CN103725043A - Preparation method of molecular self-assembly microcapsule coated ammonium polyphosphate - Google Patents
Preparation method of molecular self-assembly microcapsule coated ammonium polyphosphate Download PDFInfo
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- CN103725043A CN103725043A CN201310467609.5A CN201310467609A CN103725043A CN 103725043 A CN103725043 A CN 103725043A CN 201310467609 A CN201310467609 A CN 201310467609A CN 103725043 A CN103725043 A CN 103725043A
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Abstract
The invention belongs to the technical field of materials, and particularly relates to a preparation method of molecular self-assembly microcapsule coated ammonium polyphosphate. The method comprises the steps as follows: water and ammonium polyphosphate are added into a reaction kettle firstly, then water-soluble polyhydric alcohol are added and stirred for 10-60 min, and 2, 4-toluene diisocynate is added; and stirring and reacting are performed for 10-120 min, and filtering and drying are performed to obtain molecular self-assembly microcapsule coated ammonium polyphosphate. According to the method, ammonium polyphosphate is taken as a capsule core, water-soluble polyhydric alcohol and isocyanate are taken as polymerized monomers, microcapsule coated ammonium polyphosphate is prepared in a dispersing agent with an in-situ polymer molecular self-assembly technology, reaction conditions are mild, the technological operation process is simple, used raw materials are safe and easy to obtain, and industrial production is facilitated.
Description
Technical field
The invention belongs to material technology field, be specifically related to a kind of preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate.
background technology
Expanding halide-free fire-retardant has the advantages such as fire-retardant low cigarette, low toxicity, corrosion-free air release, is halogen-free flame retardants most with prospects, is described as the revolution in flame-retarded technology, becomes the focus of recent domestic research.Ammonium polyphosphate is as one of main component of expansion type flame retardant, because its phosphorus content is high, nitrogen content large, Heat stability is good, have simultaneously low price, toxicity lower, use the advantages such as comparatively safe, be widely used as the fire-retardant of coating, plastics, fiber, rubber etc.But ammonium polyphosphate is due to the chemical structure of himself, and water absorbability is very strong, easily reunite, poor with the consistency of polymer materials, the in the situation that of high temperature, high humidity, very easily to material surface migration, ooze out, reduce the especially flame retardant properties of comprehensive effectiveness of material.Although high polymerization degree APP water-soluble obtained remarkable improvement, still can be because of lost effective constituents such as hydrolysis when temperature is higher.
In order to reduce the water-soluble of ammonium polyphosphate, improve thermostability, the consistency of improvement and polymer base material, can carry out suitable modification to ammonium polyphosphate surface.Comparatively common ammonium polyphosphate modification technology mainly contains coupling agent modified technology, surfactant-modified technology, cyanurotriamide modified technology and microcapsule coated technology etc. at present.Wherein, with silane coupling agent, to ammonium polyphosphate modifying surface, test result shows, the ammonium polyphosphate particle surface after modification is hydrophobicity, and the dispersiveness in resin is greatly improved.But because the price of silane coupling agent own is higher and preparation technology is more complicated, be not suitable for extensive industrialization.Surfactant-modified processing ammonium polyphosphate particle surface, improves consistency and the dispersiveness of ammonium polyphosphate and organic resin, but can not improve its water absorbability.Utilizing trimeric cyanamide to carry out surface modification is also the many problems of Recent study, more commonly by a certain amount of trimeric cyanamide and ammonium polyphosphate Hybrid Heating, trimeric cyanamide is coated on to the surface of ammonium polyphosphate, but trimeric cyanamide itself is polarity, still has water absorbability problem.
Microcapsule coated technology is that research is more at present, a kind of technology that application surface is the widest.More external companies are micro encapsulation ammonium polyphosphate product as listing products such as a gram Lay benefactor department, Monsanto Company and Hoechst AG.Patent EP3531500 prepares melmac coated ammonium polyphosphate with terpolycyantoamino-formaldehyde resin micro encapsulation ammonium polyphosphate; Patent US5321027 and US5576391 use aminoresin micro encapsulation ammonium polyphosphate in formaldehyde solution; Adopt the disclosed method of above patent to carry out micro encapsulation when coated, ubiquity clad ratio is wayward, coated incomplete problem.Patent DE2949537, DE3005252 and DE3316880 disclose with melamine-formaldehyde resin or phenol-formaldehyde resin coated, and preparation has the method for the ammonium polyphosphate powder of resistant to hydrolysis performance, excellent in stability.Compared with ammonium polyphosphate without microcapsule coated processing, after coated the water-soluble obvious reduction of ammonium polyphosphate, thermostability improves.But while adopting the disclosed method of above patent to carry out microcapsule coated processing, reactor inwall there will be the knot wall phenomenon of a large amount of ammonium polyphosphates and resin, deteriorative reaction still conducts heat.In addition, the microcapsule-coated ammonium polyphosphate that adopts these class methods to obtain, the obvious chap of particle diameter, even has block to form, and needs pulverization process during use, causes breaking of microcapsule, stability decreases.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides take water-soluble polyol and 2,4 toluene diisocyanate as raw material, to the method for ammonium polyphosphate microcapsule coated, the method can improve the stability of ammonium polyphosphate, reduces its water-soluble, improves the consistency with polymer base material.The method reaction conditions gentleness, technological operation flow process is simple, raw materials used safely, be easy to get, be convenient to suitability for industrialized production.
The present invention realizes by following technical scheme:
The preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate, comprises following step:
First water and ammonium polyphosphate are joined in reactor, described water and the part by weight of ammonium polyphosphate are 1:1-5:
Then add water-soluble polyol, described water-soluble polyol and the weight ratio of ammonium polyphosphate are 1:5-30;
Stir 10-60min, then add 2,4 toluene diisocyanate, the weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:2-12;
At 0-100 ℃, stirring reaction 10-120 minute, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
Preferably, the weight ratio 1:2-4 of ammonium polyphosphate and water;
Water-soluble polyol is any in ethylene glycol, 1,2-PD, 1,3-PD;
The weight ratio of water-soluble polyol and ammonium polyphosphate is 1:10-20;
The weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:4-9.
Preferred, the weight ratio 1:3 of ammonium polyphosphate and water.
Water-soluble polyol is 1,2-PD.
The weight ratio of water-soluble polyol and ammonium polyphosphate is 1:15.
The weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:6.
Temperature of reaction is 20-40 ℃.
Adopting method of the present invention, avoided the defect of other patented method of mentioning in background technology, for example, avoided in the process of reaction, there is the knot wall phenomenon of a large amount of ammonium polyphosphates and resin in reactor inwall, the phenomenon that deteriorative reaction still conducts heat; Avoided ammonium polyphosphate microcapsule coated rate wayward, not exclusively coated, microcapsule structure designs the problems such as specific aim is not strong.
And method of the present invention obtains microcapsule-coated ammonium polyphosphate, coated completely, capsule material and capsule-core have fire-retardant synergistic effect, can the obvious chap of particle diameter, even have the formation of block, thereby need pulverization process to cause microcapsules rupture during use and then affect the phenomenon of its stability.
Adopt method of the present invention to greatly reduce the water-soluble of ammonium polyphosphate, simultaneously relative ammonium polyphosphate, its surface polarity reduces greatly, there is better dispersiveness and consistency with polymer materials, solved in ammonium polyphosphate water solubleness larger, poor with polymeric substrate consistency, be difficult to meet the gordian technique difficult problem of fire retardant material application requiring in wet environment.
The inventive method is take ammonium polyphosphate as capsule-core, water-soluble polyol and isocyanic ester are polymerization single polymerization monomer, in dispersion agent, by in-situ polymerization numerator self-assembly technique, prepare microcapsule-coated ammonium polyphosphate, reaction conditions gentleness, technological operation flow process is simple, raw materials used safely, be easy to get, be convenient to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Sreen analysis adopts U.S. Beckman company laser particle size analyzer, model LS 230.
Solubleness test: accurately take 10 grams of microcapsule-coated ammonium polyphosphates and be placed in 100ml deionized water, at 25 ℃, stir 1 hour, centrifugal settling, gets supernatant liquor 50ml and is dried to constant weight, be weighed as W gram, the solubleness of derived sample at 25 ℃ is 2W (g/100ml water).
The preparation of anti-flaming polypropylene material: by a certain amount of molecular self-assembling microcapsule-coated ammonium polyphosphate, trimeric cyanamide and polypropylene (weight ratio is 25:5:75) on twin screw extruder 180 ℃ extrude, the dried pellet of extruding is injected to sample batten (size of sample: 120mm × 13mm × 3.2mm) on injection moulding machine.
The test of vertical combustion grade: according to: UL 94-2013 standard test methods test.
Embodiment 1
In the reactor of the 1L with agitator, thermometer and condensation reflux unit, by 180g ammonium polyphosphate, 400g deionized water, 9g1, ammediol joins in reactor, dispersed with stirring 30 minutes, then by 21g2,4-tolylene diisocyanate joins in reactor, stirring reaction 60 minutes at 30 ℃, filter, dry, obtain 206g molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 2
In the reactor of the 1L with agitator, thermometer and condensation reflux unit, by 180g ammonium polyphosphate, 500g deionized water, 9g ethylene glycol joins in reactor, and dispersed with stirring 30 minutes, then by 21g2,4-tolylene diisocyanate joins in reactor, stirring reaction 60 minutes at 40 ℃, filters, dries, and obtains 203g molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 3
In the reactor of the 1L with agitator, thermometer and condensation reflux unit, by 180g ammonium polyphosphate, 500g deionized water, 18g1,2-propylene glycol joins in reactor, dispersed with stirring 20 minutes, then by 42g2,4-tolylene diisocyanate joins in reactor, stirring reaction 80 minutes at 20 ℃, filter, dry, obtain 235g molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 4
In the reactor of the 1L with agitator, thermometer and condensation reflux unit, by 180g ammonium polyphosphate, 400g deionized water, 18g1,2-propylene glycol joins in reactor, dispersed with stirring 30 minutes, then by 42g2,4-tolylene diisocyanate joins in reactor, stirring reaction 100 minutes at 30 ℃, filter, dry, obtain 238g molecular self-assembling microcapsule-coated ammonium polyphosphate.
Before and after embodiment 1-4 molecular self-assembling microcapsule coated, ammonium polyphosphate the performance test results is in Table 1;
The vertical combustion test result that before and after embodiment 1-4 molecular self-assembling microcapsule coated, ammonium polyphosphate adds the matrix material forming in polypropylene to is in Table 2.
Ammonium polyphosphate the performance test results before and after table 1 molecular self-assembling microcapsule coated
The vertical combustion test result that before and after table 2 molecular self-assembling microcapsule coated, ammonium polyphosphate adds the matrix material forming in polypropylene to
Embodiment 5
In the reactor with agitator, thermometer and condensation reflux unit, by ammonium polyphosphate, deionized water joins in reactor, the part by weight of water and ammonium polyphosphate is 1:3, add again ethylene glycol in reactor, dispersed with stirring 30 minutes, the weight ratio of ethylene glycol and ammonium polyphosphate is 1:15, then 2,4 toluene diisocyanate is joined in reactor to 2, the weight ratio of 4-tolylene diisocyanate and ammonium polyphosphate is 1:6, stirring reaction 100 minutes at 30 ℃, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 6
In the reactor with agitator, thermometer and condensation reflux unit, by ammonium polyphosphate, deionized water joins in reactor, the part by weight of water and ammonium polyphosphate is 1:1, add again ethylene glycol in reactor, dispersed with stirring 30 minutes, the weight ratio of ethylene glycol and ammonium polyphosphate is 1:5, then 2,4 toluene diisocyanate is joined in reactor to 2, the weight ratio of 4-tolylene diisocyanate and ammonium polyphosphate is 1:2, stirring reaction 100 minutes at 30 ℃, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 7
In the reactor with agitator, thermometer and condensation reflux unit, by ammonium polyphosphate, deionized water joins in reactor, the part by weight of water and ammonium polyphosphate is 1:5, add again ethylene glycol in reactor, dispersed with stirring 30 minutes, the weight ratio of ethylene glycol and ammonium polyphosphate is 1:30, then 2,4 toluene diisocyanate is joined in reactor to 2, the weight ratio of 4-tolylene diisocyanate and ammonium polyphosphate is 1:12, stirring reaction 100 minutes at 30 ℃, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 8
In the reactor with agitator, thermometer and condensation reflux unit, by ammonium polyphosphate, deionized water joins in reactor, the part by weight of water and ammonium polyphosphate is 1:5, add again 1,2-propylene glycol is in reactor, dispersed with stirring 30 minutes, the weight ratio of ethylene glycol and ammonium polyphosphate is 1:30, then by 2,4-tolylene diisocyanate joins in reactor, the weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:12, stirring reaction 100 minutes at 30 ℃, filter, dry, obtain molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 9
In the reactor with agitator, thermometer and condensation reflux unit, by ammonium polyphosphate, deionized water joins in reactor, the part by weight of water and ammonium polyphosphate is 1:3, add again 1,2-propylene glycol in reactor, dispersed with stirring 30 minutes, 1, the weight ratio of 2-propylene glycol and ammonium polyphosphate is 1:15, then 2,4 toluene diisocyanate is joined in reactor to 2, the weight ratio of 4-tolylene diisocyanate and ammonium polyphosphate is 1:6, stirring reaction 100 minutes at 30 ℃, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
Embodiment 10
In the reactor with agitator, thermometer and condensation reflux unit, by ammonium polyphosphate, deionized water joins in reactor, the part by weight of water and ammonium polyphosphate is 1:3, add again 1, ammediol in reactor, dispersed with stirring 30 minutes, 1, the weight ratio of ammediol and ammonium polyphosphate is 1:15, then 2,4 toluene diisocyanate is joined in reactor to 2, the weight ratio of 4-tolylene diisocyanate and ammonium polyphosphate is 1:6, stirring reaction 100 minutes at 30 ℃, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
Claims (10)
1. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate, comprises following step:
First water and ammonium polyphosphate are joined in reactor, described water and the part by weight of ammonium polyphosphate are 1:1-5:
Then add water-soluble polyol, described water-soluble polyol and the weight ratio of ammonium polyphosphate are 1:5-30;
Stir 10-60min, then add 2,4 toluene diisocyanate, the weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:2-12;
At 0-100 ℃, stirring reaction 10-120 minute, filters, dries, and obtains molecular self-assembling microcapsule-coated ammonium polyphosphate.
2. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate as claimed in claim 1, is characterized in that, the weight ratio 1:2-4 of ammonium polyphosphate and water.
3. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate as claimed in claim 1 or 2, is characterized in that, the weight ratio 1:3 of ammonium polyphosphate and water.
4. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate as claimed in claim 1, is characterized in that, described water-soluble polyol is any in ethylene glycol, 1,2-PD, 1,3-PD.
5. the preparation method of the molecular self-assembling microcapsule-coated ammonium polyphosphate as described in claim 1 or 4, is characterized in that, described water-soluble polyol is 1,2-PD.
6. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate as claimed in claim 1, is characterized in that, described water-soluble polyol and the weight ratio of ammonium polyphosphate are 1:10-20.
7. the preparation method of the molecular self-assembling microcapsule-coated ammonium polyphosphate as described in claim 1 or 6, is characterized in that, described water-soluble polyol and the weight ratio of ammonium polyphosphate are 1:15.
8. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate as claimed in claim 1, is characterized in that, the weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:4-9.
9. the preparation method of the molecular self-assembling microcapsule-coated ammonium polyphosphate as described in claim 1 or 8, is characterized in that, the weight ratio of 2,4 toluene diisocyanate and ammonium polyphosphate is 1:6.
10. the preparation method of molecular self-assembling microcapsule-coated ammonium polyphosphate as claimed in claim 1, is characterized in that, temperature of reaction is 20-40 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448555A (en) * | 2014-11-21 | 2015-03-25 | 济南泰星精细化工有限公司 | Preparation method of novel halogen-free fire retardant for polypropylene |
| CN105566684A (en) * | 2015-12-23 | 2016-05-11 | 山东省化工研究院 | Method for preparing microcapsule-coated ammonium polyphosphate through in-situ polymerization molecular self-assembly |
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2013
- 2013-10-09 CN CN201310467609.5A patent/CN103725043B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 李轶等: "微胶囊化聚磷酸铵及其阻燃聚丙烯的研究进展", 《中国塑料》, vol. 22, no. 12, 31 December 2008 (2008-12-31), pages 6 - 10 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448555A (en) * | 2014-11-21 | 2015-03-25 | 济南泰星精细化工有限公司 | Preparation method of novel halogen-free fire retardant for polypropylene |
| CN105566684A (en) * | 2015-12-23 | 2016-05-11 | 山东省化工研究院 | Method for preparing microcapsule-coated ammonium polyphosphate through in-situ polymerization molecular self-assembly |
| CN105566684B (en) * | 2015-12-23 | 2018-05-18 | 山东省化工研究院 | The method that in-situ polymerization molecular self-assembling prepares microcapsule-coated ammonium polyphosphate |
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