CN103709445B - A kind of preparation method of the melmac coated ammonium polyphosphate had excellent water-resistance - Google Patents
A kind of preparation method of the melmac coated ammonium polyphosphate had excellent water-resistance Download PDFInfo
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Abstract
The invention provides a kind of melmac coated ammonium polyphosphate preparation method had excellent water-resistance, relate to phosphoric acid salt fine chemistry industry preparation field, ammonium polyphosphate to add in the pretreatment solution that alcohol mixes with promoting agent as Xia ﹕ by method, reacts to obtain pre-treatment APP; In melmac solution, add amendment react to obtain coated treatment solution; Pre-treatment APP is mixed with coated treatment solution, then adds initiator, react to obtain reaction solution, reaction solution is separated to obtain wet stock, drier, to obtain final product.The present invention carries out coating modification process for the ammonium polyphosphate of common quality in a creative way, preparation technology is simple, easy to operate, prepared melmac coated ammonium polyphosphate product has good water resistance, its normal-temperature dissolution degree < 0.8g/100mL water, achieving the effect that the coated rear comprehensive water resistance of common quality ammonium polyphosphate raw material significantly promotes, is the comparatively feasible method of common quality ammonium polyphosphate coating modification.
Description
Technical field
The present invention relates to phosphoric acid salt fine chemistry industry preparation field, particularly relate to a kind of melmac coated ammonium polyphosphate preparation method had excellent water-resistance.
Background technology
Ammonium polyphosphate (hereinafter referred to as APP) product is a kind of important inorganic phosphorus flame retardant developed rapidly in recent years, belong to additive flame retardant, it is the main component of expansion type flame retardant, there is good anti-flaming function, press down cigarette, not halogen-containing, toxicity is lower, becomes the product realizing the non-halogen most prospect of fire retardant.
Along with China requires the continuous reinforcement of dynamics to flame-retarded technology, establish and improve relevant flame retardant regulation gradually, the demand of APP increased day by day, especially to the properties of product particularly water tolerance have higher requirement.But APP is because of himself chemical structure feature, and water absorbability is very strong when high temperature, high humidity, (especially the APP of low polymerization degree) can be oozed out to material surface migration, reduce flame-retarded efficiency; In addition, APP adds can make the physical strength of material itself reduce in organic materials, affect it and normally use, thus limit APP in flame retardant area, particularly the widespread use of macromolecular material flame retardant area.
Improve the APP product polymerization degree (being greater than 1000) and can water absorbability be reduced, strengthen thermostability, but only improve the polymerization degree of APP, the essence of APP as inorganics can not be avoided completely, still exist with the consistency of superpolymer bad, in macromolecular material, the problem such as not easily to disperse.Study carefully it former in ﹕ mono-aspect polymeric body surface oleophyllie hydrophobic, and APP hydrophilic and oleophobic, surface polarity differs greatly and causes objectionable intermingling between the two, and interaction force between interface is very little; On the other hand because the surface tension between inorganic particulate is large, very easily reunite, be unfavorable for the dispersion in polymeric matrix.
Therefore, need to carry out suitable surface modification treatment to APP product, reduce water absorbability, strengthen thermostability, to improve its dispersiveness in macromolecular material and consistency, expand the widespread use of APP in macromolecular material flame retardant area.Microcapsulary is adopted to be solve APP product one of effective way that there is self-defect in application process.
Microcapsulary utilizes polymer that is natural or synthesis to be coating material (as melmac, epoxy resin, urea-formaldehyde resin etc.), by coated for the small core material of solid, liquid or gas, form the minigel with semipermeability or closing membrane that diameter is 1 ~ 50 μm.APP coating modification is exactly that its effect is similar to the effect of sugar-coat in medicine at the water-fast resin adventitia of the coated last layer of the outside surface of APP solid particulate.After coated process, because adventitia has completely cut off APP and extraneous contact, therefore, it is possible to effectively reduce the water-soluble of APP, promote its water tolerance.Resin adventitia simultaneously owing to adopting belongs to macromolecular material, and be obviously better than APP with the consistency of superpolymer, coated process can improve the consistency of APP and superpolymer, widens the use range of APP.
There is patent to carry out surface of microcapsule process to II type APP both at home and abroad, to improve its shortcoming, better play the effect of APP fire retardant.US5700575, US5700575 etc. patent discloses with the coated II type APP of melamine formaldehyde resin, the method for II type APP that preparation has resistant to hydrolysis performance, that improve consistency.
From existing open source information, APP product modification is greater than 1000 mainly for the high-quality APP(polymerization degree, II type APP) product carries out, to occupying the common quality APP(polymerization degree of domestic market overwhelming majority share about 100) the rare concern of product, but, the water resistance of this type of APP poorer (have higher water-soluble), research for the low cost surface modification technologies of common quality APP product, is very useful to the range of application widening APP specially.
Summary of the invention
For above-mentioned defect and the problem of prior art, the object of this invention is to provide a kind of ammonium polyphosphate raw material (mean polymerisation degree < 100 for common quality, normal-temperature dissolution degree < 5.0g/100mL water), through melmac coating modification process, obtain the melmac coated ammonium polyphosphate had excellent water-resistance, normal-temperature dissolution degree < 0.8g/100mL water.Solve the poor water resistance of the ammonium polyphosphate raw material of existing common quality, cause the problem that it is of limited application.
In order to achieve the above object, the invention provides following Ji art Fang An ﹕
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance realizes ﹕ by following steps
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 10 ~ 100 ﹕ 1 in the mass ratio of alcohol and promoting agent, is mixed by alcohol, obtain pretreatment solution with promoting agent; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 20% ~ 60% of pretreatment solution quality, and the C atomicity of alcohol is 1-5;
The Bei ﹕ processed of step 2, coated treatment solution adds amendment, insulation reaction in the melmac solution of 40 ~ 65 DEG C, obtains coated treatment solution; Wherein, the add-on of amendment is 0.5% ~ 10% of trimeric cyanamide quality in melmac solution;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ (0.5 ~ 10), pre-treatment ammonium polyphosphate solidliquid mixture is mixed to obtain mixed solution with coated treatment solution, initiator is added again in mixed solution, obtain coated system, the add-on of described initiator is 5 ~ 30% of coated treatment solution quality, regulate pH value to 2.5 ~ 5.5 of coated system, then react 30 ~ 180 minutes at the temperature of 55 ~ 100 DEG C, obtain reaction system, again reaction system is separated and obtains wet stock, again that wet stock is dry, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
Further, ammonium polyphosphate described in step one is mean polymerisation degree < 100, the common ammonium polyphosphate of normal-temperature dissolution degree < 5.0g/100mL water.
Further, promoting agent described in step one is selected from one or more the mixture in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, when for multiple mixture, with arbitrarily than mixing.
Further, the alcohol described in step one is anhydrous methanol or dehydrated alcohol.
Particularly, be the ratio of 30 ~ 80 ﹕ 1 in the mass ratio of alcohol and promoting agent in step one, alcohol mixed with promoting agent, obtains pretreatment solution.More specifically, be the ratio of 50 ﹕ 1 in the mass ratio of alcohol and promoting agent, alcohol is mixed with promoting agent.
Particularly, in step one, the add-on of ammonium polyphosphate is 50% ~ 60% of pretreatment solution quality.
Further, in step one, the stirring reaction time is 5 ~ 30 minutes;
Further, the solution of melmac described in step 2 is adopted system with the following method and is followed successively by 1:(1 ~ 10 for arriving ﹕ according to the mass ratio of trimeric cyanamide, formaldehyde solution and water): the ratio of (30 ~ 100), trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 5.5 ~ 9.5 of mixed solution, then at the temperature of 45 ~ 100 DEG C, stirring reaction 30 ~ 180 minutes, obtains melmac solution.Wherein, the mass ratio of trimeric cyanamide, formaldehyde solution and water is followed successively by 1:(1 ~ 10): the mass ratio of what (30 ~ 100) represented is trimeric cyanamide and formaldehyde solution is 1:(1 ~ 10), the mass ratio of trimeric cyanamide and water is 1:(30 ~ 100).
Particularly, described trimeric cyanamide adopts technical grade.
Particularly, be followed successively by 1:(2 ~ 8 according to the mass ratio of trimeric cyanamide, formaldehyde solution and water): the ratio of (45 ~ 80), is mixed to get mixed solution by trimeric cyanamide, formaldehyde solution and water.More specifically, 1:(2 ~ 5 are followed successively by according to the mass ratio of trimeric cyanamide, formaldehyde solution and water): the ratio of (45 ~ 60).
Preferably, in the preparation method of the solution of melmac described in step 2, regulate pH value to 7.5 ~ 9.0 of mixed solution.More preferably, pH value to 8.0 ~ 8.5 of mixed solution are regulated.
Further, amendment described in step 2 is formulated by urea, polyvinyl alcohol, Resorcinol.
Particularly, described amendment is 1:(0.5 ~ 5 in the mass ratio of urea and polyvinyl alcohol), the mass ratio of urea and Resorcinol is 1:(0.5 ~ 5) ratio formulated by urea, polyvinyl alcohol, Resorcinol, namely the mass ratio of urea, polyvinyl alcohol and Resorcinol is followed successively by 1:(0.5 ~ 5): (0.5 ~ 5).
Preferably, in step 2, the add-on of amendment is 1% ~ 6% of trimeric cyanamide quality in melmac solution; More preferably, the add-on of amendment is 1.5% ~ 4% of trimeric cyanamide quality in melmac solution; Preferred aspect ground, the add-on of amendment is 2% of trimeric cyanamide quality in melmac solution.
Further, initiator described in step 3 is be that the phosphoric acid of 90% ~ 110% is with formulated containing the fatty alcohol of 1 ~ 3 carbon atom by massfraction.Particularly, the mass ratio of phosphoric acid and fatty alcohol is 1:(1 ~ 3).More specifically, described fatty alcohol is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, when for multiple mixture, with arbitrarily than mixing.
Further, Wei ﹕ at the temperature of 70 ~ 140 DEG C 60 ~ 180 minutes by the processing mode of wet stock drying in step 3.
Particularly, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one in step 3 and step 2 obtain is the ratio of 1 ﹕ (1 ~ 5), and pre-treatment ammonium polyphosphate solidliquid mixture is mixed to obtain mixed solution with coated treatment solution.More particularly, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ (1.5 ~ 2.5).Again particularly, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 2.
Preferably, pH value to 3.5 ~ 5.5 of coated system are regulated in step 3; More preferably, pH value to 4.0 ~ 5.0 of coated system are regulated; Optimally, pH value to 4.0 ~ 5.0 of coated system are regulated.
Preferably, the add-on of initiator described in step 3 is 10 ~ 20% of coated treatment solution quality; More preferably, the add-on of described initiator is 15% of coated treatment solution quality.
The preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance provided by the invention, in a creative way for the ammonium polyphosphate of common quality, terpolycyantoamino-formaldehyde resin is adopted to carry out coating modification process to it, by stepwise reaction technique simple to operation, prepare the melmac coated ammonium polyphosphate that water tolerance is good, its normal-temperature dissolution degree < 0.8g/100mL water, achieve the effect that the coated rear comprehensive water resistance of common quality ammonium polyphosphate raw material significantly promotes, it is the comparatively feasible method of common quality ammonium polyphosphate coating modification.
It is simple that the present invention has following useful Xiao Guo ﹕ preparation technology, and easy to operate, prepared melmac coated ammonium polyphosphate product has good water resistance.Can effectively reduce the water-soluble of ammonium polyphosphate after coated, promote its water tolerance.After tested, the coated ammonium polyphosphate sample obtained with art breading of the present invention all shows the water tolerance being much better than raw material in normal-temperature dissolution degree, normal temperature water tolerance and hot water dissolving's degree three kinds test.By coated, common quality ammonium polyphosphate raw material normal-temperature water solubleness can greatly be reduced.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the SEM test pattern of the amplification 2000 times of the ammonium polyphosphate adopted in the step one of embodiments of the invention 1;
Fig. 2 is the SEM test pattern that melmac coated ammonium polyphosphate that the embodiment of the present invention 1 prepares amplifies 2000 times;
Fig. 3 is the SEM test pattern that melmac coated ammonium polyphosphate that the embodiment of the present invention 1 prepares amplifies 5000 times.
Embodiment
Below in conjunction with embodiments of the invention, be clearly and completely described technical scheme of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, is realized by following steps:
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 25 ﹕ 1 in the mass ratio of anhydrous methanol and Sodium dodecylbenzene sulfonate promoting agent, anhydrous methanol is mixed with Sodium dodecylbenzene sulfonate promoting agent, obtain pretreatment solution, pretreatment solution is joined in the reactor with heated and stirred function; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction 20 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 50% of pretreatment solution quality;
The Bei ﹕ a processed of step 2, coated treatment solution, according to technical grade trimeric cyanamide, 37%(quality) mass ratio of formaldehyde solution and water is followed successively by the ratio of 1:2:45, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 8.5 ~ 9.0 of mixed solution, then at the temperature of 80 DEG C, Keep agitation reacts 60 minutes, obtains melmac solution; After b, melmac solution a step obtained are cooled to 40 ~ 65 DEG C, then add amendment wherein, insulated and stirred reaction 30min, obtains coated treatment solution; Wherein, the add-on of amendment is 0.5% of trimeric cyanamide quality in melmac solution, and it is formulated that amendment is followed successively by the urea of 1:2:2, polyvinyl alcohol and Resorcinol by mass ratio;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 2.5, pre-treatment ammonium polyphosphate solidliquid mixture is mixed to obtain mixed solution with coated treatment solution, the mixture of coated treatment solution quality 10% initiator (initiator is 90%(massfraction) phosphoric acid and ethanol 1:1 is in mass ratio added again) in mixed solution, obtain coated system, regulate pH value to 5.0 ~ 5.5 of coated system, then react 120 minutes at the temperature of 70 DEG C, obtain reaction system, again reaction system suction filtration is obtained wet stock, again by wet stock at the temperature of 110 DEG C dry 60 minutes, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
In the present embodiment 1, the scanning electron microscope test figure of the melmac coated ammonium polyphosphate prepared shown in scanning electronic microscope (SEM) test pattern and Fig. 2 and Fig. 3 of the ammonium polyphosphate that the step one shown in comparison diagram 1 adopts, known, the present embodiment 1 pair of ammonium polyphosphate has carried out coating modification well.
Embodiment 2
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, is realized by following steps:
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 14 ﹕ 1 in the mass ratio of anhydrous methanol and sodium lauryl sulphate promoting agent, anhydrous methanol is mixed with sodium lauryl sulphate promoting agent, obtain pretreatment solution, pretreatment solution is joined in the reactor with heated and stirred function; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 60% of pretreatment solution quality;
The Bei ﹕ a processed of step 2, coated treatment solution, according to technical grade trimeric cyanamide, 37%(quality) mass ratio of formaldehyde solution and water is followed successively by the ratio of 1:3:60, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 7.5 ~ 8.0 of mixed solution, then at the temperature of 90 DEG C, Keep agitation reacts 120 minutes, obtains melmac solution; After b, melmac solution a step obtained are cooled to 40 ~ 65 DEG C, then add amendment wherein, insulated and stirred reaction 20min, obtains coated treatment solution; Wherein, the add-on of amendment is 1% of trimeric cyanamide quality in melmac solution, and it is formulated that amendment is followed successively by the urea of 1:2:2, polyvinyl alcohol and Resorcinol by mass ratio;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 2, pre-treatment ammonium polyphosphate solidliquid mixture is mixed to obtain mixed solution with coated treatment solution, the mixture of coated treatment solution quality 15% initiator (initiator is 95%(massfraction) phosphoric acid and ethanol 1:1.5 is in mass ratio added again) in mixed solution, obtain coated system, regulate pH value to 4.5 ~ 5.0 of coated system, then react 180 minutes at the temperature of 85 DEG C, obtain reaction system, again reaction system suction filtration is obtained wet stock, again by wet stock at the temperature of 110 DEG C dry 60 minutes, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
Embodiment 3
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, is realized by following steps:
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 10 ﹕ 1 in the mass ratio of dehydrated alcohol and sodium laurylsulfonate promoting agent, dehydrated alcohol is mixed with sodium laurylsulfonate promoting agent, obtain pretreatment solution, pretreatment solution is joined in the reactor with heated and stirred function; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 60% of pretreatment solution quality;
The Bei ﹕ a processed of step 2, coated treatment solution, according to technical grade trimeric cyanamide, 37%(quality) mass ratio of formaldehyde solution and water is followed successively by the ratio of 1:4:50, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 8.0 ~ 8.5 of mixed solution, then at the temperature of 85 DEG C, Keep agitation reacts 80 minutes, obtains melmac solution; After b, melmac solution a step obtained are cooled to 40 ~ 65 DEG C, then add amendment wherein, insulated and stirred reaction 30min, obtains coated treatment solution; Wherein, the add-on of amendment is 1.5% of trimeric cyanamide quality in melmac solution, and it is formulated that amendment is followed successively by the urea of 1:5:5, polyvinyl alcohol and Resorcinol by mass ratio;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 2, mixed solution is mixed to obtain after pre-treatment ammonium polyphosphate solidliquid mixture is stirred 10 minutes with coated treatment solution, the mixture of coated treatment solution quality 15% initiator (initiator is 95%(massfraction) phosphoric acid and ethanol 1:2 is in mass ratio added again) in mixed solution, obtain coated system, regulate pH value to 4.0 ~ 4.5 of coated system, then react 120 minutes at the temperature of 80 DEG C, obtain reaction system, again reaction system suction filtration is obtained wet stock, again by wet stock at the temperature of 110 DEG C dry 180 minutes, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
Embodiment 4
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, is realized by following steps:
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 50 ﹕ 1 in the mass ratio of dehydrated alcohol and promoting agent (Sodium dodecylbenzene sulfonate and sodium lauryl sulphate mass ratio are the mixture of 1 ﹕ 1), dehydrated alcohol is mixed with promoting agent, obtain pretreatment solution, pretreatment solution is joined in the reactor with heated and stirred function; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 60% of pretreatment solution quality;
The Bei ﹕ a processed of step 2, coated treatment solution, according to technical grade trimeric cyanamide, 37%(quality) mass ratio of formaldehyde solution and water is followed successively by the ratio of 1:5:60, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 8.0 ~ 8.5 of mixed solution, then at the temperature of 85 DEG C, Keep agitation reacts 120 minutes, obtains melmac solution; After b, melmac solution a step obtained are cooled to 40 ~ 65 DEG C, then add amendment wherein, insulated and stirred reaction 30min, obtains coated treatment solution; Wherein, the add-on of amendment is 2% of trimeric cyanamide quality in melmac solution, and it is formulated that amendment is followed successively by the urea of 1:3:5, polyvinyl alcohol and Resorcinol by mass ratio;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 1.7, mixed solution is mixed to obtain after pre-treatment ammonium polyphosphate solidliquid mixture is stirred 10 minutes with coated treatment solution, the mixture of coated treatment solution quality 15% initiator (initiator is 110%(massfraction) phosphoric acid and methyl alcohol 1:3 is in mass ratio added again) in mixed solution, obtain coated system, regulate pH value to 4.0 ~ 4.5 of coated system, then react 180 minutes at the temperature of 85 DEG C, obtain reaction system, again reaction system suction filtration is obtained wet stock, again by wet stock at the temperature of 90 DEG C dry 180 minutes, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
Embodiment 5
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, is realized by following steps:
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 80 ﹕ 1 in the mass ratio of dehydrated alcohol and promoting agent (Sodium dodecylbenzene sulfonate and sodium laurylsulfonate mass ratio are the mixture of 1 ﹕ 1), dehydrated alcohol is mixed with promoting agent, obtain pretreatment solution, pretreatment solution is joined in the reactor with heated and stirred function; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 55% of pretreatment solution quality;
The Bei ﹕ a processed of step 2, coated treatment solution, according to technical grade trimeric cyanamide, 37%(quality) mass ratio of formaldehyde solution and water is followed successively by the ratio of 1:3:45, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 8.0 ~ 8.5 of mixed solution, then at the temperature of 80 DEG C, Keep agitation reacts 100 minutes, obtains melmac solution; After b, melmac solution a step obtained are cooled to 40 ~ 65 DEG C, then add amendment wherein, insulated and stirred reaction 25min, obtains coated treatment solution; Wherein, the add-on of amendment is 1% of trimeric cyanamide quality in melmac solution, and it is formulated that amendment is followed successively by the urea of 1:4:4, polyvinyl alcohol and Resorcinol by mass ratio;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 2, mixed solution is mixed to obtain after pre-treatment ammonium polyphosphate solidliquid mixture is stirred 10 minutes with coated treatment solution, the mixture of coated treatment solution quality 15% initiator (initiator is 100%(massfraction) phosphoric acid and methyl alcohol 1:2.5 is in mass ratio added again) in mixed solution, obtain coated system, regulate pH value to 4.0 ~ 4.5 of coated system, then react 120 minutes at the temperature of 80 DEG C, obtain reaction system, again reaction system suction filtration is obtained wet stock, again by wet stock at the temperature of 90 DEG C dry 120 minutes, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
Embodiment 6
A preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, is realized by following steps:
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 30 ﹕ 1 in the mass ratio of dehydrated alcohol and promoting agent (mass ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and sodium laurylsulfonate is the mixture of 1 ﹕ 1 ﹕ 1), dehydrated alcohol is mixed with promoting agent, obtain pretreatment solution, pretreatment solution is joined in the reactor with heated and stirred function; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 60% of pretreatment solution quality;
The Bei ﹕ a processed of step 2, coated treatment solution, according to technical grade trimeric cyanamide, 37%(quality) mass ratio of formaldehyde solution and water is followed successively by the ratio of 1:2:60, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 7.5 ~ 8.0 of mixed solution, then at the temperature of 80 DEG C, Keep agitation reacts 60 minutes, obtains melmac solution; After b, melmac solution a step obtained are cooled to 40 ~ 65 DEG C, then add amendment wherein, insulated and stirred reaction 30min, obtains coated treatment solution; Wherein, the add-on of amendment is 2% of trimeric cyanamide quality in melmac solution, and it is formulated that amendment is followed successively by the urea of 1:0.5:1, polyvinyl alcohol and Resorcinol by mass ratio;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 2, mixed solution is mixed to obtain after pre-treatment ammonium polyphosphate solidliquid mixture is stirred 10 minutes with coated treatment solution, the mixture of coated treatment solution quality 15% initiator (initiator is 90%(massfraction) phosphoric acid and ethanol 1:2 is in mass ratio added again) in mixed solution, obtain coated system, regulate pH value to 3.5 ~ 4.0 of coated system, then react 180 minutes at the temperature of 80 DEG C, obtain reaction system, again reaction system suction filtration is obtained wet stock, again by wet stock at the temperature of 90 DEG C dry 180 minutes, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
The quality index of the ammonium polyphosphate adopted in the step one of above-described embodiment 1 to enforcement 6 is as shown in table 1.
Table 1 is the quality index of the ammonium polyphosphate adopted in step one in embodiment 1 to enforcement 6.
Table 1
The present invention tests with the water tolerance of the coating modification product of the melmac coated ammonium polyphosphate prepared respectively to the ammonium polyphosphate raw material that embodiment 1 to embodiment 6 adopts, and result is as shown in table 2.
Table 2 is water resistance test results of the coating modification product of the ammonium polyphosphate raw material adopted in embodiment 1 to embodiment 6 and the melmac coated ammonium polyphosphate prepared.
Table 2
In the present invention, the method for water resistance test is as Xia ﹕
Normal-temperature dissolution degree Ce Shi ﹕ specific analytical method is undertaken by the prescriptive procedure of solubleness test in " HG/T2770-2008 industry ammonium polyphosphate ".
Normal temperature water tolerance Ce Shi ﹕ and aforementioned normal-temperature dissolution degree testing method change 8 hours into unlike the continuously stirring time, and all the other operations are with normal-temperature dissolution degree test operation method.
The ratio that 85 DEG C of hot water water tolerance Ce Shi ﹕ specify in normal-temperature dissolution degree testing method samples and configures sample aqueous solution, and keep 3 hours at 85 DEG C of temperature after stirring, operation steps is with normal-temperature dissolution degree testing method afterwards.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should described be as the criterion with the protection domain of claim.
Claims (7)
1. a preparation method for the melmac coated ammonium polyphosphate had excellent water-resistance, it is being the ﹕ realized by following steps in ﹕ that its spy levies
The Qian Chu Li ﹕ of step one, ammonium polyphosphate is the ratio of 10 ~ 100 ﹕ 1 in the mass ratio of alcohol and promoting agent, is mixed by alcohol, obtain pretreatment solution with promoting agent; Added by ammonium polyphosphate in pretreatment solution, under the temperature of reaction of 35 ~ 55 DEG C, stirring reaction, obtains pre-treatment ammonium polyphosphate solidliquid mixture, and wherein, the add-on of ammonium polyphosphate is 20% ~ 60% of pretreatment solution quality, and the C atomicity of alcohol is 1-5; Described ammonium polyphosphate is mean polymerisation degree < 100, the common ammonium polyphosphate of normal-temperature dissolution degree < 5.0g/100mL water;
The Bei ﹕ processed of step 2, coated treatment solution adds amendment, insulation reaction in the melmac solution of 40 ~ 65 DEG C, obtains coated treatment solution; Wherein, the add-on of amendment is 0.5% ~ 10% of trimeric cyanamide quality in melmac solution; Described amendment is formulated by urea, polyvinyl alcohol, Resorcinol, and the mass ratio of urea and polyvinyl alcohol is 1:0.5 ~ 5, the mass ratio of urea and Resorcinol is 1:0.5 ~ 5;
Step 3, the mass ratio of the coated treatment solution that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step one and step 2 obtain is the ratio of 1 ﹕ 0.5 ~ 10, pre-treatment ammonium polyphosphate solidliquid mixture is mixed to obtain mixed solution with coated treatment solution, initiator is added again in mixed solution, obtain coated system, the add-on of described initiator is 5 ~ 30% of coated treatment solution quality, regulate pH value to 2.5 ~ 5.5 of coated system, then react 30 ~ 180 minutes at the temperature of 55 ~ 100 DEG C, obtain reaction system, again reaction system is separated and obtains wet stock, again that wet stock is dry, obtain melmac coated ammonium polyphosphate, complete the preparation method of melmac coated ammonium polyphosphate.
2. the preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance according to claim 1, its spy levies and must arrive ﹕ to be followed successively by 1:1 ~ 10:30 ~ 100 ratio according to the mass ratio of trimeric cyanamide, formaldehyde solution and water system with the following method of adopting in melmac solution described in ﹕ step 2 is standby, trimeric cyanamide, formaldehyde solution and water are mixed to get mixed solution, regulate pH value to 5.5 ~ 9.5 of mixed solution, then at the temperature of 45 ~ 100 DEG C, stirring reaction 30 ~ 180 minutes, obtains melmac solution.
3. the preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance according to claim 2, Qi Te levies pH value to 7.5 ~ 9.0 that Yu ﹕ regulates mixed solution.
4. the preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance according to claim 1,2 or 3, Qi Te levies promoting agent described in Yu ﹕ step one and is selected from one or more the mixture in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, when for multiple mixture, with arbitrarily than mixing.
5. the preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance according to claim 1,2 or 3, it is being be that the phosphoric acid of 90% ~ 100% is with formulated containing the fatty alcohol of 1 ~ 3 carbon atom by massfraction in initiator described in ﹕ step 3 that its spy levies.
6. the preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance according to claim 5, the mass ratio that Qi Te levies Yu ﹕ phosphoric acid and fatty alcohol is 1:1 ~ 3.
7. the preparation method of a kind of melmac coated ammonium polyphosphate had excellent water-resistance according to claim 1,2 or 3, it is ﹕ at the temperature of 70 ~ 140 DEG C 60 ~ 180 minutes by the processing mode of wet stock drying that Qi Te levies in Yu ﹕ step 3.
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