CN101845058B - Hydroxymethylated hypophosphorous acid, derivative metal salt and preparation method thereof - Google Patents
Hydroxymethylated hypophosphorous acid, derivative metal salt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydroxymethylated hypophosphorous acid and a derivative metal salt thereof. The structural general formula of the metal salt is shown in the specification, wherein R is H, CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CH2CH(CH3)CH3, Ph or CH2OH; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr or Mn; and n is the number of the chemical bonds of selected metal ions. The invention also discloses methods for preparing the hydroxymethylated hypophosphorous acid and the derivative metal salt thereof. Since the selected aldehydes compounds are cheap and can be acquired easily, solvents or complex high-voltage devices are not needed in the processing procedure, no high-toxic gas is produced or no complex post-processing procedures are set, and the invention has the advantages that the production cost is greatly lowered, environmental pollution can be avoided, and the synthesis process is simple and feasible.
Description
Technical field
The invention belongs to phosphinates fire retardant material preparing technical field, be specifically related to a kind of methylolation phospho acid and derivant metal salt and its preparation method.
Background technology
The fire retardant that some metal-salt of methylolation phospho acid or hydroxymethyl hypophosphorous acid derivative can be used as macromolecular material uses.Announce two hydroxymethyl hypophosphorous acid zinc as fire retardant such as U.S.4180495, obtained fire-retardant ethylene glycol terephthalate.
As the existing pertinent literature report of the preparation of methylolation phospho acid or methylolation phosphinic acid derivatives metal-salt.For example, U.S.3513113 discloses take yellow phosphorus and Paraformaldehyde 96 as raw material, take methyl alcohol as solvent, in the presence of sodium hydroxide, prepared methylolation phospho acid sodium, but can produce the phosphine gas of severe toxicity in the preparation process of the method, this not only jeopardizes human life safety, and contaminate environment.And for example U.S.4180495 discloses Using Sodium Hypophosphite, hydrochloric acid, Paraformaldehyde 96 is raw material, the synthetic preparation method who obtains two hydroxymethyl hypophosphorous acids under normal pressure, but because the reaction process of the method need to be used a large amount of hydrochloric acid (2 kilograms of sodium hypophosphites need 4 liters of hydrochloric acid), thereby need to just can remove unnecessary hydrochloric acid having reacted rear employing multistep subsequent disposal, thereby so that cost greatly improve.U.S.5196554 discloses take inorganic hypo-aluminum orthophosphate and Paraformaldehyde 96 as raw material for another example, has syntheticly obtained two hydroxymethyl hypophosphorous acid aluminium.But this reaction needed is carried out under specific autoclave, high temperature, requires comparison in equipment precision and energy consumption large, does not meet the requirement of environmental protection.
Summary of the invention
Primary and foremost purpose of the present invention provides the new methylolation phospho acid of a class and derivant metal salt thereof, uses as additive flame retardant.
Secondary objective of the present invention is the problem that exists for prior art, and a kind of method for preparing above-mentioned methylolation phospho acid and derivant metal salt thereof is provided.
A kind of new methylolation phospho acid provided by the invention and derivant metal salt thereof, the general structure of this metal-salt is as follows:
Wherein, R is H, CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2CH
2CH
2CH
3, CH
2CH (CH
3) CH
3, Ph or CH
2OH; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr or Mn; N is the chemical combination bond number of selected metal ion.
The method of the above-mentioned methylolation phospho acid of preparation provided by the invention and derivant metal salt thereof is characterized in that the processing step of the method and condition are as follows:
1) will contain first the Hypophosporous Acid, 50 of at least one phosphorus-hydrogen bond or phosphinic acid derivatives and be heated to 40-150 ℃ after, slowly add aldehyde compound, then stirring reaction 2-15h, and contain Hypophosporous Acid, 50 or the phosphinic acid derivatives of at least one phosphorus-hydrogen bond: the mol ratio of aldehyde compound=1: 1～5;
2) temperature is transferred to 20-95 ℃ after, add and contain the Hypophosporous Acid, 50 of at least one phosphorus-hydrogen bond or the alkali metal hydroxide of phosphinic acid derivatives equivalent carries out neutralization reaction, and make methylolated phospho acid or methylolated phosphinic acid derivatives be converted into an alkali metal salt;
3) temperature is transferred to 40-100 ℃ after, add the formed metallic compound of any metal ion among Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, the Mn, and stirring reaction to precipitation separates out get final product fully, wherein adds metallic compound and the 2nd) to go on foot the mol ratio of reacting an alkali metal salt that obtains be 1: 1～10.
The used Hypophosporous Acid, 50 that contains at least a phosphorus-hydrogen bond or phosphinic acid derivatives are preferably any in Hypophosporous Acid, 50, methyl phosphonous acid, ethyl phosphonous acid, propyl group phosphonous acid, isobutyl-phosphonous acid, methyl phosphite, phosphorous acid ethyl ester, phenyl-phosphonite or the phenyl-phosphite in the aforesaid method.
Used aldehyde compound is preferably formaldehyde or Paraformaldehyde 96 in the aforesaid method.
Used alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide in the aforesaid method.
Used any formed metallic compound by among Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, the Mn is their metal oxide, metal hydroxides, metal oxide oxyhydroxide, metal sulfate, metal acetate salt, metal nitrate or metal chloride in the aforesaid method.Preferred metal oxide, metal hydroxides, metal sulfate or metal chloride wherein.
The present invention has the following advantages:
1, because the present invention not only selects is that the aldehyde compound that cheaply is easy to get comes that Hypophosporous Acid, 50 or phosphinic acid derivatives are carried out methylolation and processes, and in treating processes, neither need use solvent, can not produce hypertoxic gas again, thereby can greatly reduce production costs, avoid the pollution effect that environment is brought.
2, because synthesis technique simple possible of the present invention do not need complicated high-tension apparatus, and temperature of reaction is also lower, thereby has not only been reduced the requirement to equipment, and saved the energy, greatly reduce production cost.
3, because the present invention does not need to add the unnecessary material that the later stage need to remove in preparation process, thereby neither need to arrange complicated postprocessing working procedures, can not discharge toxic wastewater again, this has not only been avoided negative impact that environment is brought, can also avoid a series of problems that cause product cost to increase of bringing because of the later stage wastewater treatment.
Description of drawings
Fig. 1 is the present invention, and (mol ratio is Hypophosporous Acid, 50: phosphorus spectrum contrast formaldehyde=1: 1) with Hypophosporous Acid, 50 and product methylolation phospho acid.The chemical shift δ of raw material Hypophosporous Acid, 50 is mainly at 7-8ppm as can be seen from FIG.; By with formaldehyde reaction after the chemical shift δ of product hydroxymethyl hypophosphorous acid mainly at 27-29ppm, two positions of 43-45ppm go out the peak, the peak that goes out of raw material Hypophosporous Acid, 50 dies down simultaneously, the phosphorus atom that has produced new chemical shift is described, proved formaldehyde with Hypophosporous Acid, 50 on phosphorus-hydrogen bond reaction generated hydroxymethyl hypophosphorous acid.
Fig. 2 is the infrared spectrum of the hydroxymethyl hypophosphorous acid calcium for preparing of the present invention, and the main infrared absorption peak among this figure is respectively 2338cm
-1(P-H), 2895cm
-1(CH
2), 3104cm
-1(OH), 1174cm
-1(P=O), 974cm
-1(P-O).
Fig. 3 is the infrared spectrum of the hydroxymethyl phenyl phospho acid aluminium for preparing of the present invention, and the main infrared absorption peak among this figure is respectively 1294cm
-1(P=O), 1040cm
-1(P-O), 1438,1591cm
-1(ph), 2896cm
-1(CH2), 723cm
-1(P-C), 3421cm
-1(OH).
The hydrogen spectrogram of the hydroxymethyl phenyl phospho acid aluminium of Fig. 4 the present invention preparation, the Hydrochemistry displacement δ in the phenyl ring is at 7.5-7.8ppm as can be seen from FIG., and the Hydrochemistry displacement δ of the methylene radical in the methylol is at 4.4ppm.The proof Paraformaldehyde 96 with phenyl phosphorous acid in the reaction of phosphorus-hydrogen bond generated methylol.
Embodiment
The below provides embodiment so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field must belong to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention does.
Embodiment 1
The 1.0mol Hypophosporous Acid, 50 is joined in the there-necked flask with magnetic stirring apparatus, be heated to 85 ℃ after, slowly drip 2.0mol formaldehyde solution, at 85 ℃ of lower reaction 8h, obtain the methylolation phospho acid after dropwising; After being cooled to 20 ℃, slowly add the saturated sodium hydroxide solution of 1.0mol, obtain the hydroxymethyl hypophosphorous acid sodium salt; Be warming up to 40 ℃, slowly add the saturated aluminum trichloride solution of 0.33mol, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is hydroxymethyl hypophosphorous acid aluminium salt.
The 1.0mol Hypophosporous Acid, 50 is joined in the there-necked flask with magnetic stirring apparatus, be heated to 40 ℃ after, slowly drip 1.0mol formaldehyde solution, at 40 ℃ of lower reaction 15h, obtain the methylolation phospho acid after dropwising; Keeping temperature is 40 ℃, slowly adds the saturated potassium hydroxide solution of 1.0mol, obtains hydroxymethyl hypophosphorous acid sylvite; Be warming up to 60 ℃, slowly add the saturated calcium chloride solution of 0.5mol, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is the hydroxymethyl hypophosphorous acid calcium salt.
Embodiment 3
1.0mol methyl phosphorous acid is joined in the there-necked flask with magnetic stirring apparatus, be heated to 60 ℃ after, slowly drip 3.0mol formaldehyde solution, at 60 ℃ of lower reaction 12h, obtain the methylolation methyl-phosphinic acid after dropwising; Maintain the temperature at 60 ℃, slowly add the saturated sodium hydroxide solution of 1.0mol, obtain methylol methyl-phosphinic acid sodium salt; Adjust the temperature to 50 ℃, slowly add 0.33mol aluminium hydroxide, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is methylol methyl-phosphinic acid aluminium salt.
1.0mol phenyl phosphorous acid is joined in the there-necked flask with magnetic stirring apparatus, be heated to 120 ℃ after, slowly drip the 1.0mol Paraformaldehyde 96, add complete after at 120 ℃ of lower reaction 6h, obtain the methylolation phenyl phosphinic acid; After being cooled to 80 ℃, slowly add the saturated potassium hydroxide solution of 1.0mol, obtain hydroxymethyl phenyl phospho acid sylvite; Adjust the temperature to 90 ℃, slowly add the saturated aluminum trichloride solution of 0.25mol, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is hydroxymethyl phenyl phospho acid aluminium salt.
1.0mol phenyl phosphorous acid is joined in the there-necked flask with magnetic stirring apparatus, be heated to 150 ℃ after, slowly drip the 5.0mol Paraformaldehyde 96, add complete after at 150 ℃ of lower reaction 2h, obtain the methylolation phenyl phosphinic acid; After being cooled to 95 ℃, slowly add the saturated sodium hydroxide solution of 1.0mol, obtain hydroxymethyl phenyl phospho acid sodium salt; Adjust the temperature to 100 ℃, slowly add the saturated calcium chloride solution of 1.0mol, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is hydroxymethyl phenyl phospho acid calcium salt.
1.0mol methyl phosphorous acid is joined in the there-necked flask with magnetic stirring apparatus, be heated to 90 ℃ after, slowly add the 4.0mol Paraformaldehyde 96, at 90 ℃ of lower reaction 10h, obtain the methylolation methyl-phosphinic acid after dropwising; Regulate temperature at 50 ℃, slowly add the saturated potassium hydroxide solution of 1.0mol, obtain methylol methyl-phosphinic acid sylvite; Adjust the temperature to 70 ℃, slowly add 0.1mol Tai-Ace S 150, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is methylol methyl-phosphinic acid aluminium salt.
Embodiment 7
The 1.0mol Hypophosporous Acid, 50 is joined in the there-necked flask with magnetic stirring apparatus, be heated to 70 ℃ after, slowly add the 2.0mol Paraformaldehyde 96, add complete after at 70 ℃ of lower reaction 7h, obtain the methylolation phospho acid; Maintain the temperature at 70 ℃, slowly add the saturated sodium hydroxide solution of 1.0mol, obtain the hydroxymethyl hypophosphorous acid sodium salt; Be warming up to 80 ℃, slowly add the saturated aluminum trichloride solution of 0.2mol, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is hydroxymethyl hypophosphorous acid aluminium salt
The 1.0mol Hypophosporous Acid, 50 is joined in the there-necked flask with magnetic stirring apparatus, be heated to 50 ℃ after, slowly add the 1.0mol Paraformaldehyde 96, add complete after at 50 ℃ of lower reaction 4h, obtain the methylolation phospho acid; Regulate temperature at 30 ℃, slowly add the saturated potassium hydroxide solution of 1.0mol, obtain hydroxymethyl hypophosphorous acid sylvite; Be warming up to 65 ℃, slowly add the saturated calcium chloride solution of 0.16mol, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is the hydroxymethyl hypophosphorous acid calcium salt
Embodiment 9
1.0mol methyl phosphorous acid is joined in the there-necked flask with magnetic stirring apparatus, be heated to 80 ℃ after, slowly add 1.0mol formaldehyde solution, at 80 ℃ of lower reaction 5h, obtain the methylolation methyl-phosphinic acid after dropwising; Regulate temperature at 85 ℃, slowly add the saturated sodium hydroxide solution of 1.0mol, obtain methylol methyl-phosphinic acid sodium salt; Adjust the temperature to 75 ℃, slowly add the 0.14mol magnesium hydroxide, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is methylol methyl-phosphinic acid magnesium salts.
The 1.0mol Hypophosporous Acid, 50 is joined in the there-necked flask with magnetic stirring apparatus, be heated to 75 ℃ after, slowly add 2.0mol formaldehyde solution, at 75 ℃ of lower reaction 9h, obtain the methylolation phospho acid after dropwising; Maintain the temperature at 75 ℃, slowly add the saturated potassium hydroxide solution of 1.0mol, obtain hydroxymethyl hypophosphorous acid sylvite; Adjust the temperature to 85 ℃, slowly add 0.13mol zinc sulfate, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is the hydroxymethyl hypophosphorous acid zinc salt.
Claims (1)
1. the preparation method of a methylol methyl-phosphinic acid magnesium salts is characterized in that the processing step of the method and condition are as follows:
1.0mol methyl phosphorous acid is joined in the there-necked flask with magnetic stirring apparatus, be heated to 80 ℃ after, slowly add 1.0mol formaldehyde solution, at 80 ℃ of lower reaction 5h, obtain the methylolation methyl-phosphinic acid after dropwising; Regulate temperature at 85 ℃, slowly add the saturated sodium hydroxide solution of 1.0mol, obtain methylol methyl-phosphinic acid sodium salt; Adjust the temperature to 75 ℃, slowly add the 0.14mol magnesium hydroxide, and stirring reaction to precipitation separates out get final product fully, then with its suction filtration and dry, the gained powder is methylol methyl-phosphinic acid magnesium salts.
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| CN102321362B (en) * | 2011-08-05 | 2013-07-10 | 四川大学 | High-retardant polyamide |
| CN102276837B (en) * | 2011-08-19 | 2013-01-02 | 慧智科技（中国）有限公司 | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof |
| CN102352096A (en) * | 2011-09-15 | 2012-02-15 | 苏州铧茂工程塑料有限公司 | Non-halogen flame retardant PC (polycarbonate) /ABS (acrylonitrile butadiene styrene) alloy and preparation method thereof |
| 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 |
| CN105623204B (en) * | 2016-01-04 | 2017-11-10 | 江苏沃特新材料科技有限公司 | A kind of high CTI environment-friendly flame-retardant reinforced PBTs composite and preparation method thereof |
| CN105970341A (en) * | 2016-06-29 | 2016-09-28 | 马海燕 | Flame-retardant polyester monofilament and method for producing same |
| RU2624627C1 (en) | 2016-10-11 | 2017-07-05 | Общество с ограниченной ответственностью "ЭкоХимКонсалтинг" | Bis (oximethyl) phosphinic acid and its salts with biogenic metals as plant growth and development regulators |
| CN110746457B (en) * | 2019-11-12 | 2021-10-22 | 四川大学 | Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer |
| CN113480803B (en) * | 2021-07-13 | 2024-01-12 | 韩山师范学院 | Flame-retardant polyolefin composite material and preparation method and application thereof |
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| DE10006870A1 (en) * | 2000-02-16 | 2001-08-23 | Budenheim Rud A Oetker Chemie | Aluminum salts of phosphinic acid mixtures, used as flame retardant for polymer, e.g. polyamide, polyester, polycarbonate or phenolic or melamine resin, are based on reaction product of white phosphorus, formaldehyde and epoxide |
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| CN101671361A (en) * | 2008-09-09 | 2010-03-17 | 王忠卫 | Method for preparing hydroxymethylphenylphosphinic acid flame retardant |
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| JP4222601B2 (en) * | 2003-02-10 | 2009-02-12 | 日本化学工業株式会社 | Method for producing phosphate metal salt composition |
| TWI410453B (en) * | 2005-12-01 | 2013-10-01 | Supresta Llc | Flame retardant compositions containing mixtures of disubstituted phosphinate salts and monosubstituted phosphinate salts |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303674B1 (en) * | 1997-03-04 | 2001-10-16 | Ticona Gmbh | Aluminium salts of alkylhydroxymethylphosphinic acids |
| DE10006870A1 (en) * | 2000-02-16 | 2001-08-23 | Budenheim Rud A Oetker Chemie | Aluminum salts of phosphinic acid mixtures, used as flame retardant for polymer, e.g. polyamide, polyester, polycarbonate or phenolic or melamine resin, are based on reaction product of white phosphorus, formaldehyde and epoxide |
| CN101671361A (en) * | 2008-09-09 | 2010-03-17 | 王忠卫 | Method for preparing hydroxymethylphenylphosphinic acid flame retardant |
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| Title |
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| JP特开2004-238378A 2004.08.26 |
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