CN103172664A - Preparation method of dialkylphosphinate with excellent flowing property - Google Patents
Preparation method of dialkylphosphinate with excellent flowing property Download PDFInfo
- Publication number
- CN103172664A CN103172664A CN2013100619731A CN201310061973A CN103172664A CN 103172664 A CN103172664 A CN 103172664A CN 2013100619731 A CN2013100619731 A CN 2013100619731A CN 201310061973 A CN201310061973 A CN 201310061973A CN 103172664 A CN103172664 A CN 103172664A
- Authority
- CN
- China
- Prior art keywords
- phosphinic acid
- dialkyl phosphinic
- preparation
- sodium
- crystallizing agent
- 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.)
- Granted
Links
Abstract
The invention discloses a preparation method of dialkylphosphinate with an excellent flowing property. The preparation method comprises the following steps of: (a) adding an auxiliary crystallizing agent into a dialkylphosphinate and/or dialkylphosphinate alkali metal water solution to obtain the dialkylphosphinate and/or dialkylphosphinate alkali metal water solution containing the auxiliary crystallizing agent; and (b) reacting a mixture of metal compounds and water with the obtained dialkylphosphinate and/or dialkylphosphinate alkali metal water solution containing the auxiliary crystallizing agent to generate dialkylphosphinate. The dialkylphosphinate prepared by adding the auxiliary crystallizing agent is good in flowing property, and a repose angle of dialkylphosphinate can reach 20-40 degrees, thus the problems of poor flowing property and nonuniform distribution of fire retardants in resin can be fundamentally solved. The method disclosed by the invention is simple in process and convenient to operate, the production cost is greatly reduced, the production equipment is simplified, and the production efficiency is improved.
Description
Technical field
The invention belongs to the fire retardant synthesis technical field, be specifically related to a kind of preparation method with dialkylphosphinic salts of 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, and real world applications is more and more higher to the requirement of its flame retardant properties.The security of using in order to ensure synthetic materials, and satisfy the requirement of environment protection, effective means is to add halogen-free flame retardants in synthetic materials.
Dialkylphosphinic salts has been proved to be a kind of efficient halogen-free flame retardants and has been widely used in synthetic materials, but normally used dialkylphosphinic salts based flame retardant free-running property is poor, when the difficult wandering solid of this class is added resin, can affect the distribution of this based flame retardant in resin, and then cause Flame Retardancy to descend.And in some industry, particularly miniature electronic industry, require product flame retardant properties when 0.4mm still can reach UL94 V-0 rank, this has good free-running property with regard to the resin that requires to use, and this has just limited the application of resin in microelectronics industry that is added with the poor dialkylphosphinic salts based flame retardant of such free-running property greatly.
US Patent No. 0021676A1 discloses a kind of method that improves the dialkylphosphinic salts free-running property, this method is with Mg, Al, Ca, Ti, the dialkylphosphinic salts of Zn or Na, metallic soap compound and metallic compound mix, higher free-running property when having obtained to be used alone dialkyl metal phosphinate.
US Patent No. 0025643A1 reported equally dialkyl phosphinic acid aluminium and dialkyl phosphinic acid zinc mixed, higher free-running property when having obtained to use more separately dialkyl phosphinic acid aluminium.
The defective that aforesaid method exists is: only when this based flame retardant is applied to resin, by various dialkyl metal phosphinate interworkings are made to improve the free-running property of fire retardant in resin, do not solve such dialkylphosphinic salts free-running property from the source poor, the problem of skewness in resin; The interworking of various dialkyl metal phosphinates is used complex operation, implements complexity, has little significance to improving free-running property and the distribution problem of this based flame retardant in resin.
Summary of the invention
In order to overcome the poor problem of existing dialkylphosphinic salts free-running property, the object of the present invention is to provide a kind of preparation method with dialkylphosphinic salts of good free-running property.
Another object of the present invention is to dialkylphosphinic salts that aforesaid method prepares as the purposes of fire retardant.
The present invention is achieved through the following technical solutions:
A kind of preparation method with dialkylphosphinic salts of good free-running property comprises the following steps:
A) add in dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and help crystallizing agent, obtain containing the dialkyl phosphinic acid and/or the dialkyl phosphinic acid aqueous solution of alkali metal salt that help crystallizing agent;
B) just the mixture of metallic compound and water reacts with the contain dialkyl phosphinic acid and/or the dialkyl phosphinic acid aqueous solution of alkali metal salt that help crystallizing agent that obtain the dialkylphosphinic salts that generates as shown in formula I;
Wherein, the described crystallizing agent that helps is 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;
Wherein,
R
1, R
2Identical or different, be straight or branched C1-C6 alkyl;
M is Mg, Ca, and Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr or Mn are preferably Ca, Al, Mg, Fe or Zn;
M is 2 to 4.
It is oronain, Morpan BB, cetylpyridinium chloride or brocide that described positively charged ion helps crystallizing agent; 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 sodium sulfosuccinate; It is polysorbate compounds, polyoxyethylene fatty acid ester compounds, polyoxyethylene aliphatic alcohol ether class or Pluronic F68 that described nonionic helps crystallizing agent; It is Yelkin TTS, amino acid or betaine type compound that described zwitter-ion helps crystallizing agent.
Crystallizing agent preferably sodium stearate, sodium polyacrylate, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, more preferably sodium polyacrylate or the sodium laurylsulfonate of helping of the present invention.
The inventive method prepares in the dialkyl metal phosphinate process dialkyl phosphinic acid used and/or the dialkyl phosphinic acid an alkali metal salt all obtains with reference to Chinese patent CN 102050835A is synthetic.
The described crystallizing agent that helps is take the quality of dialkyl phosphinic acid or dialkyl phosphinic acid aqueous solution of alkali metal salt as benchmark, and its massfraction is 0.1% ~ 50%, and preferred 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%, preferred 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, sal epsom, 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%, preferred 20% ~ 50%.
The mol ratio 10:1 of the mixture of described metallic compound and water and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt ~ 1:10, 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 ℃, preferred 70 ~ 100 ℃.
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, preferred 0.1 ~ 1h.
In step b), the mixture of described metallic compound and water refers to contain in the mixture that the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt join metallic compound and water and reacts with containing the reaction of the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt, or the mixture of metallic compound and water joins to contain in the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and reacts; The mixture that is preferably metallic compound and water joins to contain in the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and reacts.
In step b), the residual moisture content of described dialkylphosphinic salts is 0.01 ~ 10wt%, preferred 0.1 ~ 1% wt%.
In step b), the slope of repose of described dialkylphosphinic salts is 20
°~ 40
°, preferred 25
°~ 35
°
In step b), the particle diameter of described dialkylphosphinic salts is 1 ~ 100 μ m.
In step b), the tap density of described dialkylphosphinic salts is 500 ~ 800g/L, preferred 600 ~ 800g/L.
The dialkylphosphinic salts that the present invention prepares can be used in PBT as fire retardant, prepares 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 by adding the dialkylphosphinic salts free-running property that helps crystallizing agent to prepare good, and its slope of repose can reach 20
°~ 40
°, can solve this based flame retardant free-running property resin from root poor, the problem of skewness.
The inventive method technique is simple, and is easy to operate, greatly reduces production cost, simplified production unit, improved 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 not subjected to the restriction of following embodiment.
In the listed embodiment of 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 is synthetic.
The method that the present invention estimates the 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.Take the horn cupping that stops as example, its evaluation method is to pour powder sample into funnel, and making sample drop on the below radius by funnel is that on the round flat board of r, powder is piled up gradually, until till can not continuing to pile height.Measure powder piling height h, by formula (1) calculates slope of repose α
tgα=h/r （1）
α is less, and the powder free-running property is better.It is generally acknowledged α less than 30 °, powder can unrestricted flow; α is between 30 ° to 40 °, and powder can satisfy processing request; But α surpasses 40 °, and powder just is difficult to satisfy processing request.
The tap density testing method of dialkyl metal phosphinate of the present invention is measured with reference to GB5162 " mensuration of metal-powder tap density " method.
The infrared absorption spectrum testing method of dialkylphosphinic salts of the present invention is measured with reference to GB/T6040 " infrared spectrum analysis general rule " method.
Embodiment 1
With 480g(1.0mol) 30% diethyl phospho acid sodium solution is heated to 90 ℃, the sodium polyacrylate solution that adds 0.1% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 277.5g mass percent in 45 minutes and be 40% Tai-Ace S 150 (M=666) and the mixture of water, the generation white solid, cooling, filter, with 3L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain diethyl phospho acid aluminium 124.8g, 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
With embodiment 1 preparation diethyl phospho acid aluminium, with 308.6g(1.5mol) 70% diethyl phospho acid sodium solution is heated to 150 ℃, the sodium polyacrylate solution that adds 0.5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 832.5g mass percent in 70 minutes and be 20% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 188.2g, yield 96.5%, water ratio 0.6%.
Tap density (g/L): 605; Slope of repose: 35 °
Embodiment 3
With embodiment 1 preparation diethyl phospho acid aluminium, with 493.7g(1.2mol) 35% diethyl phospho acid sodium solution is cooled to 0 ℃, the sodium polyacrylate solution that adds 1% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 333g mass percent in 45 minutes and be 40% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 150.1g, yield 96.2%, water ratio 0.6%.
Tap density (g/L): 615; Slope of repose: 32 °
Embodiment 4
With embodiment 1 preparation diethyl phospho acid aluminium, with 360g(1.0mol) 40% diethyl phospho acid sodium solution is heated to 70 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 555g mass percent in 65 minutes and be 20% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 126.8g, yield 97.5%, water ratio 0.4%.
Tap density (g/L): 670; Slope of repose: 25 °
Embodiment 5
With embodiment 1 preparation diethyl phospho acid aluminium, with 1152g(0.8mol) 10% diethyl phospho acid sodium solution is heated to 80 ℃, adds the sodium polyacrylate solution of 10% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), adds 88.8g Tai-Ace S 150 (M=666) solid in 0.1 hour, generate white solid, cooling, filter, with 2L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 99.3g, yield 95.5%, water ratio 0.9%.
Tap density (g/L): 630; Slope of repose: 31 °
Embodiment 6
With embodiment 1 preparation diethyl phospho acid aluminium, with 384g(0.8mol) 30% diethyl phospho acid sodium solution is heated to 100 ℃, the sodium polyacrylate solution that adds 25% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 177.6g mass percent in 30 minutes and be 50% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 98.3g, yield 94.5%, water ratio 1.1%.
Tap density (g/L): 600; Slope of repose: 37 °
Embodiment 7
With embodiment 1 preparation diethyl phospho acid aluminium, with 320g(2.0mol) 90% diethyl phospho acid sodium solution is heated to 50 ℃, the sodium polyacrylate solution that adds 50% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 2220g mass percent in 10 hours and be 10% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 4L deionized water wash, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 243.4g, yield 93.6%, water ratio 1.3%.
Tap density (g/L): 590; Slope of repose: 41 °
Embodiment 8
with embodiment 1 preparation diethyl phospho acid aluminium, help crystallizing agent to adopt sodium laurylsulfonate, with 480g(1.0mol) 30% diethyl phospho acid sodium solution is heated to 120 ℃, the sodium dodecyl sulfate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 370g mass percent in 40 minutes and be 30% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 125.3g, yield 96.4%, water ratio 0.5%.
Tap density (g/L): 660; Slope of repose: 27 °
Embodiment 9
With embodiment 1 preparation diethyl phospho acid aluminium, help crystallizing agent to adopt sodium stearate, with 230.4g(0.8mol) 50% diethyl phospho acid sodium solution is heated to 90 ℃, the sodium stearate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 444g mass percent in 65 minutes and be 20% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, with 2L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain diethyl phospho acid aluminium 99.8g, yield 96.0%, water ratio 0.6%.
Tap density (g/L): 640; Slope of repose: 30 °
Embodiment 10
with embodiment 1 preparation diethyl phospho acid aluminium, help crystallizing agent to adopt sodium lauryl sulphate, with 480g(1.0mol) 30% diethyl phospho acid sodium solution is heated to 60 ℃, the sodium dodecyl sulfate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 277.5g mass percent in 30 minutes and be 40% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, make diethyl phospho acid aluminium 126.1g, yield 97.0%, water ratio 0.5%.
Tap density (g/L): 660; Slope of repose: 26 °
Embodiment 11
with embodiment 1 preparation diethyl phospho acid aluminium, help crystallizing agent to adopt Sodium dodecylbenzene sulfonate, with 493.7g(1.2mol) 35% diethyl phospho acid sodium solution is heated to 100 ℃, the Sodium dodecylbenzene sulfonate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 380.6g mass percent in 50 minutes and be 35% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, make diethyl phospho acid aluminium 148.2g, yield 95.0%, water ratio 0.9%.
Tap density (g/L): 620; Slope of repose: 31 °
Embodiment 12
preparation diethyl phospho acid zinc, the metallic compound aqueous solution adopts zinc sulfate solution, with 192g(0.4mol) 30% diethyl phospho acid sodium solution is heated to 90 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 191.7g mass percent in 30min and be 30% zinc sulfate (M=287.54) and the mixture of water, generate white solid, cooling, filter, precipitate with the 1L deionized water wash, 200 ℃ of oven dry 10h, 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
Preparation diethyl phospho acid calcium, the metallic compound aqueous solution adopts calcium chloride water, with 493.7g(1.2mol) 35% diethyl phospho acid sodium solution is heated to 75 ℃, the sodium stearate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 190.3g mass percent in 30min and be 35% calcium chloride (M=111) and the mixture of water, generate white solid, cooling, filter, with 2L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain diethyl phospho acid calcium 153.1g, 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
preparation diethyl phospho acid iron, the metallic compound aqueous solution adopts ferric chloride in aqueous solution, with 2160g(3mol) 20% diethyl phospho acid sodium solution is heated to 60 ℃, the sodium dodecyl sulfate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 270.8g mass percent in 45min and be 60% iron(ic) chloride (M=162.5) and the mixture of water, generate white solid, cooling, filter, precipitate with the 6L deionized water wash, 200 ℃ of oven dry 10h, 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
preparation diethyl phospho acid magnesium, the metallic compound aqueous solution adopts magnesium sulfate solution, with 493.7g(1.2mol) 35% diethyl phospho acid sodium solution is heated to 95 ℃, the Sodium dodecylbenzene sulfonate solution that adds 5% massfraction (take the quality of diethyl sodium hypophosphite solution as benchmark), drip the 205.7g mass percent in 30min and be 35% sal epsom (M=120) and the mixture of water, generate white solid, cooling, filter, precipitate with the 3L deionized water wash, 200 ℃ of oven dry 10h, 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
Preparation diethyl phospho acid magnesium, adopt the diethyl phospho acid, with 244g(1mol) 50% diethyl phospho acid solution is heated to 90 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of diethyl Hypophosporous Acid, 50 solution as benchmark), drip the 300g mass percent in 30min and be 20% sal epsom (M=120) and the mixture of water, generate white solid, cooling, filter, with 3L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain diethyl phospho acid magnesium 129.0g, yield 97.0%, water ratio 0.4%.
Tap density (g/L): 668; Slope of repose: 29 °
Embodiment 17
Preparation dimethyl phospho acid aluminium, adopt the dimethyl phospho acid, with 235g(1mol) 40% dimethyl phospho acid solution is heated to 95 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of dimethyl Hypophosporous Acid, 50 solution as benchmark), neutralize with alkali, drip the 370g mass percent in 35min and be 30% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, with 2L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain dimethyl phospho 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
Preparation dimethyl phospho acid zinc, adopt the dimethyl phospho acid, with 805.7g(3mol) 35% dimethyl phospho acid solution is heated to 90 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of dimethyl phospho acid solution as benchmark), neutralize with alkali, drip the 1232.3g mass percent in 100min and be 35% zinc sulfate (M=287.54) and the mixture of water, generate white solid, cooling, filter, with 6L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain dimethyl phospho 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
Preparation dimethyl phospho acid calcium, adopt the dimethyl phospho acid, with 313.3g(1mol) 30% dimethyl phospho acid solution is heated to 80 ℃, the sodium stearate solution that adds 5% massfraction (take the quality of dimethyl phospho acid solution as benchmark), neutralize with alkali, drip the 185g mass percent in 15min and be 30% calcium chloride (M=111) and the mixture of water, generate white solid, cooling, filter, with 2L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain dimethyl phospho 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
Preparation dimethyl phospho acid magnesium, adopt the dimethyl phospho acid, with 2350g(5mol) 20% dimethyl phospho acid solution is heated to 110 ℃, the sodium dodecyl sulfate solution that adds 5% massfraction (take the quality of dimethyl phospho acid solution as benchmark), neutralize with alkali, drip the 750g mass percent in 70min and be 40% sal epsom (M=120) and the mixture of water, generate white solid, cooling, filter, with 10L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain dimethyl phospho 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
Preparation dimethyl phospho acid iron, adopt the dimethyl phospho acid, with 537.1g(2mol) 35% dimethyl phospho acid solution is heated to 130 ℃, the Sodium dodecylbenzene sulfonate solution that adds 5% massfraction (take the quality of dimethyl phospho acid solution as benchmark), neutralize with alkali, drip the 309.5g mass percent in 25min and be 35% iron(ic) chloride (M=162.5) and the mixture of water, generate white solid, cooling, filter, with 4L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain dimethyl phospho 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
Preparation dipropyl phospho acid aluminium, adopt dipropyl phospho acid sodium, with 1290g(1.5mol) 20% dipropyl phospho acid sodium solution is heated to 55 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of dipropyl phospho acid sodium solution as benchmark), drip the 555g mass percent in 50min and be 30% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, with 3L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain dipropyl phospho acid aluminium 232.5g, 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
Preparation dipropyl phospho acid zinc, adopt dipropyl phospho acid sodium, with 1720g(5mol) 50% dipropyl phospho acid sodium solution is heated to 85 ℃, the sodium polyacrylate solution that adds 5% massfraction (take the quality of dipropyl phospho acid sodium solution as benchmark), drip the 2396.2g mass percent in 150min and be 30% zinc sulfate (M=287.54) and the mixture of water, generate white solid, cooling, filter, with 10L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain dipropyl phospho acid zinc 878.5g, 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
Preparation dipropyl phospho acid calcium, adopt dipropyl phospho acid sodium, with 860g(1mol) 20% dipropyl phospho acid sodium solution is heated to 90 ℃, the sodium stearate solution that adds 5% massfraction (take the quality of dipropyl phospho acid sodium solution as benchmark), drip the 185g mass percent in 15min and be 30% calcium chloride (M=111) and the mixture of water, generate white solid, cooling, filter, with 2L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain dipropyl phospho acid calcium 152.9g, 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
Preparation dipropyl phospho acid magnesium, adopt dipropyl phospho acid sodium, with 1474.3g(3mol) 35% dipropyl phospho acid sodium solution is heated to 60 ℃, the sodium dodecyl sulfate solution that adds 5% massfraction (take the quality of dipropyl phospho acid sodium solution as benchmark), drip the 720g mass percent in 70min and be 25% sal epsom (M=120) and the mixture of water, generate white solid, cooling, filter, with 6L deionized water wash precipitation, 200 ℃ of oven dry 10h obtain dipropyl phospho acid magnesium 472.4g, 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
Preparation dipropyl phospho acid iron, adopt dipropyl phospho acid sodium, with 860g(2mol) 40% dipropyl phospho acid sodium solution is heated to 40 ℃, the Sodium dodecylbenzene sulfonate solution that adds 5% massfraction (take the quality of dipropyl phospho acid sodium solution as benchmark), drip the 541.7g mass percent in 50min and be 20% iron(ic) chloride (M=162.5) and the mixture of water, generate white solid, cooling, filter, with 4L deionized water wash precipitation, 180 ℃ of oven dry 20h obtain dipropyl phospho acid iron 322.6g, 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 Examples 1
With 493.7g(1.2mol) 35% diethyl phospho acid sodium solution is heated to 90 ℃, drip the 380.6g mass percent in 60min and be 35% Tai-Ace S 150 (M=666) and the mixture of water, generate white solid, cooling, filter, with 3L deionized water wash precipitation, 200 ℃ of oven dry 10h, obtain diethyl phospho acid aluminium 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 Examples 1 gained is mixed by weight 10:60:25:5 with PBT, glass, auxiliary agent at 230～260 ℃, 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 as can be known, moulding material stretching, bending and flame retardant properties that the dialkylphosphinic salts of preparation method's preparation of the present invention makes are superior, are applicable to make the polymer in-mold moulding material.
Claims (16)
1. the preparation method with dialkylphosphinic salts of good free-running property, is characterized in that, comprises the following steps:
A) add in dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and help crystallizing agent, obtain containing the dialkyl phosphinic acid and/or the dialkyl phosphinic acid aqueous solution of alkali metal salt that help crystallizing agent;
B) with the mixture of metallic compound and water and dialkyl phosphinic acid and/or the dialkylphosphinic salts of dialkyl phosphinic acid aqueous solution of alkali metal salt reaction generation as shown in formula I that helps crystallizing agent that contain that obtains;
Wherein, the described crystallizing agent that helps is 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;
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.
2. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, is characterized in that, it is oronain, Morpan BB, cetylpyridinium chloride or brocide that described positively charged ion helps crystallizing agent; 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 sodium sulfosuccinate; It is polysorbate compounds, polyoxyethylene fatty acid ester compounds, polyoxyethylene aliphatic alcohol ether class or Pluronic F68 that described nonionic helps crystallizing agent; It is Yelkin TTS, amino acid or betaine type compound that described zwitter-ion helps crystallizing agent.
3. the preparation method with dialkylphosphinic salts of good free-running property according to claim 2, it is characterized in that, the described crystallizing agent that helps is sodium stearate, sodium polyacrylate, sodium lauryl sulphate, sodium laurylsulfonate or Sodium dodecylbenzene sulfonate, optimization polypropylene acid sodium or sodium laurylsulfonate.
4. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, the described crystallizing agent that helps is take the quality of dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt as benchmark, and its massfraction is 0.1% ~ 50%, and preferred 1% ~ 10%.
5. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, 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%, preferred 30% ~ 70%.
6. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, in described 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, sal epsom, magnesium nitrate, magnesium chloride, magnesium acetate, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, calcium sulfate, nitrocalcite, calcium chloride or lime acetate.
7. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, is characterized in that, in step b), in the mixture of described metallic compound and water, the mass percent of metallic compound is 10% ~ 100%, preferred 20% ~ 50%.
8. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, in step b), the mol ratio 10:1 of the mixture of described metallic compound and water and dialkyl phosphinic acid and/or dialkyl phosphinic acid aqueous solution of alkali metal salt ~ 1:10, preferred 1:1 ~ 1:8.
9. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, 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 ℃, preferred 70 ~ 100 ℃.
10. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, 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, preferred 0.1 ~ 1h.
11. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1, it is characterized in that, in step b), the mixture of described metallic compound and water with contain the reaction of the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and refer to contain in the mixture that the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt join metallic compound and water and react, or the mixture of metallic compound and water joins to contain in the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and reacts, the mixture that is preferably metallic compound and water joins to contain in the dialkyl phosphinic acid that helps crystallizing agent and/or dialkyl phosphinic acid aqueous solution of alkali metal salt and reacts.
12. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1 is characterized in that, in step b), the residual moisture content of described dialkylphosphinic salts is 0.01 ~ 10wt%, preferred 0.1 ~ 1 wt%.
13. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1 is characterized in that, in step b), the slope of repose of described dialkylphosphinic salts is 20
°~ 40
°, preferred 25
°~ 35
°
14. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1 is characterized in that, in step b), the particle diameter of described dialkylphosphinic salts is 1 ~ 100 μ m.
15. the preparation method with dialkylphosphinic salts of good free-running property according to claim 1 is characterized in that, in step b), the tap density of described dialkylphosphinic salts is 500 ~ 800g/L, preferred 600 ~ 800g/L.
16. the dialkylphosphinic salts that the described method of claim 1-15 any one prepares is as the purposes of fire retardant.
Priority Applications (2)
| 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 |
| CN201410251925.3A CN104059101B (en) | 2013-02-27 | 2013-02-27 | A kind of dialkylphosphinic salts with good free-running property |
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 Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410251925.3A Division CN104059101B (en) | 2013-02-27 | 2013-02-27 | A kind of dialkylphosphinic salts with good free-running property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103172664A true CN103172664A (en) | 2013-06-26 |
| CN103172664B CN103172664B (en) | 2015-04-08 |
Family
ID=48632915
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410251925.3A Ceased CN104059101B (en) | 2013-02-27 | 2013-02-27 | A kind of dialkylphosphinic salts with good free-running property |
| CN201310061973.1A Expired - Fee Related CN103172664B (en) | 2013-02-27 | 2013-02-27 | Preparation method of dialkylphosphinate with excellent flowing property |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410251925.3A Ceased CN104059101B (en) | 2013-02-27 | 2013-02-27 | A kind of dialkylphosphinic salts with good free-running property |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104059101B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951700A (en) * | 2014-05-15 | 2014-07-30 | 江苏利思德新材料有限公司 | Preparation method as well as product and application of dimethyl hypophosphite |
| CN106632464A (en) * | 2016-11-21 | 2017-05-10 | 浙江传化华洋化工有限公司 | Preparation method and application of large-particle-size spherical dialkylphosphinate |
| WO2018214177A1 (en) * | 2017-05-25 | 2018-11-29 | 广州铂钡信息科技有限公司 | Additive for polymer and preparation method therefor |
| JP2019527687A (en) * | 2016-07-20 | 2019-10-03 | クラリアント・プラスティクス・アンド・コーティングス・リミテッド | Diorganylphosphinate, process for its production and use thereof |
| CN111808133A (en) * | 2020-06-23 | 2020-10-23 | 浙江新化化工股份有限公司 | Aluminum diethyl phosphinate material and preparation method thereof |
| 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 |
| CN114478625A (en) * | 2022-03-10 | 2022-05-13 | 江苏利思德新材料有限公司 | 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 |
| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | Flame retardant polyamide composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (4)
| 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 |
| CN101356220A (en) * | 2005-12-01 | 2009-01-28 | 苏普雷斯塔有限责任公司 | Flame retardant compositions containing mixtures of disubstituted phosphinate salts and monosubstituted phosphinate salts |
-
2013
- 2013-02-27 CN CN201410251925.3A patent/CN104059101B/en not_active Ceased
- 2013-02-27 CN CN201310061973.1A patent/CN103172664B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| CN101356220A (en) * | 2005-12-01 | 2009-01-28 | 苏普雷斯塔有限责任公司 | Flame retardant compositions containing mixtures of disubstituted phosphinate salts and monosubstituted phosphinate salts |
| 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 |
Cited By (15)
| 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 |
| CN103951700A (en) * | 2014-05-15 | 2014-07-30 | 江苏利思德新材料有限公司 | Preparation method as well as product and application of dimethyl hypophosphite |
| JP2019527687A (en) * | 2016-07-20 | 2019-10-03 | クラリアント・プラスティクス・アンド・コーティングス・リミテッド | Diorganylphosphinate, process for its production and use thereof |
| US11312910B2 (en) | 2016-07-20 | 2022-04-26 | Clariant International Ltd | Diorganylphosphinic acid salts, method for the production thereof and the use thereof |
| CN106632464A (en) * | 2016-11-21 | 2017-05-10 | 浙江传化华洋化工有限公司 | Preparation method and application of large-particle-size spherical dialkylphosphinate |
| 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 |
| WO2018214177A1 (en) * | 2017-05-25 | 2018-11-29 | 广州铂钡信息科技有限公司 | Additive for polymer and preparation method therefor |
| US11401416B2 (en) | 2017-10-17 | 2022-08-02 | Celanese Sales Germany Gmbh | 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 |
| CN111808133A (en) * | 2020-06-23 | 2020-10-23 | 浙江新化化工股份有限公司 | Aluminum diethyl phosphinate material and preparation method thereof |
| 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 |
| CN114478625A (en) * | 2022-03-10 | 2022-05-13 | 江苏利思德新材料有限公司 | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application 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 |
| WO2023168790A1 (en) * | 2022-03-10 | 2023-09-14 | 江苏利思德新材料有限公司 | Aluminum diethylphosphinate crystal with low fine powder content, and preparation method therefor and use 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059101B (en) | 2015-09-09 |
| CN103172664B (en) | 2015-04-08 |
| CN104059101A (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172664B (en) | Preparation method of dialkylphosphinate with excellent flowing 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 | |
| CN105085983A (en) | Halogen-free synergistic flame retardant, preparation method and composite flame retardant | |
| 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 | |
| US9982195B2 (en) | Flame retardant, flame retardant composition and shaped body | |
| CN105367823A (en) | Additive for polymer, preparing method and application of additive, and flame-retardant polymer molding composition composed of additive | |
| CN103172666B (en) | The preparation method of the dialkylphosphinic salts that a kind of thermostability is high | |
| CN104448453B (en) | The preparation method of the low cigarette of a kind of halogen acidylate, fire-retardant powder styrene butadiene rubber | |
| CN105061500A (en) | Superfine particle size dialkylphosphinate, preparation method and applications thereof, and high polymer composition comprising dialkylphosphinate | |
| CN105085988A (en) | Additive composition for polymers, preparation method of additive composition and flame-retardant thermoplastic polymer molding material containing additive composition | |
| 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 | |
| CN102492172A (en) | Preparation method and application of nanometer organic-layered composite metal hydroxide | |
| 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 | |
| CN105504346A (en) | Preparation method of novel zinc borate flame-retardant material | |
| CN106633187A (en) | Safe and environment-friendly inorganic aluminum hypophosphite flame retardant and application thereof in PBT (polybutylene terephthalate) | |
| CN110294862B (en) | Preparation method of nano-hybrid tin-based smoke suppressant | |
| CN112210123A (en) | Preparation method of low-cost coated flame-retardant smoke suppressant |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 Termination date: 20210227 |