CN103980541A - Coating modification method for melamine formaldehyde resin of ammonium polyphosphate - Google Patents
Coating modification method for melamine formaldehyde resin of ammonium polyphosphate Download PDFInfo
- Publication number
- CN103980541A CN103980541A CN201410222743.3A CN201410222743A CN103980541A CN 103980541 A CN103980541 A CN 103980541A CN 201410222743 A CN201410222743 A CN 201410222743A CN 103980541 A CN103980541 A CN 103980541A
- Authority
- CN
- China
- Prior art keywords
- ammonium polyphosphate
- trimeric cyanamide
- formaldehyde resin
- melamino
- modifying
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to a coating modification method for melamine formaldehyde resin of ammonium polyphosphate. The method comprises the following steps: firstly, heating and activating ammonium polyphosphate, partially deaminizing to form acid activated ammonium polyphosphate, and then enabling trimeric cyanamide to react with activated ammonium polyphosphate to obtain ammonium polyphosphate of which the surface is grafted with the trimeric cyanamide; finally crosslinking with the trimeric cyanamide on the surface of the ammonium polyphosphate of which the surface is grafted with the trimeric cyanamide by using formaldehyde, so as to prepare the modified ammonium polyphosphate coated with melamine formaldehyde resin. The defects that the traditional coating modification technology of the melamine formaldehyde resin is large in material consumption, difficult to recover a solvent, not tight enough to combine a resin shell layer and an ammonium polyphosphate core material are overcome, the solubility of the prepared modified ammonium polyphosphate just is 0.012g/100g of water, and is reduced by over 90% in comparison with that of the ammonium polyphosphate material, the initial decomposition temperature of the modified ammonium polyphosphate can be up to 245 DEG C, and is improved by 55 DEG C in comparison with the initial decomposition temperature of the ammonium polyphosphate material, 30wt% of polypropylene is added to prepare flame retardant composites, and the limit oxygen index of the composites can be up to 28.3%.
Description
Technical field
The present invention relates to a kind of surface modifying method of ammonium polyphosphate, especially relate to a kind of coated method of modifying of melamino-formaldehyde resin of ammonium polyphosphate, for the production field of expansion type flame retardant.
Background technology
Ammonium polyphosphate (APP) is the inorganic phosphorus flame retardant that flame retardant properties is good.The APP of take has that ignition-proof element content is high, thermal stability good, flame retardant properties is good as the composite expansion type flame retardant in basis, and nontoxicity and press down the plurality of advantages such as cigarette is widely used in the fire-retardant of the macromolecular materials such as resin, plastics, rubber and frie retardant coating etc.APP can directly add in organic polymer base material as fire retardant.But due to APP inorganic polymer, poor with the consistency of base material, non-modified makes the mechanical property of materials decline after directly adding, and APP water absorbability makes it easily from material internal, migrate to surface and run off gradually, causes the weather-proof decline of material.For the higher material of processing temperature, in the course of processing, APP thermolysis discharges ammonia, further causes the mechanical property of goods to decline.For improving consistency and the flame-proof heat-resistant processing characteristics of APP and organic polymer material, reduce water absorbability and its solubleness in water of APP, need to carry out surface modification to APP.Microcapsule coated is a kind of common method of APP modification, and conventional coated wall material comprises melamine resin, epoxy resin, ethylene-vinyl acetate copolymer (EVA) etc.Reported APP " melamino-formaldehyde resin is coated modification " technique all adopts prepolymer in-situ polymerization technique, if the people such as Wang are at < < Enhanced flame retardancy of natural rubber composite with addition of microencapsulated ammonium polyphosphate and MCM-41fillers > > (Fire Safety Journal, 2013, 62:281-288), the people such as Wu are at < < Microencapsulation of ammonium polyphosphate:Preparation, characterization, and its flame retardance in polypropylene > > (Polymer Composites, 2008, 29 (8): 854-860), the people such as Chen Jianfeng are at the research > > (coatings industry of < < micro encapsulation ammonium polyphosphate fire retarding epoxide resin, 2010, 40 (11), 15～18, 23), the people such as Hong Xiaodong are at the preparation of < < microcapsule ammonium polyphosphate and the performance study > > (coatings industry of fire retarding epoxide resin, 2012, 42 (12), 7～10), melamino-formaldehyde resin described in US Patent No. 4157983A < < Process for production of encapsulated water-dispersible materials > > is coated method of modifying, its principal character is: a certain amount of trimeric cyanamide is added to stirring and dissolving in formalin, the pH value that adds water adjusting reaction solution is 7～8, be warmed up to 80～120 ℃ of reactions and obtain terpolycyantoamino-formaldehyde resin prepolymer, then in prepolymer solution, add APP according to a certain percentage, regulate pH, reaction certain hour makes performed polymer form melamine resin shell in the polymerization of APP particle surface, through suction filtration, after filtration cakes torrefaction, obtain the APP product that micro encapsulation is processed.APP its solubleness in water after modification reduces, and increases with the consistency of polymeric substrate.Report from " melamine resin is coated modification " technique of existing APP, melamino-formaldehyde resin cladding process is all first to use formalin and trimeric cyanamide (MEL) to prepare the prepolymer of melamino-formaldehyde resin, then add APP to make prepolymer form melamino-formaldehyde resin at APP in situ Polymerization, in coating reaction process, only have part performed polymer to form wall material at APP surface aggregate, the performed polymer that does not form wall material is difficult to recycling, causes wastage of material, also has problem of environmental pollution.In addition, modification APP prepared by existing " melamine resin is coated modification " method, melamine resin is just coated on APP surface by physical adherence effect, the combination undertighten of resin wall material and APP core, the physical strength of modification APP is not high, while being processed into flame-proof composite material by banburying in adding base material (as polypropylene) to, the strong shearing in Banbury mixer and high temperature easily make the resin shell of modification APP damaged.
Summary of the invention
Object of the present invention is exactly the coated method of modifying of melamino-formaldehyde resin that a kind of ammonium polyphosphate is provided in order to overcome the deficiency of existing melamino-formaldehyde resin coated ammonium polyphosphate modification technology.
Object of the present invention can be achieved through the following technical solutions:
The coated method of modifying of melamino-formaldehyde resin of ammonium polyphosphate, comprises the following steps:
1) by ammonium polyphosphate (being called for short APP) heat-activated, part deamination forms acid activation ammonium polyphosphate;
2) alkaline trimeric cyanamide (being called for short MEL) is reacted with activation ammonium polyphosphate, make MEL scion grafting upper to activation APP, prepare the ammonium polyphosphate (being called for short MAPP) of surperficial scion grafting trimeric cyanamide;
3), by the lip-deep trimeric cyanamide crosslinking reaction of ammonium polyphosphate (MAPP) of formaldehyde and surperficial scion grafting trimeric cyanamide, prepare the ammonium polyphosphate (being called for short MFAPP) of the coated modification of melamino-formaldehyde resin.
The reaction equation of above-mentioned three steps is as follows:
(1) thermal activation of APP:
(2) activation APP reacts with MEL
(3) crosslinking reaction of MAPP and formaldehyde
Wherein, the crystalline form of described ammonium polyphosphate is I type or II type, and the polymerization degree is 100～2000.
To the temperature of ammonium polyphosphate heat-activated, be 200～290 ℃, soak time is 1～4h.
By controlling the temperature and time to ammonium polyphosphate heat-activated, while guaranteeing activation ammonium polyphosphate to be mixed with the suspension liquid of 1wt%, pH value is 3.0～5.5; And before reacting with trimeric cyanamide, activation ammonium polyphosphate is mixed with to the suspension liquid of 1wt%.
When trimeric cyanamide reacts with activation ammonium polyphosphate, the consumption of trimeric cyanamide is 4%～12% of activation ammonium polyphosphate quality.
Trimeric cyanamide is 240～300 ℃ with the temperature that activation ammonium polyphosphate reacts, and the time is 1～3h.
Before the ammonium polyphosphate crosslinking reaction of formaldehyde and surperficial scion grafting trimeric cyanamide, the ammonium polyphosphate of surperficial scion grafting trimeric cyanamide is mixed with to the suspension liquid of 1wt%, the pH value scope of this suspension liquid is 6.0～8.0.
Carry out with the ammonium polyphosphate of surperficial scion grafting trimeric cyanamide the formalin that the formaldehyde of crosslinking reaction is 30wt%～37wt%, and the mol ratio of the ammonium polyphosphate trimeric cyanamide used of formaldehyde and the surperficial scion grafting trimeric cyanamide of preparation is 1: 1～3: 1.
The temperature of reaction that the ammonium polyphosphate of formaldehyde and surperficial scion grafting trimeric cyanamide carries out crosslinking reaction is 60～90 ℃, and the reaction times is 1～3h.
The wall material of the MFAPP that the present invention makes is melamine resin, and core is APP, and the wall material of MFAPP is connected by chemical bond with core, rather than simple physical adherence is coated.
Compared with prior art, the present invention adopts the MEL of APP surface scion grafting and formaldehyde to carry out crosslinked method to prepare melamine resin wall material and be coated APP.It is to be undertaken by three steps that the melamine resin of APP is coated: first by heating, APP deamination is activated, make to form acid OH base on APP molecular chain, then MEL is reacted with the APP of thermal activation, under temperature of reaction, MEL distillation forms gaseous state MEL molecule, the alkaline NH in MEL molecule
2acid OH radical reaction on base and thermal activation APP molecular chain, obtains the APP (being MAPP) of surperficial scion grafting trimeric cyanamide, finally with formaldehyde and the lip-deep MEL crosslinking polymerization of MAPP, prepares the APP (being MFAPP) of the coated modification of melamino-formaldehyde resin.In the coated modification APP technology of melamine resin of the present invention, MEL makes melamine resin wall material be coated on APP surface by chemical bond as connecting molecule, and the combination of resin wall material and APP core is tight, and the physical strength of modification APP is high; The chemical reaction of three steps is controlled by operation condition and stoichiometric ratio, does not form performed polymer, and solvent (formaldehyde) reclaims easily.
It is large that the inventive method has overcome traditional melamino-formaldehyde resin technology coating modifying raw material consumption, difficult solvent recovery, the deficiency of the combination undertighten of resin shell and ammonium polyphosphate core.Adopt ammonium polyphosphate modified technique of the present invention, the solubleness of the ammonium polyphosphate modifying making only has 0.012g/100g water, than the solubleness of ammonium polyphosphate raw material, has declined more than 90%; The initial decomposition temperature of ammonium polyphosphate modifying reaches 245 ℃, than the initial decomposition temperature of ammonium polyphosphate raw material, has improved 55 ℃; With 30%wt addition, add in polypropylene and make flame-proof composite material, the limiting oxygen index(LOI) of matrix material reaches 28.3%.Therefore, the present invention has reduced raw material consumption, and solvent recuperation is easy, can not cause environmental pollution, and the machining property of prepared MFAPP is good.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
In the glass reactor stirring to band, add 60g APP (II type, polymerization degree >1000), stir-activating in 260 ℃ of oil baths, the NH of release
3through venting port, discharge.The pH value that activates its 1%wt suspension until APP is 3.6 o'clock, adds the MEL of raw material A PP quality 10%, after mixing in 280 ℃ of oil baths airtight stirring reaction 2h, obtain the APP (being MAPP) of scion grafting MEL; MAPP is proceeded to 500mL there-necked flask, by the solid-to-liquid ratio of 1: 2 (mass ratio), add water, then nMEL: nCH in molar ratio
2o=1: 2 add the formalin of 37wt%, airtight stirring reaction 2h in 70 ℃ of waters bath with thermostatic control.Suction filtration, washing, the 60 ℃ of forced air drying 24h of filter cake by obtaining, obtain MFAPP.The solubleness of MFAPP is 0.015g/100g water, and initial decomposition temperature is 236 ℃, with 25%wt addition, MFAPP is added in polypropylene and makes flame-proof composite material, and the limiting oxygen index(LOI) of matrix material reaches 27.8%.
Embodiment 2
In the glass reactor stirring to band, add 120g APP (II type, polymerization degree >1000), stir-activating in 240 ℃ of oil baths, the NH of release
3through venting port, discharge.The pH value that activates its 1%wt suspension until APP is 3.9 o'clock, adds the MEL of raw material A PP quality 8%, after mixing in 260 ℃ of oil baths airtight stirring reaction 2h, obtain the APP (MAPP) of MEL scion grafting; MAPP is proceeded to 1000mL there-necked flask, by the solid-to-liquid ratio of 1: 2, add water, then nMEL: nCH in molar ratio
2o=1: 2 add the formalin of 35wt%, airtight stirring reaction 2h in 80 ℃ of waters bath with thermostatic control.Suction filtration, washing, by the dry 60 ℃ of forced air drying 24h of the filter cake obtaining, obtains the MFAPP of modification.The solubleness of MFAPP is 0.012g/100g water, and the initial decomposition temperature of ammonium polyphosphate modifying reaches 245 ℃, with 30%wt addition, MFAPP is added in polypropylene and makes flame-proof composite material, and the limiting oxygen index(LOI) of matrix material reaches 28.3%.
Embodiment 3
The coated method of modifying of melamino-formaldehyde resin of ammonium polyphosphate, comprises the following steps:
1) by crystalline form, be I type, the polymerization degree ammonium polyphosphate (being called for short APP) that is 100 at 200 ℃ of heat-activated 2h, part deamination forms acid activation ammonium polyphosphate, while guaranteeing activation ammonium polyphosphate to be mixed with the suspension liquid of 1wt%, pH value is 3.0; And before reacting with trimeric cyanamide, activation ammonium polyphosphate is mixed with to the suspension liquid of 1wt%;
2) alkaline trimeric cyanamide (being called for short MEL) is reacted with activation ammonium polyphosphate, temperature is 240 ℃, time is 2.5h, the consumption of trimeric cyanamide is 4% of activation ammonium polyphosphate quality, make MEL scion grafting to activation APP, prepare the ammonium polyphosphate (being called for short MAPP) of surperficial scion grafting trimeric cyanamide, the ammonium polyphosphate of surperficial scion grafting trimeric cyanamide is mixed with to the suspension liquid of 1wt%, the pH value of this suspension liquid is 6.0;
3) with the formalin of 37wt% and the lip-deep trimeric cyanamide of ammonium polyphosphate (MAPP) of surperficial scion grafting trimeric cyanamide, carry out crosslinking reaction, temperature of reaction is 60 ℃, reaction times is 3h, formaldehyde is 1: 1 with the mol ratio of preparation MAPP trimeric cyanamide used, prepares the ammonium polyphosphate (being called for short MFAPP) of the coated modification of melamino-formaldehyde resin.
The solubleness of the MFAPP that the present embodiment prepares is 0.029g/100g water, the initial decomposition temperature of ammonium polyphosphate modifying reaches 233 ℃, with 30%wt addition, MFAPP is added in polypropylene and makes flame-proof composite material, the limiting oxygen index(LOI) of matrix material reaches 27.8%.
Embodiment 4
The coated method of modifying of melamino-formaldehyde resin of ammonium polyphosphate, comprises the following steps:
1) by crystalline form, be II type, the polymerization degree ammonium polyphosphate (being called for short APP) that is 2000 at 290 ℃ of heat-activated 1.5h, part deamination forms acid activation ammonium polyphosphate, while guaranteeing activation ammonium polyphosphate to be mixed with the suspension liquid of 1wt%, pH value is 5.5; And before reacting with trimeric cyanamide, activation ammonium polyphosphate is mixed with to the suspension liquid of 1wt%;
2) alkaline trimeric cyanamide (being called for short MEL) is reacted with activation ammonium polyphosphate, temperature is 300 ℃, time is 1.5h, the consumption of trimeric cyanamide is 12% of activation ammonium polyphosphate quality, make MEL scion grafting to activation APP, prepare the ammonium polyphosphate (being called for short MAPP) of surperficial scion grafting trimeric cyanamide, the ammonium polyphosphate of surperficial scion grafting trimeric cyanamide is mixed with to the suspension liquid of 1wt%, the pH value of this suspension liquid is 8.0;
3) with the formalin of 32wt% and the lip-deep trimeric cyanamide of ammonium polyphosphate (MAPP) of surperficial scion grafting trimeric cyanamide, carry out crosslinking reaction, temperature of reaction is 90 ℃, reaction times is 1h, formaldehyde is 3: 1 with the mol ratio of preparation MAPP trimeric cyanamide used, prepares the ammonium polyphosphate (being called for short MFAPP) of the coated modification of melamino-formaldehyde resin.
The solubleness of the MFAPP that the present embodiment prepares is 0.013g/100g water, the initial decomposition temperature of ammonium polyphosphate modifying reaches 241 ℃, with 30%wt addition, MFAPP is added in polypropylene and makes flame-proof composite material, the limiting oxygen index(LOI) of matrix material reaches 28.0%.
The above-mentioned description to embodiment is can understand and use invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (9)
1. the coated method of modifying of the melamino-formaldehyde resin of ammonium polyphosphate, is characterized in that, comprises the following steps:
1), by ammonium polyphosphate heat-activated, part deamination forms acid activation ammonium polyphosphate;
2) trimeric cyanamide is reacted to the ammonium polyphosphate for preparing surperficial scion grafting trimeric cyanamide with activation ammonium polyphosphate;
3), by the lip-deep trimeric cyanamide crosslinking reaction of ammonium polyphosphate of formaldehyde and surperficial scion grafting trimeric cyanamide, prepare the ammonium polyphosphate of the coated modification of melamino-formaldehyde resin.
2. the coated method of modifying of the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1, is characterized in that, the crystalline form of described ammonium polyphosphate is I type or II type, and the polymerization degree is 100～2000.
3. the coated method of modifying of the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1, is characterized in that, to the temperature of ammonium polyphosphate heat-activated, is 200～290 ℃, and soak time is 1～4h.
4. the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1 is coated method of modifying, it is characterized in that, by controlling the temperature and time to ammonium polyphosphate heat-activated, while guaranteeing activation ammonium polyphosphate to be mixed with the suspension liquid of 1wt%, pH value is 3.0～5.5; And before reacting with trimeric cyanamide, activation ammonium polyphosphate is mixed with to the suspension liquid of 1wt%.
5. the coated method of modifying of the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1, is characterized in that, when trimeric cyanamide reacts with activation ammonium polyphosphate, the consumption of trimeric cyanamide is 4%～12% of activation ammonium polyphosphate quality.
6. the coated method of modifying of the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1, is characterized in that, trimeric cyanamide is 240～300 ℃ with the temperature that activation ammonium polyphosphate reacts, and the time is 1～3h.
7. the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1 is coated method of modifying, it is characterized in that, before the ammonium polyphosphate crosslinking reaction of formaldehyde and surperficial scion grafting trimeric cyanamide, the ammonium polyphosphate of surperficial scion grafting trimeric cyanamide is mixed with to the suspension liquid of 1wt%, the pH value scope of this suspension liquid is 6.0～8.0.
8. the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1 is coated method of modifying, it is characterized in that, carry out with the ammonium polyphosphate of surperficial scion grafting trimeric cyanamide the formalin that the formaldehyde of crosslinking reaction is 30wt%～37wt%, and the mol ratio of the ammonium polyphosphate trimeric cyanamide used of formaldehyde and the surperficial scion grafting trimeric cyanamide of preparation is 1: 1～3: 1.
9. the coated method of modifying of the melamino-formaldehyde resin of a kind of ammonium polyphosphate according to claim 1, is characterized in that, the temperature of reaction that the ammonium polyphosphate of formaldehyde and surperficial scion grafting trimeric cyanamide carries out crosslinking reaction is 60～90 ℃, and the reaction times is 1～3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410222743.3A CN103980541B (en) | 2014-05-23 | 2014-05-23 | A kind of melamino-formaldehyde resin coating modification method of ammonium polyphosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410222743.3A CN103980541B (en) | 2014-05-23 | 2014-05-23 | A kind of melamino-formaldehyde resin coating modification method of ammonium polyphosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103980541A true CN103980541A (en) | 2014-08-13 |
| CN103980541B CN103980541B (en) | 2016-06-15 |
Family
ID=51272724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410222743.3A Expired - Fee Related CN103980541B (en) | 2014-05-23 | 2014-05-23 | A kind of melamino-formaldehyde resin coating modification method of ammonium polyphosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980541B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927060A (en) * | 2015-02-07 | 2015-09-23 | 南阳理工学院 | Intumescent flame retardant and preparation method thereof |
| CN109133021A (en) * | 2018-11-07 | 2019-01-04 | 武汉联德化学品有限公司 | A kind of preparation method for fire-retardant biphosphate potassium granular formulation |
| CN112111094A (en) * | 2020-09-25 | 2020-12-22 | 常州大学 | Resin-coated diethyl aluminum hypophosphite flame-retardant low-density polyethylene and preparation method thereof |
| CN113801482A (en) * | 2021-09-29 | 2021-12-17 | 武汉工程大学 | Bio-based microencapsulated MFAPP flame retardant and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1480253A (en) * | 2003-04-10 | 2004-03-10 | 上海化工研究院 | Method for making ammonium polyphosphate clad by microcapsules |
| CN101829527A (en) * | 2010-04-01 | 2010-09-15 | 河北大学 | Method for preparing microcapsule-coated ammonium polyphosphate |
| CN102936429A (en) * | 2012-10-26 | 2013-02-20 | 清远市普塞呋磷化学有限公司 | Preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate (APP) |
-
2014
- 2014-05-23 CN CN201410222743.3A patent/CN103980541B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1480253A (en) * | 2003-04-10 | 2004-03-10 | 上海化工研究院 | Method for making ammonium polyphosphate clad by microcapsules |
| CN101829527A (en) * | 2010-04-01 | 2010-09-15 | 河北大学 | Method for preparing microcapsule-coated ammonium polyphosphate |
| CN102936429A (en) * | 2012-10-26 | 2013-02-20 | 清远市普塞呋磷化学有限公司 | Preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate (APP) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927060A (en) * | 2015-02-07 | 2015-09-23 | 南阳理工学院 | Intumescent flame retardant and preparation method thereof |
| CN104927060B (en) * | 2015-02-07 | 2017-10-24 | 南阳理工学院 | A kind of expansion type flame retardant and preparation method thereof |
| CN109133021A (en) * | 2018-11-07 | 2019-01-04 | 武汉联德化学品有限公司 | A kind of preparation method for fire-retardant biphosphate potassium granular formulation |
| CN112111094A (en) * | 2020-09-25 | 2020-12-22 | 常州大学 | Resin-coated diethyl aluminum hypophosphite flame-retardant low-density polyethylene and preparation method thereof |
| CN113801482A (en) * | 2021-09-29 | 2021-12-17 | 武汉工程大学 | Bio-based microencapsulated MFAPP flame retardant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103980541B (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103980541B (en) | A kind of melamino-formaldehyde resin coating modification method of ammonium polyphosphate | |
| CN101838224B (en) | Method for reducing grain size of AC foaming agent | |
| CN109503860B (en) | Modified lignin for intumescent flame retardant and preparation method thereof, intumescent flame retardant and preparation method thereof | |
| CN102827399A (en) | Phosphorus and nitrogen fire retardant and preparation method thereof | |
| CN102690379A (en) | Method for preparing polyvinyl butyral high-polymer resin | |
| CN107586461B (en) | A kind of preparation method of formaldehydeless flame retardant type fiberboard | |
| CN102030905B (en) | Method for preparing solvent-free high hydrogen containing silicone oil | |
| CN104629662B (en) | The urea-formaldehyde resin adhesive of a kind of ultra-low formaldehyde release and preparation technology thereof | |
| CN109762013A (en) | Melamine cyanurate with silane structure, preparation method and its application | |
| CN107304255B (en) | Composite flame-retardant agent, flame-retardant pitch and preparation method thereof | |
| CN106916269A (en) | A kind of preparation method of high stability melamine resin | |
| CN100478374C (en) | High solid content melamine resin and production method thereof | |
| CN104558481B (en) | Preparation method of thermal-insulation lignin-base polyurethane foam | |
| CN103772640B (en) | A kind of flame retardant type wood adhesive and its preparation method and application | |
| CN104559185A (en) | Compound type microencapsulated ammonium polyphosphate master batch | |
| CN105585681A (en) | Preparation method of melamino-formaldehyde resin powder | |
| CN108727548A (en) | Environmental-protection flame-retardant high water solubility imino group melamine resin and its production method | |
| CN106117155A (en) | A kind of trimethylol melamine and hexakis(hydroxymethyl)melamine co-production | |
| CN106008870A (en) | Method for synthesizing high imino etherification amino resin from trimethylol melamine and hexamethylolmelamine | |
| CN105153470A (en) | Fire retardant preparation method | |
| CN106243299B (en) | A kind of technique of continuous production melamine resin | |
| CN104098789B (en) | A kind of ammonium polyphosphate of silane-containing structure and preparation method thereof and application in main chain | |
| CN101024680B (en) | Binaphthyl-radicle-contained di-phenol A-type resin and its preparing method | |
| CN107603513A (en) | A kind of method of cassava oxidized starch base adhesive | |
| CN106009170A (en) | Flame-retardant wood-plastic material 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160615 Termination date: 20180523 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |