive octene, isooctene, 1-decene, 1,2-cyclooctadiene, 1,3 cyclopentadiene, dicyclopentadiene, tetrahydrobenzene, cyclopentenes, suberene, vinylbenzene.Described initiator is cyclohexanone peroxide, dibenzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Concrete preparation method of the present invention is:
The first step reaction: monoalkyl-phosphonic acid ester synthetic
Alkyl dichloro phosphine and alcohol reaction obtain the monoalkyl-phosphonic acid ester
Used alkyl dichloro phosphorus molecular structural formula is as follows:
Reaction formula is as follows:
The second step reaction: dialkyl phosphinic acid ester synthetic
Monoalkyl-phosphonic acid ester and alkene generation free radical reaction obtain the dialkyl phosphinic acid ester, and its reaction examination is as follows:
R
3The expression alkyl.
Used alkene:
Aliphatics alkene: comprise ethene, positive propylene, different propylene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene, dissident's alkene, positive octene, isooctene, 1-decene, 1,2-cyclooctadiene, 1,3 cyclopentadiene, dicyclopentadiene.
Cyclic olefin; Tetrahydrobenzene, cyclopentenes, suberene
Aromatic olefin: vinylbenzene,
Used initiator:
Organic peroxide evocating agent is as cyclohexanone peroxide, dibenzoyl peroxide, tertbutyl peroxide etc.;
Azo-initiator is as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
Three-step reaction: dialkylphosphinic salts synthetic
The metallic compound of dialkyl hypophosphorous acid ester and electron deficiency (Lewis acid) reaction obtains dialkyl metal phosphinate, and its reaction formula is as follows:
According to the difference of used metal-salt, this reaction is available or without solvent.Solvent for use is mainly the stronger high boiling solvent of polarity.As oil of mirbane, dimethyl sulfoxide (DMSO), N, the N-dimethyl adds acid amides, N,N-dimethylacetamide or paraffin oil.
The present invention adopts new technology and has synthesized dialkylphosphinic salts, and the preparation method is simple.Reaction conditions gentleness of the present invention, the product Heat stability is good of preparation, yield height, yield can reach 87.6% in the methyl-phosphorous acid butyl ester, and this technology suitability for industrialized is produced.
Embodiment
Below in conjunction with embodiment the present invention is described further:
Synthesizing of embodiment 1 methyl phosphonous acid mono:
With the ethanol of 2.0M and the N of 1M, the N-xylidene(s) is dissolved in the Skellysolve A or normal hexane of 5-6 times of volume, after being chilled to 0 degree, under stirring fast, drip the dichloromethyl phosphine of 1M, warm 0-5 degree in keeping, after adding, under the 0-5 degree, stirred 1 hour, be raised to room temperature, under the 20-25 degree, stirred 2 hours, refluxed then 1 hour.Be as cold as room temperature, filter, use the solvent wash filter cake, after filtrate desolventized, product was collected in underpressure distillation.Gas chromatographic analysis, the about 91-93% of content of methyl phosphonous acid ethyl ester, yield: about 87%.
Synthesizing of embodiment 2 methyl phosphonous acid monos:
With the propyl carbinol of 2.0M and the N of 1M, the N-xylidene(s) is dissolved in the Skellysolve A or normal hexane of 5-6 times of volume, after being chilled to 0 degree, under stirring fast, drip the dichloromethyl phosphine of 1M, warm 0-5 degree in keeping, after adding, under the 0-5 degree, stirred 1 hour, be raised to room temperature, under the 20-25 degree, stirred 2 hours, refluxed then 1 hour.Be as cold as room temperature, filter, use washing with acetone, after filtrate desolventized, product was collected in underpressure distillation.Gas chromatographic analysis, the about 95-96% of content of methyl phosphonous acid mono, yield: about 90%.
Synthesizing of embodiment 3 methylethyl phospho acid butyl esters:
1 mole of methyl phosphonous acid mono joined in 2 liters the pressure reactor, be heated to 85 ℃ then, be pushed down into ethene, in 30 minutes, pump into the solution of Diisopropyl azodicarboxylate in 50 milliliters of hexanaphthenes of volume pump with 0.02 mole at 2Mpa pressure.Temperature of reaction was kept under 90 ℃ 4 hours, during this period, the ethylene pressure that has descended is adjusted to 2Mpa frequently, with the mixture cooling, fractionation plant is used in release instead, tells the solvent hexanaphthene then.
Synthesizing of embodiment 4 methylcyclohexyl Hypophosporous Acid, 50 butyl esters:
Methyl phosphonous acid mono and 1 mole of tetrahydrobenzene of getting 1 mole join in the flask, start stirring, are warmed up to 85 ℃, add the solution of azo-bis-isobutyl cyanide in 50 milliliters of hexanaphthenes in 30 minutes, temperature of reaction is refluxed down at 90 ℃ stir 4h.Use water distilling apparatus at last instead, tell the solvent hexanaphthene, obtain methylcyclohexyl Hypophosporous Acid, 50 butyl ester.
Synthesizing of embodiment 5 methylbenzene ethyl Hypophosporous Acid, 50 butyl esters:
Methyl phosphonous acid mono and 1 mole of vinylbenzene of getting 1 mole join in the flask, start stirring, are warmed up to 85 ℃, add the solution of azo-bis-isobutyl cyanide in 50 milliliters of hexanaphthenes in 30 minutes, temperature of reaction is refluxed down at 90 ℃ stir 4h.Use fractionation plant at last instead, tell the solvent hexanaphthene, obtain methylbenzene ethyl Hypophosporous Acid, 50 butyl ester.
Synthesizing of embodiment 6 methylcyclohexyl phospho acid zinc:
Get the methylbenzene ethyl Hypophosporous Acid, 50 butyl ester that 1 mole of embodiment, 5 reactions make; the Zinc Chloride Anhydrous that adds 0.5 mole; start agitator; be warming up to 120 ℃ under nitrogen protection, the limit coronite fractionates out the chlorobutane that generates in the reaction process, reaction 2.5h; cooling; filter filter cake washing with acetone, vacuum-drying.
Synthesizing of embodiment 7 methylcyclohexyl phospho acid aluminium:
Get the methylbenzene ethyl Hypophosporous Acid, 50 butyl ester that 1.2 moles of embodiment, 5 reactions make; add 300 milliliters of oil of mirbane; the aluminum trichloride (anhydrous) that adds 0.4 mole starts agitator, is warming up to 120 ℃ under nitrogen protection; the limit coronite fractionates out the chlorobutane that generates in the reaction process; reaction 3.0h, cooling is filtered; the filter cake washing with acetone, vacuum-drying.
Synthesizing of embodiment 8 methylbenzene ethylphosphonic acid aluminium
Get the methylbenzene ethyl Hypophosporous Acid, 50 butyl ester that 1.2 moles of embodiment, 5 reactions make; add 300 milliliters of oil of mirbane; the aluminum trichloride (anhydrous) that adds 0.4 mole again starts agitator, is warming up to 120 ℃ under nitrogen protection; the limit coronite fractionates out the chlorobutane that generates in the reaction process; behind the reaction 3.0h, cooling is filtered; the filter cake washing with acetone, vacuum-drying.
Synthesizing of implementation column 9 methylbenzene ethyl phospho acid zinc:
Get the methylbenzene ethyl Hypophosporous Acid, 50 butyl ester that 1 mole of embodiment, 5 reactions make; add 300 milliliters of dimethyl sulfoxide (DMSO); the Zinc Chloride Anhydrous that adds 0.5 mole starts agitator, is warming up to 120 ℃ under nitrogen protection; the limit coronite fractionates out the chlorobutane that generates in the reaction process; reaction 2.5h, cooling is filtered; the filter cake washing with acetone, vacuum-drying.
Embodiment 10 methylcyclohexyl phospho acid aluminium
(1), methylcyclohexyl phosphonic acids butyl ester is synthetic
Methyl phosphonous acid mono and 1 mole of tetrahydrobenzene of getting 1 mole join in the flask, start stirring, are warmed up to 85 ℃, add the solution of azo-bis-isobutyl cyanide in 50 milliliters of hexanaphthenes in 30 minutes, temperature of reaction is refluxed down at 90 ℃ stir 4h.Use water distilling apparatus at last instead, tell the solvent hexanaphthene, obtain methylcyclohexyl Hypophosporous Acid, 50 butyl ester.Its reaction equation is as follows:
(2), methylcyclohexyl phospho acid aluminium is synthetic
Get 1.2 moles of methylcyclohexyl phosphonic acids butyl esters; add 300 milliliters of dimethyl sulfoxide (DMSO); the aluminum trichloride (anhydrous) that adds 0.4 mole again starts agitator, is warming up to 120 ℃ under nitrogen protection; the limit coronite fractionates out the chlorobutane that generates in the reaction process; behind the reaction 3.0h, cooling is filtered; the filter cake washing with acetone, vacuum-drying.
The analytical results table
Detected result shows that the content of methyl-phosphorous acid mono reaches 86.5%.
Claims (10)
1. dialkyl metal phosphinate, its structural formula is as follows:
R wherein
1The expression alkyl, M represents metal ion, n represents the integer of 1-3, R
2Expression aliphatics alkene.
2. a kind of dialkyl metal phosphinate according to claim 1, wherein R
1Expression methyl, ethyl or propyl group.
3. a kind of dialkyl metal phosphinate according to claim 1, wherein M represents iron ion, aluminum ion, zine ion or stannous ion.
4. a kind of dialkyl metal phosphinate according to claim 1, wherein R
2Expression vinyl, positive propenyl, pseudoallyl, n-butene base, isobutenyl, positive pentenyl, isopentene group, n-hexylene base, dissident's thiazolinyl, positive octenyl, isooctene base, 1-decene base, 1,2-cyclooctadiene base, 1,3 cyclopentadienyl, dicyclopentadiene base, cyclohexenyl, cyclopentenyl, cycloheptenyl or styryl.
5. a kind of dialkyl metal phosphinate according to claim 1, wherein R
1Expression methyl, M represent aluminum ion, R
2Expression styryl or cyclohexenyl.
6. the synthesis technique of a dialkyl metal phosphinate fire retardant, it may further comprise the steps:
(1), with alkyl dichloro phosphine and alcohol reaction, obtain the monoalkyl-phosphonic acid ester;
(2), with the monoalkyl-phosphonic acid ester under action of evocating with alkene generation free radical reaction, obtain the dialkyl phosphinic acid ester;
(3), with the reaction of dialkyl hypophosphorous acid ester and Lewis acid, obtain the dialkyl metal phosphinate fire retardant.
7. the synthesis technique of a kind of dialkyl metal phosphinate fire retardant according to claim 6, wherein said Lewis acid are iron trichloride, aluminum chloride, zinc chloride or tin protochloride.
8. the synthesis technique of a kind of dialkyl metal phosphinate fire retardant according to claim 6, wherein said alcohol are methyl alcohol, ethanol, butanols, n-dodecanol, Virahol or isooctyl alcohol.
9. the synthesis technique of a kind of dialkyl metal phosphinate fire retardant according to claim 6, wherein said alkene is ethene, positive propylene, different propylene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene, dissident's alkene, positive octene, isooctene, 1-decene, 1,2-cyclooctadiene, 1,3 cyclopentadiene, dicyclopentadiene, tetrahydrobenzene, cyclopentenes, suberene, vinylbenzene.Used initiator:.
10. the synthesis technique of a kind of dialkyl metal phosphinate fire retardant according to claim 6, wherein said initiator are cyclohexanone peroxide, dibenzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
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| CN102241872A (en) * | 2011-06-28 | 2011-11-16 | 江汉大学 | Aluminum methylcyclohexyl phosphinate/epoxy resin flame-retardant composite material |
| CN102321118A (en) * | 2011-07-26 | 2012-01-18 | 江西科技师范学院 | Preparation method of dicyclohexyl-methyl-phosphinic acid |
| CN102924508A (en) * | 2012-09-19 | 2013-02-13 | 浙江新化化工股份有限公司 | Preparation method for dialkyl phosphinates |
| CN103435643A (en) * | 2013-08-08 | 2013-12-11 | 清远市普塞呋磷化学有限公司 | Preparation method of monohydroxy dialkyl phosphinic acid metal salt fire retardant |
| CN103694273A (en) * | 2013-01-10 | 2014-04-02 | 中国科学院上海有机化学研究所 | Preparation method and application of dialkyl phosphinate compounds and salts thereof |
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| US9850263B2 (en) | 2014-05-13 | 2017-12-26 | Bayer Cropscience Aktiengesellschaft | Process for preparing phosphorus containing cyanohydrins |
| US10961265B2 (en) | 2014-05-13 | 2021-03-30 | Basf Se | Process for preparing phosphorus containing cyanohydrins |
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| CN111763232B (en) * | 2020-05-09 | 2022-11-04 | 北京工商大学 | Phosphaphenanthrene/hypophosphite biradical flame retardant containing reactive groups and preparation method thereof |
| CN113480574A (en) * | 2020-12-10 | 2021-10-08 | 洪湖市一泰科技有限公司 | Recycling method of phosphorus-containing composite salt |
| 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 |
| CN113493478A (en) * | 2021-07-28 | 2021-10-12 | 南通江山农药化工股份有限公司 | MPE synthesis process and MPE |
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