CN103172908A - Method for coating ammonium polyphosphate by using binary composite coating agent - Google Patents
Method for coating ammonium polyphosphate by using binary composite coating agent Download PDFInfo
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- CN103172908A CN103172908A CN2013100693388A CN201310069338A CN103172908A CN 103172908 A CN103172908 A CN 103172908A CN 2013100693388 A CN2013100693388 A CN 2013100693388A CN 201310069338 A CN201310069338 A CN 201310069338A CN 103172908 A CN103172908 A CN 103172908A
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- ammonium polyphosphate
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Abstract
The invention belongs to the technical field of materials, and specifically relates to a method for coating ammonium polyphosphate by using a binary composite coating agent. According to the invention, 100g of ammonium polyphosphate, 5-20g of the binary composite coating agent, and 150-200g of a dispersing agent are added into a 1L reaction kettle; stirring is carried out for 0.5-2h under a temperature of 30-110 DEG C, until ammonium polyphosphate and the binary composite coating agent are completely dissolved; the pH is regulated to 3.5-5 by using acetic acid; heating is stopped; the solution is cooled, clarified, and stratified; a supernatant is removed; a precipitate is washed by using an organic solvent, and is bake-dried and grinded, such that ammonium polyphosphate coated by the binary composite coating agent is obtained. Compared with uncoated ammonium polyphosphate, the coated ammonium polyphosphate has substantially reduced water solubility, and uniform particle size distribution. When the material is doped into polypropylene, the flame retardant performance of formed composite material is improved, and low influence is caused on mechanical properties.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of method of binary compound coating agent coated ammonium polyphosphate.
Background technology
Expansion type flame retardant (IFR) is a kind of typical halogen-free flame retardants.Ammonium polyphosphate is one of IFR component commonly used, the ammonium polyphosphate strong dewatering agent polyphosphoric acid of rear generation that is heated, it can impel organism (as tetramethylolmethane) surface dewatering Formed compound, thereby forms foamed char in stromal surface, isolated air and play fire retardation.Ammonium polyphosphate good flame retardation effect, cost are low, nonpoisonous and tasteless, do not produce toxic gas after its thermolysis, meet the development trend of current fire retardant halogen-free environmental.Yet ammonium polyphosphate is porous particles shape material, and the surface has erratic composition, thus hygroscopic effect easily occurs, and also itself and matrix consistency are poor, easily ooze out the mechanical property of adversely affecting substrate; In addition, poor heat stability, decomposition temperature are generally lower than the matrix processing temperature.
In order to reduce the water-soluble of ammonium polyphosphate, improve the consistency of itself and matrix, improve thermostability, can carry out suitable surface modification to ammonium polyphosphate, at present, modification technology commonly used comprises: microcapsulary; Surfactant-modified technology; Cyanurotriamide modified technology and coupling agent modified technology etc.Wherein, the APP after surfactant-modified can be used as the fire retardant (particularly polyolefins) of various kinds of resin, and material not only can waterproof, also has good insulating property.But tensio-active agent is processed in APP and is used organic solvent, will remove unnecessary organic solvent in last handling process, needs special aftertreatment technology, must improve production cost.PP particle surface after the organic coupling agent modification is hydrophobicity, and the dispersiveness of resin is greatly improved, but because the coupling agent price is higher, makes it processing cost and improve.Adopt trimeric cyanamide to be coated on the surface of APP, can improve the bonding between molecular chain, improve water absorbability, on the low side but this method is produced productive rate, resistance to water soak improves little, and unstable result is unfavorable for suitability for industrialized production.
Microcapsulary is that research is more at present, a kind of technology that application surface is the widest, refer to utilize natural or synthetic high-polymer encapsulated material, the small core material of solid, liquid or even gas is coated, form a kind of minigel with semipermeability or closing membrane of diameter 1～50 μ m.At present more external companies such as Hoechst AG, Monsanto Company and the Albright Wilson product that lists a company is micro encapsulation ammonium polyphosphate product.Patent EP3531500 makes with terpolycyantoamino-formaldehyde resin micro encapsulation ammonium polyphosphate the ammonium polyphosphate that melamine formaldehyde resin coats; Patent US5321057 and US5576391 use amino (plastics) resin microcapsule ammonium polyphosphate in formaldehyde solution; Patent US6291068 uses the thermoplastic resin coated ammonium polyphosphate adding under the condition of tensio-active agent; The resin temperature resistant grade that above patent coats is not high, and Vicat softening point is on the low side, and the microcapsule that cause these methods to coat can not be applied to the higher polymer materials of processing environment.Patent DE2949537DE3005252 and DE3316880 coat with melamine-formaldehyde resin or phenol-formaldehyde resin, and preparation has the good ammonium polyphosphate coating material of resistant to hydrolysis performance.But in the coating process, the reactor inwall has ammonium polyphosphate and resin knot wall causes the reactor heat transfer deterioration.In addition, the ammonium polyphosphate particle diameter after coating is larger, needs pulverization process during use, but can cause the breakage of coating face bad, stability decreases.
Summary of the invention
In order to overcome determining of above-mentioned prior art, the invention provides a kind of method of binary compound coating agent coated ammonium polyphosphate, the method is intended to reduce the water-soluble of ammonium polyphosphate, the flame retardant resistance of raising and matrix etc.
Technical scheme of the present invention is:
A kind of method of binary compound coating agent coated ammonium polyphosphate, take ammonium polyphosphate as core, with binary compound coating agent coated ammonium polyphosphate, concrete steps are as follows:
With agitator, in the 1L reactor of thermometer and condensation reflux unit, the ammonium polyphosphate of 100g and the binary compound coating agent of 5-20g and the dispersion agent of 150-200g are joined in reactor, stir 0.5-2h under 30-110 ℃, until ammonium polyphosphate and the agent of binary compound coating are dissolved fully, with the second acid for adjusting pH to 3.5-5, stopped heating, lonely, layering, remove supernatant liquid, with throw out with the organic solvent washing post-drying, grind, obtain the ammonium polyphosphate that the agent of binary compound coating coats.
Described binary compound coating agent preparation method is, adding under the condition of auxiliary agent, with maleic anhydride, a kind of in succinyl oxide and partially stupid three acid anhydrides mixes with Ethenylbenzene methyl ether or Ethenylbenzene ether, extrudes by twin screw extruder, is cooled to room temperature.
Described dispersion agent is a kind of in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, trichloroethane, Neotran and Penticidum.
Described dispersion agent is a kind of in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, trichloroethane, 1,1 methylene dichloride, 1,2 methylene dichloride and Isosorbide-5-Nitrae methylene dichloride.In the present invention, dispersant dosage is too low, and binary compound coating agent dispersion effect in ammonium polyphosphate is not good enough, affects covered effect, and dispersant dosage is too high, and the solvent recuperation expense is too high.
In binary compound coating agent preparation process, described auxiliary agent is methyl alcohol, ethanol, propyl alcohol, acetone, 2,3-dimethyl-2, a kind of in the 3-diphenyl butane.In the present invention, adding of auxiliary agent mixes two kinds of raw materials, sufficient reacting.
Described promoter addition is the 10-40% of binary compound coating agent total amount.
Described twin screw extruder head temperature is 50-90 ℃.
Embodiment
Performance test data in the present invention in each embodiment records by following method:
1. U.S. Beckman company laser particle size analyzer, model LS 100Q are adopted in sreen analysis.
2. solubleness test: accurately take 10g left and right ammonium polyphosphate, real with filter paper packet, then pack tightly with cotton, bind 25 ℃ of insulation 72h in the distilled water that is placed on 1000mL with cotton thread, take out oven dry and weigh.Solubleness
s(
g/ 100
mLWater)=
3. the preparation of anti-flaming polypropylene material: with the ammonium polyphosphate after a certain amount of parcel, plasticizing polypropylene and nylon 6 powder (mass ratio: 18:73:9) 180 ℃ of mixing 15min on twin-roll plastic mixing mill well, 180 ℃ of hot pressing on vulcanizing press successively, normal temperature coldmoulding, and the universal sampling machine sample preparation (size of sample: 120 mm * 6mm * 4mm).
4. oxygen index test: according to the GB/T2406-1993 standard test methods; Vertical combustion grade test: according to the GB/T24082-1996 standard test methods; Tensile strength is tested according to GB/T 1040-1992; Shock strength is tested according to GB/T 1843-1996.
The below further illustrates the present invention with embodiment, but the present invention is in no way limited to these embodiment.
Embodiment 1
With agitator, in the 1L reactor of thermometer and condensation reflux unit, the ammonium polyphosphate of 100g and the binary compound coating agent of 7g and the trichloroethane of 160 parts are joined in reactor, stir 1h under 60 ℃, until ammonium polyphosphate and the agent of binary compound coating are dissolved fully, with second acid for adjusting pH to 3.5, stopped heating, supernatant liquid is removed in lonely, layering, with throw out with the organic solvent washing post-drying, grind, obtain the ammonium polyphosphate that the agent of 107.07g binary compound coating coats.
Wherein, binary compound coating agent preparation method is, under the condition that adds 1.41g methyl alcohol, is that the 6.11g maleic anhydride mixes with the Ethenylbenzene methyl ether with total amount, extrudes by twin screw extruder, is cooled to room temperature.
Embodiment 2
With agitator, in the 1L reactor of thermometer and condensation reflux unit, the ammonium polyphosphate of 100g and the binary compound coating agent of 12g and the ethylene dichloride of 200 parts are joined in reactor, stir 0.5h under 90 ℃, until ammonium polyphosphate and the agent of binary compound coating are dissolved fully, with second acid for adjusting pH to 5, stopped heating, supernatant liquid is removed in lonely, layering, with throw out with the organic solvent washing post-drying, grind, obtain the ammonium polyphosphate that the agent of 112.11g binary compound coating coats.
Wherein, binary compound coating agent preparation method is, under the condition that adds the 2.28g propyl alcohol, the 9.85g succinyl oxide mixed with the Ethenylbenzene ether, extrudes by twin screw extruder, is cooled to room temperature.
Embodiment 3
With agitator, in the 1L reactor of thermometer and condensation reflux unit, the ammonium polyphosphate of 100g and the binary compound coating agent of 20g and the Penticidum of 180 parts are joined in reactor, stir 2h under 110 ℃, until ammonium polyphosphate and the agent of binary compound coating are dissolved fully, with second acid for adjusting pH to 4, stopped heating, supernatant liquid is removed in lonely, layering, with throw out with the organic solvent washing post-drying, grind, obtain the ammonium polyphosphate that the agent of 120.17g binary compound coating coats.
Wherein, binary compound coating agent preparation method is, adding 4.2g 2, and under the condition of 3-diphenyl butane, mix the 16.1g maleic anhydride 3-dimethyl-2 with the Ethenylbenzene ether, extrude by twin screw extruder, is cooled to room temperature.
Embodiment 4
With agitator, in the 1L reactor of thermometer and condensation reflux unit, the ammonium polyphosphate of 100g and the binary compound coating agent of 15g and the trichloromethane of 170 parts are joined in reactor, stir 1h under 60 ℃, until ammonium polyphosphate and the agent of binary compound coating are dissolved fully, with second acid for adjusting pH to 3, stopped heating, supernatant liquid is removed in lonely, layering, with throw out with the organic solvent washing post-drying, grind, obtain the ammonium polyphosphate that the agent of 115.09g binary compound coating coats.
Wherein, binary compound coating agent preparation method is, under the condition that adds 3.12g ethanol, partially stupid three acid anhydrides of 11.95g mixed with the Ethenylbenzene methyl ether, extrudes by twin screw extruder, is cooled to room temperature.
Above-mentioned ammonium polyphosphate used is crystal I-type ammonium polyphosphate;
Ammonium polyphosphate the performance test results before and after embodiment 1-4 coats sees Table 1;
Ammonium polyphosphate before and after embodiment 1-4 coats is doped to and forms composite material test in polypropylene and the results are shown in Table 2.
Ammonium polyphosphate the performance test results after table 1 coats
| Embodiment | Median size (μ m) | Solubleness ( g/100 mLWater) | The microcapsule Micro-Structure Analysis |
| Do not coat | 8.4 | 0.57 | Be evenly distributed |
| 1 | 13.6 | 0.083 | Be evenly distributed, most of even compact that coats |
| 2 | 14.7 | 0.058 | Be evenly distributed, coat even compact |
| 3 | 16.1 | 0.074 | A small amount of agglomeration is arranged, coat even compact |
| 4 | 14.1 | 0.065 | Be evenly distributed, coat even compact |
Ammonium polyphosphate after table 2 coats is doped to and forms the composite material test result in polypropylene
| Embodiment | Oxygen index (LOI) | The burning grade | Tensile strength (MPa) | Shock strength (kJ/m 2) |
| Do not coat | 20.4 | UL-94 V-1 | 36.2 | 7.1 |
| 1 | 31.2 | UL-94 V-0 | 34.1 | 6.8 |
| 2 | 33.6 | UL-94 V-0 | 30.5 | 6.1 |
| 3 | 34.0 | UL-94 V-1 | 31.2 | 6.3 |
| 4 | 33.7 | UL-94 V-0 | 32.9 | 6.6 |
Claims (7)
1. the method for a binary compound coating agent coated ammonium polyphosphate, is characterized in that the method comprises the following steps:
With agitator, in the 1L reactor of thermometer and condensation reflux unit, the ammonium polyphosphate of 100g and the binary compound coating agent of 5-20g and the dispersion agent of 150-200g are joined in reactor, stir 0.5-2h under 30-110 ℃, until ammonium polyphosphate and the agent of binary compound coating are dissolved fully, with the second acid for adjusting pH to 3.5-5, stopped heating, lonely, layering, remove supernatant liquid, with throw out with the organic solvent washing post-drying, grind, obtain the ammonium polyphosphate that the agent of binary compound coating coats.
2. the method for a kind of binary compound coating agent coated ammonium polyphosphate described according to right 1, it is characterized in that: described binary compound coating agent preparation method is, adding under the condition of auxiliary agent, with maleic anhydride, a kind of in succinyl oxide and partially stupid three acid anhydrides mixes with Ethenylbenzene methyl ether or Ethenylbenzene ether, extrude by twin screw extruder, be cooled to room temperature.
3. the method for a kind of binary compound coating agent coated ammonium polyphosphate described according to right 1 is characterized in that: described dispersion agent is a kind of in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, trichloroethane, Neotran and Penticidum.
4. the method for a kind of binary compound coating agent coated ammonium polyphosphate described according to right 1, it is characterized in that: described dispersion agent is monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, trichloroethane, 1,1 methylene dichloride, 1, a kind of in 2 methylene dichloride and Isosorbide-5-Nitrae methylene dichloride.
5. the method for a kind of binary compound coating agent coated ammonium polyphosphate described according to right 2, it is characterized in that: described auxiliary agent is methyl alcohol, ethanol, propyl alcohol, acetone, 2,3-dimethyl-2, a kind of in the 3-diphenyl butane.
6. the method for a kind of binary compound coating agent coated ammonium polyphosphate described according to right 2, it is characterized in that: described promoter addition is the 10-40% of binary compound coating agent total amount.
7. the method for a kind of binary compound coating agent coated ammonium polyphosphate described according to right 2, it is characterized in that: described twin screw extruder head temperature is 50-90 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834063A (en) * | 2014-01-16 | 2014-06-04 | 云南磷化集团有限公司 | Method for coating ammonium polyphosphate with binary composite coating agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4467056A (en) * | 1979-12-08 | 1984-08-21 | Hoechst Aktiengesellschaft | Particulate agent for impeding the combustibility of combustible materials |
| CN101429291A (en) * | 2008-12-16 | 2009-05-13 | 四川大学 | Method for coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule |
| CN101829527A (en) * | 2010-04-01 | 2010-09-15 | 河北大学 | Method for preparing microcapsule-coated ammonium polyphosphate |
-
2013
- 2013-03-05 CN CN2013100693388A patent/CN103172908A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4467056A (en) * | 1979-12-08 | 1984-08-21 | Hoechst Aktiengesellschaft | Particulate agent for impeding the combustibility of combustible materials |
| CN101429291A (en) * | 2008-12-16 | 2009-05-13 | 四川大学 | Method for coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule |
| CN101829527A (en) * | 2010-04-01 | 2010-09-15 | 河北大学 | Method for preparing microcapsule-coated ammonium polyphosphate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834063A (en) * | 2014-01-16 | 2014-06-04 | 云南磷化集团有限公司 | Method for coating ammonium polyphosphate with binary composite coating agent |
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Application publication date: 20130626 |