CN104059101B - A kind of dialkylphosphinic salts with good free-running property - Google Patents
A kind of dialkylphosphinic salts with good free-running property Download PDFInfo
- Publication number
- CN104059101B CN104059101B CN201410251925.3A CN201410251925A CN104059101B CN 104059101 B CN104059101 B CN 104059101B CN 201410251925 A CN201410251925 A CN 201410251925A CN 104059101 B CN104059101 B CN 104059101B
- Authority
- CN
- China
- Prior art keywords
- solution
- sodium
- dialkylphosphinic salts
- running property
- phosphinic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Abstract
The invention discloses a kind of dialkylphosphinic salts with good free-running property, slope of repose is 20
°~ 40
°, preparation method comprises step: a) adding in dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and help crystallizing agent, obtaining dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt containing helping crystallizing agent; B) mixture of metallic compound and water and reacting containing the dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt that help crystallizing agent of obtaining are generated dialkylphosphinic salts.The present invention is good by adding the dialkylphosphinic salts free-running property helping crystallizing agent to prepare, and its slope of repose can reach 20
°~ 40
°, this based flame retardant free-running property in resin can be solved from root poor, the problem of skewness.
Description
The application is the patent No. is 201310061973.1, and the applying date is 2013.02.27, and invention and created name is the divisional application of " a kind of preparation method with the dialkylphosphinic salts of good free-running property ".
Technical field
The invention belongs to fire-retardant FRW technical field, be specifically related to a kind of dialkylphosphinic salts with good free-running property.
Background technology
Macromolecular material (plastics, rubber, chemical fibre etc.) is widely used in building trade, automotive industry, health care and household appliance technical field.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, but normally used dialkylphosphinic salts based flame retardant free-running property is poor, when this kind of not easily wandering solid is added resin, the distribution of this based flame retardant in resin can be affected, and then cause Flame Retardancy to decline.And in some industry, particularly microelectronic industry, require that product flame retardant properties when 0.4mm still can reach UL94 V-0 rank, this just requires that the resin used has excellent free-running property, and this just significantly limit the application of resin in microelectronics industry of the dialkylphosphinic salts based flame retardant being added with such free-running property difference.
US Patent No. 0021676A1 discloses a kind of method improving dialkylphosphinic salts free-running property, this method is by Mg, Al, Ca, Ti, the mixing of the dialkylphosphinic salts of Zn or Na, metallic soap compound and metallic compound, obtains free-running property higher when being comparatively used alone a kind of dialkyl metal phosphinate.
US Patent No. 0025643A1 reports equally by dialkyl phosphinic acid aluminium and the mixing of dialkyl phosphinic acid zinc, obtains free-running property higher when being comparatively used alone dialkyl phosphinic acid aluminium.
The defect that aforesaid method exists is: only when this based flame retardant is applied to resin, by various dialkyl metal phosphinate interworking being made for improving the free-running property of fire retardant in resin, do not solve such dialkylphosphinic salts free-running property from source poor, the problem of skewness in resin; The interworking of various dialkyl metal phosphinate uses complex operation, implements complicated, to improving the free-running property of this based flame retardant in resin and distribution problem has little significance.
Summary of the invention
In order to overcome the problem of existing dialkylphosphinic salts free-running property difference, the object of the present invention is to provide a kind of dialkylphosphinic salts with good free-running property.
The present invention is achieved through the following technical solutions:
There is a preparation method for the dialkylphosphinic salts of good free-running property, comprise the following steps:
A) adding in dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and help crystallizing agent, obtaining dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt containing helping crystallizing agent;
B) just metallic compound and water mixture with obtain react containing the dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt that help crystallizing agent the dialkylphosphinic salts generated as shown in formula I;
Wherein, crystallizing agent is helped to be that positively charged ion helps crystallizing agent, anionic retention aid crystallizing agent, nonionic to help crystallizing agent and/or zwitter-ion to help crystallizing agent described in;
Wherein,
R
1, R
2identical or different, be straight or branched C1-C6 alkyl;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn, is preferably Ca, Al, Mg, Fe or Zn;
M is 2 to 4.
Described positively charged ion helps crystallizing agent to be oronain, Morpan BB, cetylpyridinium chloride or brocide; Described anionic retention aid crystallizing agent is sodium stearate, sodium polyacrylate, sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or dioctyl succinate disulfonate acid; Described nonionic helps crystallizing agent to be polysorbate compounds, polyoxyethylene fatty acid ester compounds, polyoxyethylene aliphatic alcohol ether class or Pluronic F68; Described zwitter-ion helps crystallizing agent to be Yelkin TTS, amino acid or betaine type compound.
Of the present inventionly help crystallizing agent preferably sodium stearate, sodium polyacrylate, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, more preferably sodium polyacrylate or sodium laurylsulfonate.
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.
Describedly help crystallizing agent with the quality of dialkyl phosphinic acid or dialkyl phosphinic acid aqueous solution of alkali metal salt for benchmark, its massfraction is 0.1% ~ 50%, preferably 1% ~ 10%.
In step a), the mass concentration of described dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt is 10% ~ 90%, preferably 30% ~ 70%.
In step b), 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 step b), in the mixture of described metallic compound and water, the mass percent of metallic compound is 10% ~ 100%, preferably 20% ~ 50%.
Mol ratio 10:1 ~ the 1:10 of the mixture of described metallic compound and water and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt, preferred 1:1 ~ 1:8.
In step b), the temperature of reaction of the mixture of described metallic compound and water and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt is 0 ~ 150 DEG C, preferably 70 ~ 100 DEG C.
In step b), the reaction times of the mixture of described metallic compound and water and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt is 0.1 ~ 10h, preferably 0.1 ~ 1h.
In step b), the mixture of described metallic compound and water reacts containing helping the dialkyl phosphinic acid of crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt to join in the mixture of metallic compound and water with containing helping the dialkyl phosphinic acid of crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt to react to refer to, or the mixture of metallic compound and water joins and reacts containing helping in the dialkyl phosphinic acid of crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt; The mixture being preferably metallic compound and water joins and reacts containing helping in the dialkyl phosphinic acid of crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt.
In step b), the residual moisture content of described dialkylphosphinic salts is 0.01 ~ 10wt%, preferably 0.1 ~ 1% wt%.
In step b), the slope of repose of described dialkylphosphinic salts is 20
°~ 40
°, preferably 25
°~ 35
°.
In step b), the particle diameter of described dialkylphosphinic salts is 1 ~ 100 μm.
In step b), the tap density of described dialkylphosphinic salts is 500 ~ 800g/L, preferably 600 ~ 800g/L.
The dialkylphosphinic salts that the present invention prepares is used as fire retardant, can be used in PBT, prepare high performance flame-proofed polymer material in PA, PET, PC, PS etc.
The present invention compared with prior art, has following beneficial effect:
The present invention is good by adding the dialkylphosphinic salts free-running property helping crystallizing agent to prepare, and its slope of repose can reach 20
°~ 40
°, this based flame retardant free-running property in resin can be solved from root poor, the problem of skewness.
The inventive 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 concrete embodiment of the present invention, but embodiments of the present invention are 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 method that the present invention evaluates dialkylphosphinic salts free-running property is the horn cupping that stops, spatula horn cupping, take-off rate method, intensity of compression method and/or aggegation degree method.For the horn cupping that stops, its evaluation method pours powder sample into funnel, and sample is dropped on the round flat board that lower radius is r by funnel, and powder is piled up gradually, till can not continuing heap height.Measure powder piling height h, calculate slope of repose α by formula (1)
tgα=h/r （1）
α is less, and powder free-running property is better.It is generally acknowledged that α is less than 30 °, powder can unrestricted flow; α is between 30 ° to 40 °, and powder can meet processing request; But α is more than 40 °, powder is just difficult to meet processing request.
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 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
By 480g(1.0mol) the diethyl phospho acid sodium solution of 30% is heated to 90 DEG C, add the sodium polyacrylate solution of 0.1% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 277.5g mass percent in 45 minutes is the Tai-Ace S 150 (M=666) of 40% and the mixture of water, generates white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 124.8g for 200 DEG C, yield 96.0%, water ratio 0.6%.
Tap density (g/L): 600; Slope of repose: 38 °
IR： 778cm
-1, 1076 cm
-1, 1151cm
-1, 2881 cm
-1, 2959 cm
-1
embodiment 2
Aluminum diethylphosphinate is prepared with embodiment 1, by 308.6g(1.5mol) the diethyl phospho acid sodium solution of 70% is heated to 150 DEG C, add the sodium polyacrylate solution of 0.5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 832.5g mass percent in 70 minutes is the Tai-Ace S 150 (M=666) of 20% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 188.2g, yield 96.5%, water ratio 0.6%.
Tap density (g/L): 605; Slope of repose: 35 °
embodiment 3
Aluminum diethylphosphinate is prepared with embodiment 1, by 493.7g(1.2mol) the diethyl phospho acid sodium solution of 35% is cooled to 0 DEG C, add the sodium polyacrylate solution of 1% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 333g mass percent in 45 minutes is the Tai-Ace S 150 (M=666) of 40% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 150.1g, yield 96.2%, water ratio 0.6%.
Tap density (g/L): 615; Slope of repose: 32 °
embodiment 4
Aluminum diethylphosphinate is prepared with embodiment 1, by 360g(1.0mol) the diethyl phospho acid sodium solution of 40% is heated to 70 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 555g mass percent in 65 minutes is the Tai-Ace S 150 (M=666) of 20% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 126.8g, yield 97.5%, water ratio 0.4%.
Tap density (g/L): 670; Slope of repose: 25 °
embodiment 5
Aluminum diethylphosphinate is prepared with embodiment 1, by 1152g(0.8mol) the diethyl phospho acid sodium solution of 10% is heated to 80 DEG C, and add the sodium polyacrylate solution of 10% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), in 0.1 hour, add 88.8g Tai-Ace S 150 (M=666) solid, generate white solid, cooling, filters, precipitates with 2L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 99.3g, yield 95.5%, water ratio 0.9%.
Tap density (g/L): 630; Slope of repose: 31 °
embodiment 6
Aluminum diethylphosphinate is prepared with embodiment 1, by 384g(0.8mol) the diethyl phospho acid sodium solution of 30% is heated to 100 DEG C, add the sodium polyacrylate solution of 25% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 177.6g mass percent in 30 minutes is the Tai-Ace S 150 (M=666) of 50% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 98.3g, yield 94.5%, water ratio 1.1%.
Tap density (g/L): 600; Slope of repose: 37 °
embodiment 7
Aluminum diethylphosphinate is prepared with embodiment 1, by 320g(2.0mol) the diethyl phospho acid sodium solution of 90% is heated to 50 DEG C, add the sodium polyacrylate solution of 50% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 2220g mass percent in 10 hours is the Tai-Ace S 150 (M=666) of 10% and the mixture of water, generate white solid, cooling, filter, precipitate with 4L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 243.4g, yield 93.6%, water ratio 1.3%.
Tap density (g/L): 590; Slope of repose: 41 °
embodiment 8
Aluminum diethylphosphinate is prepared with embodiment 1, crystallizing agent is helped to adopt sodium laurylsulfonate, by 480g(1.0mol) the diethyl phospho acid sodium solution of 30% is heated to 120 DEG C, add the sodium dodecyl sulfate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 370g mass percent in 40 minutes is the Tai-Ace S 150 (M=666) of 30% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 125.3g, yield 96.4%, water ratio 0.5%.
Tap density (g/L): 660; Slope of repose: 27 °
embodiment 9
Aluminum diethylphosphinate is prepared with embodiment 1, crystallizing agent is helped to adopt sodium stearate, by 230.4g(0.8mol) the diethyl phospho acid sodium solution of 50% is heated to 90 DEG C, add the sodium stearate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 444g mass percent in 65 minutes is the Tai-Ace S 150 (M=666) of 20% and the mixture of water, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain aluminum diethylphosphinate 99.8g for 200 DEG C, yield 96.0%, water ratio 0.6%.
Tap density (g/L): 640; Slope of repose: 30 °
embodiment 10
Aluminum diethylphosphinate is prepared with embodiment 1, crystallizing agent is helped to adopt sodium lauryl sulphate, by 480g(1.0mol) the diethyl phospho acid sodium solution of 30% is heated to 60 DEG C, add the sodium dodecyl sulfate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 277.5g mass percent in 30 minutes is the Tai-Ace S 150 (M=666) of 40% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtained aluminum diethylphosphinate 126.1g, yield 97.0%, water ratio 0.5%.
Tap density (g/L): 660; Slope of repose: 26 °
embodiment 11
Aluminum diethylphosphinate is prepared with embodiment 1, crystallizing agent is helped to adopt Sodium dodecylbenzene sulfonate, by 493.7g(1.2mol) the diethyl phospho acid sodium solution of 35% is heated to 100 DEG C, add the Sodium dodecylbenzene sulfonate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 380.6g mass percent in 50 minutes is the Tai-Ace S 150 (M=666) of 35% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtained aluminum diethylphosphinate 148.2g, yield 95.0%, water ratio 0.9%.
Tap density (g/L): 620; Slope of repose: 31 °
embodiment 12
Prepare diethyl phospho acid zinc, the metallic compound aqueous solution adopts zinc sulfate solution, by 192g(0.4mol) the diethyl phospho acid sodium solution of 30% is heated to 90 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 191.7g mass percent in 30min is the zinc sulfate (M=287.54) of 30% and the mixture of water, generate white solid, cooling, filter, precipitate with 1L deionized water wash, dry 10h for 200 DEG C, obtain diethyl phospho acid zinc 58.9g, yield 96.0%, water ratio 0.6%.
Tap density (g/L): 685; Slope of repose: 27 °
IR： 776cm
-1, 1056 cm
-1, 1133cm
-1, 2882 cm
-1, 2942 cm
-1, 2972cm
-1
embodiment 13
Prepare diethyl phospho acid calcium, the metallic compound aqueous solution adopts calcium chloride water, by 493.7g(1.2mol) the diethyl phospho acid sodium solution of 35% is heated to 75 DEG C, add the sodium stearate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 190.3g mass percent in 30min is the calcium chloride (M=111) of 35% and the mixture of water, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain diethyl phospho acid calcium 153.1g for 200 DEG C, yield 90.5%, water ratio 0.6%.
Tap density (g/L): 655; Slope of repose: 30 °
IR： 776cm
-1, 1060 cm
-1, 1108cm
-1, 2880 cm
-1, 2940cm
-1, 2960cm
-1
embodiment 14
Prepare diethyl phospho acid iron, the metallic compound aqueous solution adopts ferric chloride in aqueous solution, by 2160g(3mol) the diethyl phospho acid sodium solution of 20% is heated to 60 DEG C, add the sodium dodecyl sulfate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 270.8g mass percent in 45min is the iron(ic) chloride (M=162.5) of 60% and the mixture of water, generate white solid, cooling, filter, precipitate with 6L deionized water wash, dry 10h for 200 DEG C, obtain diethyl phospho acid iron 403.1g, yield 96.2%, water ratio 0.5%.
Tap density (g/L): 658; Slope of repose: 31 °
IR： 776cm
-1, 1045 cm
-1, 1108cm
-1, 2880 cm
-1, 2940 cm
-1, 2960cm
-1
embodiment 15
Prepare diethyl phospho acid magnesium, the metallic compound aqueous solution adopts magnesium sulfate solution, by 493.7g(1.2mol) the diethyl phospho acid sodium solution of 35% is heated to 95 DEG C, add the Sodium dodecylbenzene sulfonate solution of 5% massfraction (with the quality of diethyl sodium hypophosphite solution for benchmark), dripping 205.7g mass percent in 30min is the magnesium sulfate (M=120) of 35% and the mixture of water, generate white solid, cooling, filter, precipitate with 3L deionized water wash, dry 10h for 200 DEG C, obtain diethyl phospho acid magnesium 155.5g, yield 97.4%, water ratio 0.3%.
Tap density (g/L): 676; Slope of repose: 28 °
IR： 776cm
-1, 1088 cm
-1, 1170cm
-1, 2880 cm
-1, 2940 cm
-1, 2959 cm
-1
embodiment 16
Prepare diethyl phospho acid magnesium, adopt diethyl phospho acid, by 244g(1mol) the diethyl phospho acid solution of 50% is heated to 90 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of diethyl Hypophosporous Acid, 50 solution for benchmark), dripping 300g mass percent in 30min is the magnesium sulfate (M=120) of 20% and the mixture of water, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain diethyl phospho acid magnesium 129.0g for 200 DEG C, yield 97.0%, water ratio 0.4%.
Tap density (g/L): 668; Slope of repose: 29 °
embodiment 17
Prepare dimethylphosphinic acid aluminium, adopt dimethylphosphinic acid, by 235g(1mol) the dimethylphosphinic acid solution of 40% is heated to 95 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of dimethyl Hypophosporous Acid, 50 solution for benchmark), neutralize with alkali, dripping 370g mass percent in 35min is the Tai-Ace S 150 (M=666) of 30% and the mixture of water, generate white solid, cooling, filters, precipitates with 2L deionized water wash, dry 10h for 200 DEG C, obtain dimethylphosphinic acid aluminium 99.1g, yield 97.2%, water ratio 0.4%.
Tap density (g/L): 667; Slope of repose: 30 °
IR： 776 cm
-1, 1076cm
-1, 1150 cm
-1, 2879 cm
-1, 2930 cm
-1
embodiment 18
Prepare dimethylphosphinic acid zinc, adopt dimethylphosphinic acid, by 805.7g(3mol) the dimethylphosphinic acid solution of 35% is heated to 90 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of dimethylphosphinic acid solution for benchmark), neutralize with alkali, dripping 1232.3g mass percent in 100min is the zinc sulfate (M=287.54) of 35% and the mixture of water, generate white solid, cooling, filters, precipitates with 6L deionized water wash, dry 10h for 200 DEG C, obtain dimethylphosphinic acid zinc 362.9g, yield 96.4%, water ratio 0.5%.
Tap density (g/L): 680; Slope of repose: 28 °
IR： 776cm
-1, 1081 cm
-1, 1156cm
-1, 2886cm
-1, 2971cm
-1
embodiment 19
Prepare dimethylphosphinic acid calcium, adopt dimethylphosphinic acid, by 313.3g(1mol) the dimethylphosphinic acid solution of 30% is heated to 80 DEG C, add the sodium stearate solution of 5% massfraction (with the quality of dimethylphosphinic acid solution for benchmark), neutralize with alkali, dripping 185g mass percent in 15min is the calcium chloride (M=111) of 30% and the mixture of water, generate white solid, cooling, filters, precipitates with 2L deionized water wash, dry 10h for 200 DEG C, obtain dimethylphosphinic acid calcium 100.5g, yield 88.9%, water ratio 0.6%.
Tap density (g/L): 650; Slope of repose: 31 °
IR： 777cm
-1, 1076 cm
-1, 1158cm
-1, 2888 cm
-1, 2960cm
-1
embodiment 20
Prepare dimethylphosphinic acid magnesium, adopt dimethylphosphinic acid, by 2350g(5mol) the dimethylphosphinic acid solution of 20% is heated to 110 DEG C, add the sodium dodecyl sulfate solution of 5% massfraction (with the quality of dimethylphosphinic acid solution for benchmark), neutralize with alkali, dripping 750g mass percent in 70min is the magnesium sulfate (M=120) of 40% and the mixture of water, generate white solid, cooling, filters, precipitates with 10L deionized water wash, dry 10h for 200 DEG C, obtain dimethylphosphinic acid magnesium 510.8g, yield 97.3%, water ratio 0.3%.
Tap density (g/L): 653; Slope of repose: 33 °
IR： 776cm
-1, 1072 cm
-1, 1149cm
-1, 2881 cm
-1, 2952 cm
-1
embodiment 21
Prepare dimethylphosphinic acid iron, adopt dimethylphosphinic acid, by 537.1g(2mol) the dimethylphosphinic acid solution of 35% is heated to 130 DEG C, add the Sodium dodecylbenzene sulfonate solution of 5% massfraction (with the quality of dimethylphosphinic acid solution for benchmark), neutralize with alkali, dripping 309.5g mass percent in 25min is the iron(ic) chloride (M=162.5) of 35% and the mixture of water, generate white solid, cooling, filters, precipitates with 4L deionized water wash, dry 10h for 200 DEG C, obtain dimethylphosphinic acid iron 216.2g, yield 96.8%, water ratio 0.5%.
Tap density (g/L): 670; Slope of repose: 30 °
IR： 776cm
-1, 1072 cm
-1, 1145cm
-1, 2878 cm
-1, 2950 cm
-1
embodiment 22
Prepare dipropyl phospho acid aluminium, adopt dipropyl phospho acid sodium, by 1290g(1.5mol) the dipropyl phospho acid sodium solution of 20% is heated to 55 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of dipropyl phospho acid sodium solution for benchmark), dripping 555g mass percent in 50min is the Tai-Ace S 150 (M=666) of 30% and the mixture of water, generate white solid, cooling, filter, by 3L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid aluminium 232.5g for 200 DEG C, yield 98.1%, water ratio 0.2%.
Tap density (g/L): 675; Slope of repose: 30 °
IR： 775cm
-1, 1070 cm
-1, 1150cm
-1, 2882 cm
-1, 2989cm
-1
embodiment 23
Prepare dipropyl phospho acid zinc, adopt dipropyl phospho acid sodium, by 1720g(5mol) the dipropyl phospho acid sodium solution of 50% is heated to 85 DEG C, add the sodium polyacrylate solution of 5% massfraction (with the quality of dipropyl phospho acid sodium solution for benchmark), dripping 2396.2g mass percent in 150min is the zinc sulfate (M=287.54) of 30% and the mixture of water, generate white solid, cooling, filter, by 10L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid zinc 878.5g for 200 DEG C, yield 96.8%, water ratio 0.4%.
Tap density (g/L): 690; Slope of repose: 27 °
IR： 778cm
-1, 1069 cm
-1, 1152cm
-1, 2881 cm
-1, 2960cm
-1
embodiment 24
Prepare dipropyl phospho acid calcium, adopt dipropyl phospho acid sodium, by 860g(1mol) the dipropyl phospho acid sodium solution of 20% is heated to 90 DEG C, add the sodium stearate solution of 5% massfraction (with the quality of dipropyl phospho acid sodium solution for benchmark), dripping 185g mass percent in 15min is the calcium chloride (M=111) of 30% and the mixture of water, generate white solid, cooling, filter, by 2L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid calcium 152.9g for 200 DEG C, yield 90.5%, water ratio 0.4%.
Tap density (g/L): 667; Slope of repose: 29 °
IR： 776cm
-1, 1059 cm
-1, 1108cm
-1, 2880 cm
-1, 2940cm
-1, 2960cm
-1
embodiment 25
Prepare dipropyl phospho acid magnesium, adopt dipropyl phospho acid sodium, by 1474.3g(3mol) the dipropyl phospho acid sodium solution of 35% is heated to 60 DEG C, add the sodium dodecyl sulfate solution of 5% massfraction (with the quality of dipropyl phospho acid sodium solution for benchmark), dripping 720g mass percent in 70min is the magnesium sulfate (M=120) of 25% and the mixture of water, generate white solid, cooling, filter, by 6L deionized water wash precipitation, dry 10h, obtain dipropyl phospho acid magnesium 472.4g for 200 DEG C, yield 97.8%, water ratio 0.3%.
Tap density (g/L): 665; Slope of repose: 30 °
IR： 770cm
-1, 1070cm
-1, 1150cm
-1, 2886 cm
-1, 2978cm
-1
embodiment 26
Prepare dipropyl phospho acid iron, adopt dipropyl phospho acid sodium, by 860g(2mol) the dipropyl phospho acid sodium solution of 40% is heated to 40 DEG C, add the Sodium dodecylbenzene sulfonate solution of 5% massfraction (with the quality of dipropyl phospho acid sodium solution for benchmark), dripping 541.7g mass percent in 50min is the iron(ic) chloride (M=162.5) of 20% and the mixture of water, generate white solid, cooling, filter, by 4L deionized water wash precipitation, dry 20h, obtain dipropyl phospho acid iron 322.6g for 180 DEG C, yield 96.2%, water ratio 0.5%.
Tap density (g/L): 680; Slope of repose: 28 °
IR： 774cm
-1, 1072 cm
-1, 1151cm
-1, 2881 cm
-1, 2988cm
-1
comparative example 1
By 493.7g(1.2mol) the diethyl phospho acid sodium solution of 35% is heated to 90 DEG C, dripping 380.6g mass percent in 60min is the Tai-Ace S 150 (M=666) of 35% and the mixture of water, generate white solid, cooling, filters, precipitates with 3L deionized water wash, dry 10h for 200 DEG C, obtain aluminum diethylphosphinate 147.9g, yield 94.8%, water ratio 1 %.
Tap density (g/L): 580; Slope of repose: 42 °
embodiment 27
The dialkyl metal phosphinate of embodiment 1 ~ 26 and comparative example 1 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 as shown in table 1:
Table 1
each performance test is undertaken by following standard:
Tensile strength: GB1040-1992 plastic tensile method for testing performance;
Flexural strength: GB9341-2000 Plastics-Oetermination of flexural properties method;
Amount of deflection: GB9341-2000 Plastics-Oetermination of flexural properties method;
Combustionproperty: UL94 Plastics Combustion performance test;
From upper table 1, the moulding material that dialkylphosphinic salts prepared by preparation method of the present invention obtains stretches, bending and superior flame retardant property, is applicable to make polymer in-mold moulding material.
Claims (6)
1. the dialkylphosphinic salts with good free-running property shown in following formula I,
Wherein,
R
1, R
2identical or different, be straight or branched C1-C6 alkyl;
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn;
M is 2 to 4;
The slope of repose of described dialkylphosphinic salts is 25 ° ~ 35 °.
2. the dialkylphosphinic salts with good free-running property according to claim 1, is characterized in that, the residual moisture content of described dialkylphosphinic salts is 0.01 ~ 10wt%.
3. the dialkylphosphinic salts with good free-running property according to claim 2, is characterized in that, the residual moisture content of described dialkylphosphinic salts is 0.1 ~ 1 wt%.
4. the dialkylphosphinic salts with good free-running property according to claim 1, is characterized in that, the particle diameter of described dialkylphosphinic salts is 1 ~ 100 μm.
5. the dialkylphosphinic salts with good free-running property according to claim 1, is characterized in that, the tap density of described dialkylphosphinic salts is 500 ~ 800g/L.
6. the dialkylphosphinic salts with good free-running property according to claim 5, is characterized in that, the tap density of described dialkylphosphinic salts is 600 ~ 800g/L.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310061973.1A CN103172664B (en) | 2013-02-27 | 2013-02-27 | Preparation method of dialkylphosphinate with excellent flowing property |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310061973.1A Division CN103172664B (en) | 2013-02-27 | 2013-02-27 | Preparation method of dialkylphosphinate with excellent flowing property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059101A CN104059101A (en) | 2014-09-24 |
| CN104059101B true CN104059101B (en) | 2015-09-09 |
Family
ID=48632915
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310061973.1A Expired - Fee Related CN103172664B (en) | 2013-02-27 | 2013-02-27 | Preparation method of dialkylphosphinate with excellent flowing property |
| CN201410251925.3A Ceased CN104059101B (en) | 2013-02-27 | 2013-02-27 | A kind of dialkylphosphinic salts with good free-running property |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310061973.1A Expired - Fee Related CN103172664B (en) | 2013-02-27 | 2013-02-27 | Preparation method of dialkylphosphinate with excellent flowing property |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN103172664B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951700B (en) * | 2014-05-15 | 2016-06-29 | 江苏利思德新材料有限公司 | Preparation method of a kind of dimethyl hypophosphites and products thereof and application |
| DE102016213280B4 (en) * | 2016-07-20 | 2024-03-07 | Clariant International Ltd | Diorganylphosphinic acid salts, a process for their preparation and their use |
| CN107828207B (en) | 2016-09-15 | 2020-12-25 | 科莱恩塑料和涂料有限公司 | Flame retardant-stabilizer combinations for thermoplastic polymers |
| CN107828084A (en) | 2016-09-15 | 2018-03-23 | 科莱恩塑料和涂料有限公司 | Fire retardant combination of stabilizers for thermoplastic polymer |
| CN106632464B (en) * | 2016-11-21 | 2019-07-02 | 浙江传化华洋化工有限公司 | A kind of preparation method and application of big partial size spherical shape dialkylphosphinic salts |
| CN107141511B (en) * | 2017-05-25 | 2019-07-12 | 广州铂钡信息科技有限公司 | A kind of additive and preparation method thereof for polymer |
| CN111315810A (en) | 2017-10-17 | 2020-06-19 | 塞拉尼斯销售德国有限公司 | 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 |
| CN111808133B (en) * | 2020-06-23 | 2023-05-02 | 浙江新化化工股份有限公司 | Diethyl phosphinate aluminum material and preparation method thereof |
| CN114478625B (en) * | 2022-03-10 | 2022-11-25 | 江苏利思德新材料股份有限公司 | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application thereof |
| CN114806249A (en) * | 2022-04-12 | 2022-07-29 | 广州龙文建材有限公司 | Building fireproof coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2311675C (en) * | 1997-11-28 | 2009-03-17 | Clariant Gmbh | Method for producing salts of dialkylphosphinic acids |
| ATE427976T1 (en) * | 2005-12-01 | 2009-04-15 | Supresta Llc | FLAME-RESISTANT COMPOSITIONS CONTAINING MIXTURES OF DISUBSTITUTED PHOSPHINATE SALTS AND MONOSUBTITUTED PHOSPHINATE SALTS |
| DE102006010352A1 (en) * | 2006-03-07 | 2007-09-13 | Clariant International Limited | Mixtures of mono-carboxyl-functionalized dialkylphosphinic salts and other components, a process for their preparation and use |
-
2013
- 2013-02-27 CN CN201310061973.1A patent/CN103172664B/en not_active Expired - Fee Related
- 2013-02-27 CN CN201410251925.3A patent/CN104059101B/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103172664B (en) | 2015-04-08 |
| CN103172664A (en) | 2013-06-26 |
| CN104059101A (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104059101B (en) | A kind of dialkylphosphinic salts with good free-running property | |
| CN103172663B (en) | A kind of preparation method of dialkyl metal phosphinate | |
| CN103102367B (en) | Preparation method and application of dialkyl phosphinate with high density and large diameter | |
| CN103172667B (en) | A kind of size controlling method of dialkylphosphinic salts and application thereof | |
| CN104371142A (en) | Additive composition for polymer, preparation method of additive composition and flame-retardant thermoplastic polymer molding material by using additive composition | |
| CN103951700B (en) | Preparation method of a kind of dimethyl hypophosphites and products thereof and application | |
| CN103172666B (en) | The preparation method of the dialkylphosphinic salts that a kind of thermostability is high | |
| CN106674598A (en) | Preparation method for efficient modified layered double-hydroxide flame retardant additive | |
| CN104448453B (en) | The preparation method of the low cigarette of a kind of halogen acidylate, fire-retardant powder styrene butadiene rubber | |
| US9982195B2 (en) | Flame retardant, flame retardant composition and shaped body | |
| CN105085988A (en) | Additive composition for polymers, preparation method of additive composition and flame-retardant thermoplastic polymer molding material containing additive composition | |
| CN105061500A (en) | Superfine particle size dialkylphosphinate, preparation method and applications thereof, and high polymer composition comprising dialkylphosphinate | |
| CN103172665B (en) | Preparation method and application of dialkyl phosphinate with high density and large particle size | |
| CN104693237A (en) | Preparing method for dialkyl phosphinate salt | |
| WO2021139073A1 (en) | Organophosphorus compound flame retardant, and preparation method therefor and application thereof | |
| JP7012334B2 (en) | Hydrotalcite compounds, resin compositions containing the hydrotalcite compounds, and molded articles thereof. | |
| CN105646938A (en) | Additive composition for polymers, preparation method thereof and flame-retardant thermoplastic polymer molding material composed of same | |
| CN106633187A (en) | Safe and environment-friendly inorganic aluminum hypophosphite flame retardant and application thereof in PBT (polybutylene terephthalate) | |
| CN104448452A (en) | Preparation method of halogenated acylated, low-smoke and flame retardant powdered styrene butadiene rubber | |
| CN103102508B (en) | Nano organic metal phosphonate flame retardant and preparation method thereof | |
| CN107141511B (en) | A kind of additive and preparation method thereof for polymer | |
| CN105504346A (en) | Preparation method of novel zinc borate flame-retardant material | |
| CN110294862B (en) | Preparation method of nano-hybrid tin-based smoke suppressant | |
| CN112210123A (en) | Preparation method of low-cost coated flame-retardant smoke suppressant | |
| CN105271149B (en) | Nano hybridization fire retardant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 510520 Guangdong Province, Guangzhou high tech Industrial Development Zone, No. 31 Southern China Science City Ke Feng Lu new materials innovation park building G1 No. 1005 Patentee after: Guangzhou Kingsky Material Co., Ltd. Address before: Science City Moon road high tech Development Zone in Guangzhou City, Guangdong province 510520 Integrated Services Building No. 80 Guangzhou science and technology innovation base Patentee before: Guangzhou Kingsky Material Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150909 Termination date: 20200227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| IW01 | Full invalidation of patent right |
Decision date of declaring invalidation: 20161031 Decision number of declaring invalidation: 30366 Granted publication date: 20150909 |
|
| IW01 | Full invalidation of patent right |