CN102775637A - Carboxylic methyl acrylic acid phosphinate flame retardant and preparation method thereof - Google Patents
Carboxylic methyl acrylic acid phosphinate flame retardant and preparation method thereof Download PDFInfo
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- CN102775637A CN102775637A CN2012102474906A CN201210247490A CN102775637A CN 102775637 A CN102775637 A CN 102775637A CN 2012102474906 A CN2012102474906 A CN 2012102474906A CN 201210247490 A CN201210247490 A CN 201210247490A CN 102775637 A CN102775637 A CN 102775637A
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Abstract
The invention discloses a carboxylic methyl acrylic acid phosphinate flame retardant and a preparation method thereof. The structural formula of the carboxylic methyl acrylic acid phosphinate flame retardant is shown in the specification, wherein M represents metal, and n represents an integer ranging from 1 to 4. The flame retardant can be blended with matrix resin in the form of carboxyl chemical bond to improve the compatibility between the flame retardant and the resin as well as the stability of a phase structure of the flame retardant in the material, and avoid the disadvantages such as poor compatibility and easiness in seepage of an additive flame retardant, so that the flame retardancy, mechanical properties and heat resistance of the material are all improved. Meanwhile, a synthesis method of the carboxylic methyl acrylic acid phosphinate flame retardant takes cyclic phosphorus pentoxide as a starting phosphoric source, and a target product can be obtained through two steps of reaction, namely hydrolysis and neutralization. The synthesis method is simple in synthesis process, mild in reaction conditions and high in yield which can reach above 95%; solvent and residue in the reaction can be recycled; the synthesis method has no pollution to the environment, and is applicable to industrial production.
Description
Technical field
The present invention relates to flame retardant area, particularly a kind of carboxylic methylpropanoic acid phosphinates fire retardant and preparation method thereof.
Background technology
Halogen containing polymers or have good flame retardant property with flame-retardant mixture that halogen containing flame-retardant combines, the Ceng Zuowei fire retardant material is widely used.But when fire took place, this type Halogen fire retardant material can produce a large amount of smog and deleterious corrosive hydrogen halides gas, caused secondary harm.New halogen-free flame-retardant system, the amount of being fuming is little during burning, does not produce poisonous, corrosive gases, becomes the BACN that meets the international standard development trend.The dialkyl phosphinic acid based flame retardant is a kind of common halogen-free flame retardants, has good flame-retardant effect.
The present commercialization of dialkylphosphinic salts based flame retardant is used, and mainly is to be the dialkylphosphinic salts that representative was developed with German Clariant company, and the alkyl structure in its structure does not have reactive, and only the fire retardant as addition type uses; In recent years; Exploitation with dialkylphosphinic salts of active function groups becomes focus gradually, contains the dialkylphosphinic salts of active function groups, adds in the polymkeric substance; Can be through the form and the matrix resin blend of chemical bond; Improved the consistency between fire retardant and the resin, and in the material phase structure of fire retardant stability, avoided the additive flame retardant consistency poor, shortcoming such as be prone to ooze out, thereby flame retardant resistance, mechanical property, the thermotolerance of material all are improved.Publication number is that the patent of CN 101830926 discloses a kind of dialkylphosphinic salts, only needs less dosage, just can obtain flame retardant properties preferably, and it is applied to the fire-retardant of epoxide resin material, and application prospect is considerable in electronic apparatus industry.In the method for conventional synthetic phosphinates; The dialkylphosphinic salts that does not contain response type functional group such as hydroxyl, carboxyl, amido; Clariant company adopts is that yellow phosphorus or Hypophosporous Acid, 50 or phosphinates are starting raw material; Obtain through the addition reaction with alkene at HTHP, the ultimate aim product is the mixture that contains the dialkylphosphinic salts of monoalkyl phosphinates.Gram Lay benefactor department had announced the following functionalized dialkylphosphinic salts of mono carboxylic of structural formula with the vinyl esters of carboxylic acids preparation in 2011:
What adopt is that phospho acid are raw material, through twice addition reaction, obtains title product through steps such as reduction reactions again.Publication number is that method that the patent of CN 101830926 provides is to be the synthetic monoalkyl phosphoric acid esters of raw material with alkyl dichloro phosphine, carries out free radical reaction with alkene again and obtains the dialkyl phosphinic acid ester, at last through obtaining dialkylphosphinic salts with the Lewis acid reaction.But these method synthetic yields are not high, and complicated steps.
Summary of the invention
In order to solve prior art problems, the embodiment of the invention provides a kind of carboxylic methylpropanoic acid phosphinates fire retardant and preparation method thereof.Said technical scheme is following:
A kind of carboxylic methylpropanoic acid phosphinates fire retardant, its structural formula is following:
Wherein, M representes metal or NH
4 +, n representes the integer of 1-4.
Preferably, said M is the metal of second main group in the periodic table of elements, the 3rd main group, the Ge of the 4th main group, Sn, Pb, the As of the 5th main group, Sb, Bi, the Se of the 6th main group, Te; Or the Ti in the subgroup, V, Co, V, Cr, Cu, Ni, Fe, Zn, Cd; Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, In.
Preferred, said M is Mg, Al, Fe, Zn, Sn, Ti, Zr, Bi, Mn.
A kind of method for preparing above-mentioned carboxylic methylpropanoic acid phosphinates fire retardant, its step comprises: the first step, with 2-methyl-2,5-dioxy-1, the hydrolysis of 2-oxygen phospholane obtains methyl-prop acidic group phospho acid;
Second step, said methyl-prop acidic group phospho acid in the slightly acidic solvent, are reacted down at 50-100 ℃ with MOX or oxyhydroxide, promptly obtain said carboxylic methylpropanoic acid phosphinates fire retardant.
The first step reactive chemistry equation is following:
The second step reactive chemistry equation is following:
Preferably, said metal hydroxides is white lake, calcium hydroxide or ironic hydroxide, and said MOX is zinc oxide, quicklime, Cadmium oxide or Natural manganese dioxide.Most preferably be white lake.
Said the first step hydrolytic process is in water, acetone or the two mixture, to carry out.Preferably, the mol ratio of water and acetone is 5:3.
The temperature of said the first step hydrolysis reaction is 20-100 ℃, and the reaction times is 0.5-3 hour.Most preferred, temperature of reaction is 50 ℃, and the reaction times is 0.5 hour.
Preferably, the said second step temperature of reaction is 90 ℃, and the reaction times is 2 hours.
Said slightly acidic solvent is that Glacial acetic acid min. 99.5, PH are the alcohol of phosphoric acid buffer, the phenylformic acid aqueous solution or 1-7 the carbon atom of 5-6.Be preferably the phosphoric acid buffer that Glacial acetic acid min. 99.5 or PH are 5-6.Most preferably be Glacial acetic acid min. 99.5.
The beneficial effect that the technical scheme that the embodiment of the invention provides is brought is:
Carboxylic methylpropanoic acid phosphinates fire retardant provided by the invention; Can be through the form and the matrix resin blend of carboxyl chemical bond; Improved the consistency between fire retardant and the resin; And in the material phase structure of fire retardant stability, avoided the additive flame retardant consistency poor, shortcoming such as be prone to ooze out, thereby flame retardant resistance, mechanical property, the thermotolerance of material all are improved.Therefore only need less dosage, just can obtain flame retardant properties preferably, it is applied to the fire-retardant of epoxide resin material; 25% dosage (is example with aluminium salt) just can make the limiting oxygen index(LOI) of material reach 29.4, and testing vertical flammability reaches the V-0 level, and the carbon yield that product is 700 ℃ can reach 29.8%; The good mechanical property of its matrix material, color and luster is good, and smoke density is lower; The CTI value is higher, and application prospect is considerable in electronic apparatus industry.Simultaneously; The compound method of the carboxylic methylpropanoic acid phosphinates of the present invention fire retardant is with a kind of ring-type phosphoric anhydride 2-methyl-2; 5-dioxy-1,2-oxygen phospholane are initial phosphine source, through hydrolysis with in two-step reaction can obtain title product; Synthesis technique is simple, reaction conditions is gentle, productive rate is high, can arrive more than 95%.Solvent in the reaction and residue can reclaim, recycle, and environmentally safe is suitable for suitability for industrialized production.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, will combine specific embodiment that embodiment of the present invention is done to describe in detail further below.
Embodiment 1
The first step; With the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane are dissolved in the mixing solutions of 5mol water and 3mol acetone; 50 ℃ of following stirring and refluxing after about 0.5 hour; Be warming up to 70 ℃, after fractionation by distillation goes out the acetone and portion water in the mixed system, obtain methyl-prop acidic group phospho acid.
Second step; The above-mentioned methyl-prop acidic group phospho acid of 3mol and the white lake of 1mol are joined in the flask of the methyl alcohol that fills 3 times of volumes, after 2.5 hours, cool off in 80 ℃ of following stir abouts; Filter; Filter cake washs with glacial acetic acid, and vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid aluminium salt 1.
Embodiment 2
The first step, with the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane is dissolved in the 5mol water, and after about 1 hour, fractionation by distillation goes out the water in the mixed system 100 ℃ of following stirring and refluxing, obtains methyl-prop acidic group phospho acid.
Second step; The zinc oxide of the above-mentioned methyl-prop acidic group phospho acid of 2mol and 1mol is joined in the flask of phosphoric acid buffer that the PH that fills 3 times of volumes is 5-6, in 100 ℃ of following stirring and refluxing after about 2 hours, cooling; Filter; Filter cake washs with glacial acetic acid, and vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid zinc salt 2.
Embodiment 3
The first step, with the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane is dissolved in the 5mol acetone, and after 3 hours, fractionation by distillation goes out the acetone in the mixed system at 20 ℃ of following stir abouts, obtains methyl-prop acidic group phospho acid.
Second step; The above-mentioned methyl-prop acidic group phospho acid of 2mol and the calcium hydroxide of 1mol are joined in the flask of the phenylformic acid aqueous solution that fills 3 times of volumes, after about 3 hours, cool off in 50 ℃ of following stirring and refluxing; Filter; Filter cake washs with glacial acetic acid, and vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid calcium salt 3.
Embodiment 4
The first step; With the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane are dissolved in the mixing solutions of 5mol water and 3mol acetone; 50 ℃ of following stirring and refluxing after about 0.5 hour; Be warming up to 70 ℃, after fractionation by distillation goes out the acetone and portion water in the mixed system, obtain methyl-prop acidic group phospho acid.
Second step; The above-mentioned methyl-prop acidic group phospho acid of 2mol and the Cadmium oxide of 1mol are joined in the flask of the methyl alcohol that fills 3 times of volumes, after about 2 hours, cool off in 60 ℃ of following stirring and refluxing; Filter; Filter cake washs with glacial acetic acid, and vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid cadmium salt 4.
Embodiment 5
The first step; With the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane are dissolved in the mixing solutions of 5mol water and 3mol acetone; 50 ℃ of following stirring and refluxing after about 0.5 hour; Be warming up to 70 ℃, after fractionation by distillation goes out the acetone and portion water in the mixed system, obtain methyl-prop acidic group phospho acid.
In second step, the above-mentioned methyl-prop acidic group phospho acid of 4mol and the zirconium white of 1mol are joined in the flask of the enanthol that fills 3 times of volumes, in 100 ℃ of following stir abouts after 3 hours; Cooling is filtered, and filter cake washs with glacial acetic acid; Vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid zirconates 5.
Embodiment 6
The first step; With the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane are dissolved in the mixing solutions of 5mol water and 3mol acetone; 50 ℃ of following stirring and refluxing after about 0.5 hour; Be warming up to 70 ℃, after fractionation by distillation goes out the acetone and portion water in the mixed system, obtain methyl-prop acidic group phospho acid.
Second step; The above-mentioned methyl-prop acidic group phospho acid of 3mol and the ironic hydroxide of 1mol are joined in the flask of the n-hexyl alcohol that fills 3 times of volumes, after 3 hours, cool off in 80 ℃ of following stir abouts; Filter; Filter cake washs with glacial acetic acid, and vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid molysite 6.
Embodiment 7
The first step; With the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane are dissolved in the mixing solutions of 5mol water and 3mol acetone; 50 ℃ of following stirring and refluxing after about 0.5 hour; Be warming up to 70 ℃, after fractionation by distillation goes out the acetone and portion water in the mixed system, obtain methyl-prop acidic group phospho acid.
Second step; The above-mentioned methyl-prop acidic group phospho acid of 2mol and the Marinco H of 1mol are joined in the flask of the glacial acetic acid that fills 3 times of volumes, after 2 hours, cool off in 90 ℃ of following stir abouts; Filter; Filter cake washs with glacial acetic acid, and vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid magnesium salts 7.
Embodiment 8
The first step; With the 2-methyl-2 of 1mol, 5-dioxy-1,2-oxygen phospholane are dissolved in the mixing solutions of 5mol water and 3mol acetone; 50 ℃ of following stirring and refluxing after about 0.5 hour; Be warming up to 70 ℃, after fractionation by distillation goes out the acetone and portion water in the mixed system, obtain methyl-prop acidic group phospho acid.
Second step joined the above-mentioned methyl-prop acidic group phospho acid of 2mol and the iron protoxide of 1mol in the flask of the glacial acetic acid that fills 3 times of volumes, logical nitrogen protection; In 95 ℃ of following stir abouts after 4 hours; Cooling is filtered, and filter cake washs with glacial acetic acid; Vacuum-drying obtains said carboxylic methylpropanoic acid phospho acid ferrous salt 8.
Embodiment 9
Carboxylic methylpropanoic acid phospho acid aluminium salt 1 among the embodiment 1 with 25% addition (with respect to the mass percent of epoxy resin), is added in epoxy resin (EP)/diaminodiphenyl-methane (DDM) curing system.Because carboxyl can react with epoxide group, so fire retardant can not move from matrix material.Flame-proof composite material after the curing, limiting oxygen index(LOI) (LOI) reaches 29.4%, and UL94 reaches the V-0 rank, and the carbon yield that product is 700 ℃ is 29.81%.
Embodiment 10
Carboxylic methylpropanoic acid phospho acid zinc salt 2 among the embodiment 2 with 25% addition (with respect to the mass percent of epoxy resin), is added in epoxy resin (EP)/diaminodiphenyl-methane (DDM) curing system.Because carboxyl can react with epoxide group, so fire retardant can not move from matrix material.Flame-proof composite material after the curing, limiting oxygen index(LOI) (LOI) reaches 30.3%, and UL94 reaches the V-0 rank, and the carbon yield that product is 700 ℃ is 30.25%.
Embodiment 11
Carboxylic methylpropanoic acid phospho acid calcium salt 3 among the embodiment 3 with 25% addition (with respect to the mass percent of epoxy resin), is added in epoxy resin (EP)/diaminodiphenyl-methane (DDM) curing system.Because carboxyl can react with epoxide group, so fire retardant can not move from matrix material.Flame-proof composite material after the curing, limiting oxygen index(LOI) (LOI) reaches 29.4%, and UL94 reaches the V-0 rank, and the carbon yield that product is 700 ℃ is 28.66%.
Embodiment 12
Carboxylic methylpropanoic acid phospho acid molysite 6 among the embodiment 6 with 25% addition (with respect to the mass percent of epoxy resin), is added in epoxy resin (EP)/diaminodiphenyl-methane (DDM) curing system.Because carboxyl can react with epoxide group, so fire retardant can not move from matrix material.Flame-proof composite material after the curing, limiting oxygen index(LOI) (LOI) reaches 26.8%, and UL94 reaches the V-1 rank, and the carbon yield that product is 700 ℃ is 27.83%.
Embodiment 13
Carboxylic methylpropanoic acid phospho acid magnesium salts 7 among the embodiment 7 with 20% addition (with respect to the mass percent of epoxy resin), is added in epoxy resin (EP)/diaminodiphenyl-methane (DDM) curing system.Because carboxyl can react with epoxide group, so fire retardant can not move from matrix material.Flame-proof composite material after the curing, limiting oxygen index(LOI) (LOI) reaches 29.8%, and UL94 reaches the V-0 rank, and the carbon yield that product is 700 ℃ is 32.82%.
Embodiment 14
Carboxylic methylpropanoic acid phospho acid ferrous salt 8 among the embodiment 8 with 25% addition (with respect to the mass percent of epoxy resin), is added in epoxy resin (EP)/diaminodiphenyl-methane (DDM) curing system.Because carboxyl can react with epoxide group, so fire retardant can not move from matrix material.Flame-proof composite material after the curing, limiting oxygen index(LOI) (LOI) reaches 27.2%, and UL94 reaches the V-1 rank, and the carbon yield that product is 700 ℃ is 27.26%.
Need to prove: the foregoing description is just listed and is lifted the minority structure, and other structures those of ordinary skills can adopt that method can obtain corresponding construction among the embodiment, only have on the data and revise, and do not enumerate one by one.
The invention described above embodiment sequence number is not represented the quality of embodiment just to description.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. carboxylic methylpropanoic acid phosphinates fire retardant, its structure is that formula is following:
Wherein, M representes metal or NH
4 +, n representes the integer of 1-4.
2. according to the said carboxylic methylpropanoic acid phosphinates fire retardant of claim 1, it is characterized in that: said M is the metal of second main group in the periodic table of elements, the 3rd main group, the Ge of the 4th main group, Sn, Pb, the As of the 5th main group, Sb, Bi; The Se of the 6th main group, Te, or the Ti in the subgroup, V, Co, V, Cr, Cu; Ni, Fe, Zn, Cd, Y, Zr, Nb; Mo, Tc, Ru, Rh, Pd, Ag, In.
3. according to the said carboxylic methylpropanoic acid phosphinates fire retardant of claim 1, it is characterized in that: said M is Mg, Al, Fe, Zn, Sn, Ti, Zr, Bi, Mn.
4. method for preparing the described carboxylic methylpropanoic acid phosphinates fire retardant of claim 1 comprises:
The first step, with 2-methyl-2,5-dioxy-1, the hydrolysis of 2-oxygen phospholane obtains methyl-prop acidic group phospho acid;
Second step, said methyl-prop acidic group phospho acid in the slightly acidic solvent, are reacted down at 50-100 ℃ with MOX or oxyhydroxide, promptly obtain said carboxylic methylpropanoic acid phosphinates fire retardant.
5. method according to claim 4 is characterized in that: said metal hydroxides is white lake or ironic hydroxide, and said MOX is zinc oxide, quicklime, Cadmium oxide or Natural manganese dioxide.
6. method according to claim 4 is characterized in that: said the first step hydrolytic process is in water, acetone or the two mixture, to carry out.
7. method according to claim 4 is characterized in that: the temperature of said the first step hydrolysis reaction is 20-100 ℃, and the reaction times is 0.5-3 hour.
8. method according to claim 4 is characterized in that: the said second step temperature of reaction is 90 ℃, and the reaction times is 2 hours.
9. method according to claim 4 is characterized in that: said slightly acidic solvent is that Glacial acetic acid min. 99.5, PH are the alcohol of phosphoric acid buffer, the phenylformic acid aqueous solution or 1-7 the carbon atom of 5-6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788493A (en) * | 2015-03-26 | 2015-07-22 | 洪湖市一泰科技有限公司 | Preparation method for dialkyl phosphinic acid and salt thereof |
| CN108641091A (en) * | 2018-04-24 | 2018-10-12 | 利尔化学股份有限公司 | Poly- methyl hypophosphorous acid glycol ester aluminium salt and its preparation method and application |
| CN109400927A (en) * | 2018-10-17 | 2019-03-01 | 江汉大学 | High transparent and fire-retardant polyvinyl alcohol film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007070615A (en) * | 2005-08-11 | 2007-03-22 | Polyplastics Co | Flame-retardant resin composition |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070615A (en) * | 2005-08-11 | 2007-03-22 | Polyplastics Co | Flame-retardant resin composition |
Non-Patent Citations (1)
| Title |
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| 陈佳等: "《2012年中国阻燃学术年会论文集》", 6 May 2012 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788493A (en) * | 2015-03-26 | 2015-07-22 | 洪湖市一泰科技有限公司 | Preparation method for dialkyl phosphinic acid and salt thereof |
| CN108641091A (en) * | 2018-04-24 | 2018-10-12 | 利尔化学股份有限公司 | Poly- methyl hypophosphorous acid glycol ester aluminium salt and its preparation method and application |
| CN108641091B (en) * | 2018-04-24 | 2021-03-30 | 利尔化学股份有限公司 | Polymethyl ethylene glycol hypophosphite aluminum salt and preparation method and application thereof |
| CN109400927A (en) * | 2018-10-17 | 2019-03-01 | 江汉大学 | High transparent and fire-retardant polyvinyl alcohol film and preparation method thereof |
| CN109400927B (en) * | 2018-10-17 | 2021-07-27 | 江汉大学 | High-transparency flame-retardant polyvinyl alcohol film and preparation method thereof |
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