CN103172665B - Preparation method and application of dialkyl phosphinate with high density and large particle size - Google Patents
Preparation method and application of dialkyl phosphinate with high density and large particle size Download PDFInfo
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- CN103172665B CN103172665B CN201310061975.0A CN201310061975A CN103172665B CN 103172665 B CN103172665 B CN 103172665B CN 201310061975 A CN201310061975 A CN 201310061975A CN 103172665 B CN103172665 B CN 103172665B
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Abstract
The invention discloses a preparation method of dialkyl phosphinate with high density and large particle size. The preparation method comprises the following steps of: (a) stirring and mixing a mixture of a metallic compound and water with an alkaline solution to homogeneous phase; (b) reacting the metallic compound alkaline solution stirred and mixed to the homogeneous phase with dialkyl phosphinic acid and/or a dialkyl phosphinic acid alkali metal salt water solution; and (c) neutralizing by use of acid to obtain dialkyl phosphinic acid metal salt as shown in a formula (I), wherein R1 and R2 are same or different and are expressed as methyl, ethyl, propyl, butyl, amyl, cyclopentyl, cyclohexyl or octyl; M is Mg, Ca, Al, Fe, Zn, Sb, Sn, Ge, Ti, Zr or Sr; and m is 2-4. The dialkyl phosphinic acid metal salt obtained by preparation has the characteristics of high density and large particle size. The preparation method is simple in process and convenient to operate and can be used for preparing a fire retardant.
Description
Technical field
The invention belongs to fire-retardant FRW field, be specifically related to a kind of preparation method and application thereof of high-density Large stone dialkylphosphinic salts.
Background technology
The macromolecular materials such as plastics, rubber, chemical fibre are widely used in building trade, automotive industry, health care and household appliance technical field due to features such as light weight, inexpensive, acid-alkali-corrosive-resistings.But macromolecular material is usually inflammable or flammable, the requirement of real world applications to its flame retardant properties is more and more higher.In order to ensure the security that synthetic materials uses, and meet the requirement of environment protection, most effective means adds halogen-free flame retardants in synthetic materials.
Dialkylphosphinic salts has been proved to be a kind of halogen-free flame retardants efficiently and has been widely used in synthetic materials, and such flame retardant products has, and consumption is little, good mechanical property, color and luster are good, the features such as smoke density is low, have application prospect very much in electronic apparatus industry.But normally used dialkylphosphinic salts based flame retardant due to density low, particle diameter is little, easily causes this based flame retardant airborne dust in blanking process, contaminate environment, and product can be caused cannot to mix with resin, and then impact is added with the mechanical property of the material of this based flame retardant.
In order to solve the problem, German patent DE 0241376A1 adopts the method for shock compaction to improve the tap density of dialkylphosphinic salts based flame retardant to a certain extent, but this method wastes time and energy and is difficult to be accepted; German patent DE 0241375A1 improves the tap density of dialkylphosphinic salts based flame retardant to a great extent by melting method, but this method adds a large amount of wax and other subsidiary in the product, is unfavorable for the forming process of resin.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, an object of the present invention is the preparation method of the dialkylphosphinic salts providing a kind of high-density Large stone.
The present invention is achieved by the following technical solutions:
A preparation method for high-density Large stone dialkylphosphinic salts, comprises the steps:
A) mixture of metallic compound and water and strong base solution are uniformly mixed into the metallic compound strong base solution of homogeneous phase;
B) react being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt;
C) with acid neutralization, obtain as shown in formula I dialkyl metal phosphinate;
Wherein, R
1, R
2identical or different, be expressed as methyl, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group; M is Mg, Ca, Al, Fe, Zn, Sb, Sn, Ge, Ti, Zr or Sr; M is 2 ~ 4.
In described step a), strong base solution is selected from sodium hydroxide solution or potassium hydroxide solution.
In described step a), the concentration of strong base solution is 5% ~ 90%, is preferably 20% ~ 70%.
In described step a), metallic compound is selected from one or more mixtures of Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum oxide, aluminium hydroxide, ferric sulfate, iron nitrate, iron(ic) chloride, ironic acetate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, calcium sulfate, nitrocalcite, calcium chloride, lime acetate.
In described step a) metallic compound and water mixture in the mass percent of metallic compound be 10% ~ 100%, be preferably 20% ~ 50%.
In described step a), the mixture of metallic compound and water and the mol ratio of strong base solution are 1:1 ~ 1:10, are preferably 1:2 ~ 1:8.
In described step b), dialkyl phosphinic acid is selected from one or more mixtures of dimethylphosphinic acid, methylethyl phospho acid, diethyl phospho acid, butyl ethyl phospho acid, dipropyl phospho acid, methylpropylphosphinic acid, ethyl propyl phospho acid, butyl phospho acid, dibutyl phospho acid, is preferably dimethylphosphinic acid, diethyl phospho acid or dipropyl phospho acid.
In described step b), dialkyl phosphinic acid an alkali metal salt is selected from one or more mixtures of dimethylphosphinic acid sodium, methylethyl phospho acid sodium, diethyl phospho acid sodium, butyl ethyl phospho acid sodium, dipropyl phospho acid sodium, methylpropylphosphinic acid sodium, ethyl propyl phospho acid sodium, butyl phospho acid sodium, dibutyl phospho acid sodium, is preferably dimethylphosphinic acid sodium, diethyl phospho acid sodium or dipropyl phospho acid sodium.
The inventive method is prepared dialkyl phosphinic acid used and/or dialkyl phosphinic acid an alkali metal salt in dialkyl metal phosphinate process and is all obtained with reference to Chinese patent CN 102050835A synthesis.
In described step b), the mass concentration of dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt is 10% ~ 90%, is preferably 30% ~ 70%.
In described step b), the mixture of metallic compound and water and the mol ratio of dialkyl phosphinic acid and/or dialkyl phosphinic acid an alkali metal salt are 10:1 ~ 1:101:10 ~ 10:1; Be preferably 1:1 ~ 1:8.
Being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt temperature of reaction in described step b) is 0 ~ 150 DEG C, is preferably 70 ~ 100 DEG C.
Being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt reaction times in described step b) is 0.1 ~ 10h, is preferably 0.1 ~ 3h.
In described step b), dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and the metallic compound strong base solution being uniformly mixed into homogeneous phase react and refer to that dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln join in the metallic compound strong base solution being uniformly mixed into homogeneous phase and react; Or the strong base solution being uniformly mixed into homogeneous phase joins in dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and reacts; The strong base solution being preferably uniformly mixed into homogeneous phase joins in dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and reacts.
In described step c), acid is selected from one or more mixtures of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid, oxalic acid.
In described step c), the particle diameter of dialkyl metal phosphinate is 10 ~ 150 μm, is preferably 30 ~ 90 μm.
In described step c), the tap density of dialkyl metal phosphinate is 500 ~ 850g/L, is preferably 600 ~ 750g/L.
Residual moisture content 0.01 ~ the 10wt% of dialkyl metal phosphinate in described step c), is preferably 0.1 ~ 1wt%.
The invention also discloses the purposes that above-specified high density Large stone dialkylphosphinic salts is used as fire retardant.
The present invention compared with prior art, has following beneficial effect:
1) the dialkyl metal phosphinate density prepared of the method for the invention is high, and particle diameter is large, can solve such flame retardant products easily airborne dust, problem of not easily mixing with resin in the application.
2) the method for the invention only changes the order of addition(of ingredients) in building-up process, can obtain the dialkyl metal phosphinate of high-density Large stone, and this method technique is simple, easy to operate, greatly reduces production cost, simplifies production unit, improve production efficiency.
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.
In embodiment listed by the inventive method, dialkyl phosphinic acid used and/or dialkyl phosphinic acid an alkali metal salt all obtain with reference to Chinese patent CN 102050835A synthesis.
The tap density testing method of dialkyl metal phosphinate of the present invention measures with reference to GB5162 " mensuration of metal-powder tap density " method.
The size distribution testing method of dialkylphosphinic salts of the present invention measures with reference to GB/T 19077.1 " sreen analysis laser diffractometry " method.
The infrared absorption spectrum testing method of dialkylphosphinic salts of the present invention measures with reference to GB/T6040 " infrared spectrum analysis general rule " method.
embodiment 1: the preparation of dimethyl hypo-aluminum orthophosphate
By 666g mass percent be 20% Tai-Ace S 150 (M=666) and water mixture agitation condition under join in the sodium hydroxide solution of 96g 50%.Until both stir after, this metallic compound strong base solution is joined the 322.3g(1.2mol being heated to 150 DEG C in advance in 60min) in the dimethylphosphinic acid solution of 35%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid aluminium 119.8g, yield 97.9%, water ratio 0.2% for 200 DEG C;
Tap density (g/L): 705; Particle diameter (μm) distributes: D (10): 31.472; D (50): 62.713; D (90): 89.826;
IR：777 cm
-1，1076cm
-1，1150 cm
-1，2880cm
-1，2930 cm
-1。
embodiment 2: the preparation of dimethyl hypo-aluminum orthophosphate
Join under 34g aluminum acetate (M=204) solid agitation condition in the sodium hydroxide solution of 66.7g 30%.Until both stir after, this metallic compound strong base solution is joined the 470g(0.5mol being heated to 90 DEG C in advance in 0.1h) in the dimethylphosphinic acid solution of 10%; With acetic acid neutralization, generate white solid, cooling, filter, by 1L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid aluminium 49.7g, yield 97.5%, water ratio 0.2% for 200 DEG C;
Tap density (g/L): 739; Particle diameter (μm) distributes: D (10): 33.541; D (50): 63.472; D (90): 88.538;
IR：774 cm
-1，1075cm
-1，1152 cm
-1，2879cm
-1，2932 cm
-1。
embodiment 3: the preparation of dimethyl ferric hypophosphite
By 541.7g mass percent be 50% iron(ic) chloride (M=162.5) and water mixture agitation condition under join in the sodium hydroxide solution of 4000g 5%, until both stir after, this metallic compound strong base solution is joined the 522.2g(5mol being cooled to 0 DEG C in advance in 10h) in the dimethylphosphinic acid solution of 90%; With hydrochloric acid neutralization, generate white solid, cooling, filter, by 15L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid iron 537.1g, yield 96.2%, water ratio 0.4% for 200 DEG C;
Tap density (g/L): 682; Particle diameter (μm) distributes: D (10): 30.156; D (50): 69.147; D (90): 86.483;
IR：774cm
-1，1072 cm
-1，1146cm
-1，2878 cm
-1，2949 cm
-1。
embodiment 4: the preparation of dimethyl magnesium hypophosphite
By 1800g mass percent be 10% magnesium sulfate (M=120) and water mixture agitation condition under join in the sodium hydroxide solution of 133.3g 90%, until both stir after, this metallic compound strong base solution is joined the 402.9g(3mol being heated to 70 DEG C in advance in 3h) in the dimethylphosphinic acid solution of 70%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 10L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid magnesium 306.8g, yield 97.4%, water ratio 0.3% for 200 DEG C;
Tap density (g/L): 716; Particle diameter (μm) distributes: D (10): 34.510.; D (50): 65.173; D (90): 87.890;
IR：774cm
-1，1072 cm
-1，1150cm
-1，2881 cm
-1，2950 cm
-1。
embodiment 5: the preparation of dimethyl zinc hypophosphite
By 318.3g mass percent be 35% zinc sulfate (M=287.54) and water mixture agitation condition under join in the sodium hydroxide solution of 106.6g 30%, until both stir after, this metallic compound strong base solution is joined the 214.9g(0.8mol being heated to 90 DEG C in advance in 30min) in the dimethylphosphinic acid solution of 35%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid zinc 95.3g, yield 94.9%, water ratio 0.6% for 200 DEG C;
Tap density (g/L): 676; Particle diameter (μm) distributes: D (10): 29.142; D (50): 58.783; D (90): 86.471;
IR：776cm
-1，1082 cm
-1，1156cm
-1，2886cm
-1，2972cm
-1。
embodiment 6: the preparation of dimethyl calcium propionate
By 166.5g mass percent be 40% calcium chloride (M=111) and water mixture agitation condition under join in the sodium hydroxide solution of 120g 40%, until both stir after, this metallic compound strong base solution is joined the 376g(1.2mol being heated to 100 DEG C in advance in 30min) in the dimethylphosphinic acid solution of 30%; With hydrochloric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid calcium 118.4g, yield 87.3%, water ratio 0.6% for 200 DEG C;
Tap density (g/L): 659; Particle diameter (μm) distributes: D (10): 28.472; D (50): 66.379; D (90): 86.726;
IR：776cm
-1，1076 cm
-1，1158cm
-1，2889 cm
-1， 2959cm
-1。
embodiment 7: the preparation of aluminum diethylphosphinate
With embodiment 1, adopt diethyl phospho acid, by 222g mass percent be 60% Tai-Ace S 150 (M=666) and water mixture agitation condition under join in the sodium hydroxide solution of 96g 50%, until both stir after, this metallic compound strong base solution is joined the 488g(1.2mol being heated to 90 DEG C in advance in 20min) in the diethyl phospho acid solution of 30%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 152.1g, yield 97.5%, water ratio 0.2% for 200 DEG C;
Tap density (g/L): 725; Particle diameter (μm) distributes: D (10): 30.153; D (50): 60.287; D (90): 90.459;
IR：776cm
-1，1074 cm
-1，1151cm
-1，2881 cm
-1，2959 cm
-1。
embodiment 8: the preparation of aluminum diethylphosphinate
With embodiment 2, adopt diethyl phospho acid, by 340g mass percent be 20% aluminum acetate (M=204) and water mixture agitation condition under join in the sodium hydroxide solution of 200g 20%, until both stir after, this metallic compound strong base solution is joined the 244g(1mol being heated to 80 DEG C in advance in 50min) in the diethyl phospho acid solution of 50%; With acetic acid neutralization, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 125.3g, yield 96.4%, water ratio 0.4% for 200 DEG C;
Tap density (g/L): 745; Particle diameter (μm) distributes: D (10): 32.348; D (50): 63.562; D (90): 85.054;
IR：775cm
-1，1076cm
-1，1149 cm
-1，2880cm
-1， 2958 cm
-1。
embodiment 9: the preparation of diethyl phospho acid iron
With embodiment 3, adopt diethyl phospho acid, by 270.8g mass percent be 30% iron(ic) chloride (M=162.5) and water mixture agitation condition under join in the sodium hydroxide solution of 120g 50%, until both stir after, this metallic compound strong base solution is joined the 261.4g(1.5mol being heated to 50 DEG C in advance in 35min) in the diethyl phospho acid solution of 70%; With hydrochloric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain diethyl phospho acid iron 202.2g, yield 96.5%, water ratio 0.4% for 200 DEG C;
Tap density (g/L): 692; Particle diameter (μm) distributes: D (10): 31.562; D (50): 62.304; D (90): 91.892;
IR：776cm
-1，1046 cm
-1，1108cm
-1，2882 cm
-1，2940 cm
-1，2958 cm
-1。
embodiment 10: the preparation of diethyl phospho acid magnesium
With embodiment 4, adopt diethyl phospho acid, by 225g mass percent be 40% magnesium sulfate (M=120) and water mixture agitation condition under join in the sodium hydroxide solution of 300g 20%.Until both stir after, this metallic compound strong base solution is joined the 457.5g(1.5mol being heated to 110 DEG C in advance in 45min) in the diethyl phospho acid solution of 40%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain diethyl phospho acid magnesium 194.1g, yield 97.3%, water ratio 0.3% for 200 DEG C;
Tap density (g/L): 712; Particle diameter (μm) distributes: D (10): 33.671; D (50): 64.526; D (90): 90.735;
IR：774cm
-1，1088 cm
-1，1169cm
-1，2880 cm
-1，2939 cm
-1，2960 cm
-1。
embodiment 11: the preparation of diethyl phospho acid zinc
With embodiment 5, adopt diethyl phospho acid, by 255.6g mass percent be 45% zinc sulfate (M=287.54) and water mixture agitation condition under join in the sodium hydroxide solution of 106.7g 30%.Until both stir after, this metallic compound strong base solution is joined the 278.9g(0.8mol being heated to 70 DEG C in advance in 40min) in the diethyl phospho acid solution of 35%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain diethyl phospho acid zinc 116.9g, yield 95.2%, water ratio 0.5% for 200 DEG C;
Tap density (g/L): 680; Particle diameter (μm) distributes: D (10): 35.425; D (50): 57.814; D (90): 85.328;
IR：776cm
-1，1055 cm
-1，1133cm
-1，2880 cm
-1，2942 cm
-1，2973cm
-1。
embodiment 12: the preparation of diethyl phospho acid calcium
With embodiment 6, adopt diethyl phospho acid, by 185g mass percent be 30% calcium chloride (M=111) and water mixture agitation condition under join in the sodium hydroxide solution of 133.3g 30%, until both stir after, this metallic compound strong base solution is joined the 244g(1mol being heated to 90 DEG C in advance in 25min) in the diethyl phospho acid solution of 50%; With hydrochloric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain diethyl phospho acid calcium 124.9g, yield 88.6%, water ratio 0.6% for 200 DEG C;
Tap density (g/L): 663; Particle diameter (μm) distributes: D (10): 28.167; D (50): 68.835; D (90): 89.624;
IR：778cm
-1，1060 cm
-1，1108cm
-1，2882 cm
-1，2940cm
-1，2959cm
-1。
embodiment 13: the preparation of dipropyl phospho acid aluminium
With embodiment 1, adopt dipropyl phospho acid sodium, by 555g mass percent be 30% Tai-Ace S 150 (M=666) and water mixture agitation condition under join in the sodium hydroxide solution of 150g 40%, until both stir after, this metallic compound strong base solution is joined the 1290g(1.5mol being heated to 130 DEG C in advance in 20min) in the dipropyl phospho acid sodium solution of 20%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid aluminium 232.5g, yield 98.1%, water ratio 0.2% for 200 DEG C;
Tap density (g/L): 689; Particle diameter (μm) distributes: D (10): 30.204; D (50): 67.518; D (90): 90.459;
IR：776cm
-1，1070 cm
-1，1150cm
-1，2880 cm
-1，2989cm
-1。
embodiment 14: the preparation of dipropyl phospho acid aluminium
With embodiment 2, adopt dipropyl phospho acid sodium, by 340g mass percent be 20% aluminum acetate (M=204) and water mixture agitation condition under join in the sodium hydroxide solution of 100g 40%, until both stir after, this metallic compound strong base solution is joined the 860g(1mol being heated to 90 DEG C in advance in 40min) in the dipropyl phospho acid sodium solution of 20%; With acetic acid neutralization, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 125.8g, yield 96.8%, water ratio 0.3% for 200 DEG C;
Tap density (g/L): 745; Particle diameter (μm) distributes: D (10): 33.408; D (50): 65.851; D (90): 88.904;
IR：776cm
-1，1072cm
-1，1152 cm
-1，2880cm
-1，2992 cm
-1。
embodiment 15: the preparation of dipropyl phospho acid iron
With embodiment 3, adopt dipropyl phospho acid sodium, by 541.7g mass percent be 20% iron(ic) chloride (M=162.5) and water mixture agitation condition under join in the sodium hydroxide solution of 266.7g 30%, until both stir after, this metallic compound strong base solution is joined the 860g(2mol being heated to 75 DEG C in advance in 50min) in the dipropyl phospho acid sodium solution of 40%; With hydrochloric acid neutralization, generate white solid, cooling, filter, by 4L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid iron 322.6g, yield 96.2%, water ratio 0.5% for 200 DEG C;
Tap density (g/L): 645; Particle diameter (μm) distributes: D (10): 25.601; D (50): 58.987; D(90): 83.542;
IR：776cm
-1，1070 cm
-1，1151cm
-1，2881 cm
-1，2988cm
-1。
embodiment 16: the preparation of dipropyl phospho acid magnesium
With embodiment 4, adopt dipropyl phospho acid sodium, by 720g mass percent be 25% magnesium sulfate (M=120) and water mixture agitation condition under join in the sodium hydroxide solution of 342.9g 35%.Until both stir after, this metallic compound strong base solution is joined the 1474.3g(3mol being heated to 95 DEG C in advance in 80min) in the dipropyl phospho acid sodium solution of 35%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 6L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid magnesium 472.4g, yield 97.8%, water ratio 0.3% for 200 DEG C;
Tap density (g/L): 653; Particle diameter (μm) distributes: D (10): 35.879; D (50): 66.054; D(90): 89.156;
IR：770cm
-1，1069 cm
-1，1149cm
-1，2886 cm
-1，2980cm
-1。
embodiment 17: the preparation of dipropyl phospho acid zinc
With embodiment 5, adopt dipropyl phospho acid sodium, by 2396.2g mass percent be 30% zinc sulfate (M=287.54) and water mixture agitation condition under join in the sodium hydroxide solution of 400g 50%.Until both stir after, this metallic compound strong base solution is joined the 1720g(5mol being heated to 120 DEG C in advance in 150min) in the dipropyl phospho acid sodium solution of 50%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 10L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid zinc 878.5g, yield 96.8%, water ratio 0.4% for 200 DEG C;
Tap density (g/L): 658; Particle diameter (μm) distributes: D (10): 36.237; D (50): 59.154; D(90): 88.802;
IR：778cm
-1，1069 cm
-1，1152cm
-1，2881 cm
-1，2960cm
-1。
embodiment 18: the preparation of dipropyl phospho acid calcium
With embodiment 6, adopt dipropyl phospho acid sodium, by 860g mass percent be 20% calcium chloride (M=111) and water mixture agitation condition under join in the sodium hydroxide solution of 133.3g 30%, until both stir after, this metallic compound strong base solution is joined the 244g(1mol being heated to 90 DEG C in advance in 30min) in the diethyl phospho acid solution of 50%; With hydrochloric acid neutralization, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid calcium 152.9g, yield 90.5%, water ratio 0.4% for 200 DEG C;
Tap density (g/L): 646; Particle diameter (μm) distributes: D (10): 30.049; D (50): 69.348; D(90): 90.013;
IR：770cm
-1，1070cm
-1，1150cm
-1，2882cm
-1，2971cm
-1。
embodiment 19: the preparation of dimethylphosphinic acid aluminium
With embodiment 1, adopt dimethylphosphinic acid sodium, by 1480g mass percent be 30% Tai-Ace S 150 (M=666) and water mixture agitation condition under join in the potassium hydroxide solution of 800g 20%.Until both stir after, this metallic compound strong base solution is joined the 1546.7g(4mol being heated to 30 DEG C in advance in 120min) in the dimethylphosphinic acid sodium solution of 30%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 8L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid aluminium 401.9g, yield 98.5%, water ratio 0.1% for 200 DEG C;
Tap density (g/L): 750; Particle diameter (μm) distributes: D (10): 30.042; D (50): 59.158; D (90): 90.004;
IR：774 cm
-1，1075cm
-1，1153 cm
-1，2880cm
-1，2932 cm
-1。
embodiment 20: the preparation of aluminum diethylphosphinate
With embodiment 7, adopt diethyl phospho acid sodium, by 444g mass percent be 50% Tai-Ace S 150 (M=666) and water mixture agitation condition under join in the sodium hydroxide solution of 114.3g 70%.Until both stir after, this metallic compound strong base solution is joined the 960g(2mol being heated to 90 DEG C in advance in 60min) in the diethyl phospho acid sodium solution of 30%; With sulfuric acid neutralization, generate white solid, cooling, filter, by 4L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 246.5g, yield 94.8%, water ratio 1.0% for 200 DEG C;
Tap density (g/L): 600; Particle diameter (μm) distributes: D (10): 38.053; D (50): 70.303; D (90): 95.124.
IR： 776cm
-1, 1076cm
-1, 1149cm
-1, 2881 cm
-1, 2959 cm
-1
comparative example 1: the preparation of dimethyl hypo-aluminum orthophosphate
By 313.3g(1mol) the dimethylphosphinic acid solution of 30% is heated to 90 DEG C, neutralize with the sodium hydroxide solution of 100g 40%, drip the mixture that 370g mass percent is 30% Tai-Ace S 150 (M=666) and water in 30min, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain dimethylphosphinic acid aluminium 99.9g for 200 DEG C, yield 98.0%, water ratio 0.2%;
Tap density (g/L): 367; Particle diameter (μm) distributes: D (10): 10.782; D (50): 36.846; D (90): 67.338;
IR：776cm
-1，1075cm
-1，1152 cm
-1，2880cm
-1，2930 cm
-1。
comparative example 2: the preparation of diethyl hypo-aluminum orthophosphate
By 576g(2mol) the diethyl phospho acid sodium solution of 50% is heated to 90 DEG C, neutralize with the sodium hydroxide solution of 400g 20%, drip the mixture that 1110g mass percent is 20% Tai-Ace S 150 (M=666) and water in 80min, generate white solid, cooling, filter, by 4L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 255.6g for 200 DEG C, yield 98.3%, water ratio 0.2%;
Tap density (g/L): 385; Particle diameter (μm) distributes: D (10): 11.259; D (50): 40.186; D (90): 68.318;
IR：774cm
-1，1074cm
-1，1152cm
-1，2882 cm
-1，2960 cm
-1。
The dialkylphosphinic salts of embodiment 1 ~ 20 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, its combustionproperty and mechanical property are tested in sample preparation, record result and see table 1:
The moulding material combustionproperty that table 1 high-density Large stone 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 stretching of high-density Large stone dialkylphosphinic salts sample preparation prepared by preparation method of the present invention, bending and superior flame retardant property.
Claims (1)
1. a preparation method for high-density Large stone dialkylphosphinic salts, comprises the steps:
A) mixture of metallic compound and water and strong base solution are uniformly mixed into the metallic compound strong base solution of homogeneous phase;
B) react being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt;
C) with acid neutralization, obtain as shown in formula I dialkyl metal phosphinate;
Wherein, R
1, R
2identical or different, be expressed as methyl, ethyl, propyl group, butyl, amyl group, cyclopentyl, cyclohexyl or octyl group; M is Mg, Ca, Al, Fe, Zn, Sb, Sn, Ge, Ti, Zr or Sr; M is 2 ~ 4.
2, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step a), strong base solution is selected from sodium hydroxide solution or potassium hydroxide solution.
3, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step a), the mass concentration of strong base solution is 5% ~ 90%.
4, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 3, is characterized in that, in described step a), the mass concentration of strong base solution is 20% ~ 70%.
5, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, it is characterized in that, in described step a), metallic compound is selected from one or more mixtures of Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum oxide, aluminium hydroxide, ferric sulfate, iron nitrate, iron(ic) chloride, ironic acetate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium acetate, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, calcium sulfate, nitrocalcite, calcium chloride, lime acetate.
6, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step a) metallic compound and water mixture in the mass percent of metallic compound be 10% ~ 100%.
7, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 6, is characterized in that, in described step a) metallic compound and water mixture in the mass percent of metallic compound be 20% ~ 50%.
8, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step a), the mixture of metallic compound and water and the mol ratio of strong base solution are 1:1 ~ 1:10.
9, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 8, is characterized in that, in described step a), the mixture of metallic compound and water and the mol ratio of strong base solution are 1:2 ~ 1:8.
10, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, it is characterized in that, in described step b), dialkyl phosphinic acid is selected from one or more mixtures of dimethylphosphinic acid, methylethyl phospho acid, diethyl phospho acid, butyl ethyl phospho acid, dipropyl phospho acid, methylpropylphosphinic acid, ethyl propyl phospho acid, butyl phospho acid, dibutyl phospho acid.
11, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 10, is characterized in that, in described step b), dialkyl phosphinic acid is dimethylphosphinic acid, diethyl phospho acid or dipropyl phospho acid.
12, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, it is characterized in that, in described step b), dialkyl phosphinic acid an alkali metal salt is selected from one or more mixtures of dimethylphosphinic acid sodium, methylethyl phospho acid sodium, diethyl phospho acid sodium, butyl ethyl phospho acid sodium, dipropyl phospho acid sodium, methylpropylphosphinic acid sodium, ethyl propyl phospho acid sodium, butyl phospho acid sodium, dibutyl phospho acid sodium.
13, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 12, is characterized in that, in described step b), dialkyl phosphinic acid an alkali metal salt is dimethylphosphinic acid sodium, diethyl phospho acid sodium or dipropyl phospho acid sodium.
The dialkylphosphinic salts preparation method of the high-density Large stone 14, according to claim 1,10 or 12, is characterized in that, in described step b), the mass concentration of dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt is 10% ~ 90%.
15, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 14, is characterized in that, in described step b), the mass concentration of dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt is 30% ~ 70%.
16, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, it is characterized in that, in described step b), the mixture of metallic compound and water and the mol ratio of dialkyl phosphinic acid and/or dialkyl phosphinic acid an alkali metal salt are 10:1 ~ 1:10.
17, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 16, is characterized in that, in described step b), the mixture of metallic compound and water and the mol ratio of dialkyl phosphinic acid and/or dialkyl phosphinic acid an alkali metal salt are
1:1~1:8。
18, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, it is characterized in that, being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt temperature of reaction in described step b) is 0 ~ 150 DEG C.
19, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 18, it is characterized in that, being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt temperature of reaction in described step b) is 70 ~ 100 DEG C.
20, the size controlling method of dialkylphosphinic salts according to claim 1, it is characterized in that, being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt reaction times in described step b) is 0.1 ~ 10h.
21, the size controlling method of dialkylphosphinic salts according to claim 20, it is characterized in that, being uniformly mixed into the metallic compound strong base solution of homogeneous phase and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt reaction times in described step b) is 0.1 ~ 3h.
22, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, it is characterized in that, in described step b), dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and the metallic compound strong base solution being uniformly mixed into homogeneous phase react and refer to that dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln join in the metallic compound strong base solution being uniformly mixed into homogeneous phase and react; Or the metallic compound strong base solution being uniformly mixed into homogeneous phase joins in dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and reacts.
23, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 22, it is characterized in that, in described step b), dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and the metallic compound strong base solution being uniformly mixed into homogeneous phase react and refer to that the metallic compound strong base solution being uniformly mixed into homogeneous phase joins in dialkyl phosphinic acid and/or dialkyl phosphinic acid alkali metal salt soln and react.
24, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step c), acid is selected from one or more mixtures of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid, oxalic acid.
25, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step c), the particle diameter of dialkyl metal phosphinate is 10 ~ 150 μm.
26, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 25, is characterized in that, in described step c), the particle diameter of dialkyl metal phosphinate is 30 ~ 90 μm.
27, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, in described step c), the tap density of dialkyl metal phosphinate is 500 ~ 850g/L.
28, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 27, is characterized in that, in described step c), the tap density of dialkyl metal phosphinate is 600 ~ 750g/L.
29, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 1, is characterized in that, the residual moisture content 0.01 ~ 10wt% of dialkyl metal phosphinate in described step c).
30, the dialkylphosphinic salts preparation method of high-density Large stone according to claim 29, is characterized in that, in described step c), the residual moisture content of dialkyl metal phosphinate is 0.1 ~ 1wt%.
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| DE102016213280B4 (en) | 2016-07-20 | 2024-03-07 | Clariant International Ltd | Diorganylphosphinic acid salts, a process for their preparation and their use |
| KR20200062336A (en) | 2017-10-17 | 2020-06-03 | 셀라니즈 세일즈 저머니 게엠베하 | Flame retardant polyamide composition |
| CN109879909B (en) * | 2019-03-07 | 2021-10-01 | 清远市普塞呋磷化学有限公司 | Preparation method of dialkyl phosphinate with large particle size |
| CN111320781B (en) * | 2020-03-13 | 2021-09-07 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280583A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing salts of dialkylphosphinic acids |
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
| 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 |
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