CN100400544C - Metallic ion modified polyphosphoric acid melamine salt and its preparation method - Google Patents
Metallic ion modified polyphosphoric acid melamine salt and its preparation method Download PDFInfo
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- CN100400544C CN100400544C CNB2005100102557A CN200510010255A CN100400544C CN 100400544 C CN100400544 C CN 100400544C CN B2005100102557 A CNB2005100102557 A CN B2005100102557A CN 200510010255 A CN200510010255 A CN 200510010255A CN 100400544 C CN100400544 C CN 100400544C
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Abstract
The present invention relates to a metallic ion modified polyphosphoric acid melamine salt and a preparing method thereof, particularly to a phosphorus-nitrogen containing flame retardant with high thermal stability and a preparing technology thereof. The present invention aims at solving the problems that the polyphosphoric acid melamine salt has low stability and has high acidity and low flame-retardant performance in water. The product of the present invention is prepared from the ingredients according to the following weight percentages: 21% to 25% of oxygen, 15% to 18% of carbon, 1% to 3% of hydrogen, 13% to 16% of phosphorus, 37% to 42% of nitrogen and 0.2% to 6% of metal ion. The preparing method of the present invention comprises the following steps: metal hydroxide, oxide or carbonate is dissolved or dispersed in a phosphoric acid solution with the concentration of 80% to 90%; water, the phosphoric acid solution which comprises dihydric phosphate, and melamine react in a reaction kettle for two hours; the modified phosphoric acid melamine salt is heated at 260 DEG C to 330 DEG C, and polymerization reaction lasts 8 to 12 hours. The product of the present invention has the advantages of improved stability of thermal decomposition, reduced acidity, and improved flame-retardant performance of engineering plastics, such as nylon, etc. The method of the present invention has the advantages of simple and convenient steps, no environmental pollution and high rate of finished products.
Description
Technical field:
The present invention relates to a kind of phosphorus-nitrogen flame retardant and preparation technology thereof with high thermal stability.
Background technology:
Halogenless fire retarded polymer is the focus of the fire-retardant research and development of polymkeric substance, and phosphoric melamine salt is one of halogen-free flame retardants research and development most active fields.As phosphoric melamine salt, melamine pyrophosphate salt, polyphosphoric acid melamine salt etc., about their synthetic existing document and patent report, as Japanese Patent: the spy opens flat 8-81480, and the spy opens flat 9-124670, JP2001026597; United States Patent (USP) 2001/0005745: document " phosphoric melamine salt in the anti-flaming dope and melamine pyrophosphate salt ", Journal of CoatingsTechnology, 1994,66 (839): 75～82 etc.One of main flame-retardant composition of initial they conducts is mainly used in expanding fire-proof paint, is applied to the polyolefine halogen-free expanded flame-retardant simultaneously.The synthetic thermostability that has improved phosphoric melamine salt significantly of polyphosphoric acid melamine salt can be used for engineering plastics, and particularly nylon is fire-retardant, shows good flame-retardant effect.Discover in the fire retardant material processing in engineering plastics such as nylon, need that fire retardant has higher thermostability, lower acid and flame retardant properties more efficiently in water.And present polyphosphoric acid melamine salt also is difficult to satisfy above-mentioned requirements, and the thermostability of existing polyphosphoric acid melamine salt is lower, and initial heat decomposition temperature is that 310 ℃, acidity are bigger, and the pH value is lower than 5.The acid catalysis nylon degraded that polyphosphoric acid melamine salt is emitted after decomposing descends material property.
Summary of the invention:
The objective of the invention is shortcoming lower for the thermostability that solves existing polyphosphoric acid melamine salt, that the acidity in water is big, flame retardant properties is low, a kind of metallic ion modified polyphosphoric acid melamine salt and preparation method thereof is provided.Product of the present invention has thermostability height, acid low in water and the characteristics of flame retardant properties more efficiently.Method of the present invention has that step is simple and direct, non-environmental-pollution, characteristics that the finished product rate is high.Metallic ion modified polyphosphoric acid melamine salt of the present invention is made of by weight percentage following ingredients: oxygen: 21～25%, carbon: 15～18%, hydrogen: 1～3%, phosphorus: 13～16%, nitrogen: 37～42%, metal ion: 0.2～6%.Preparation method of the present invention is: the first, with metal hydroxides, oxide compound or dissolves carbonate (reaction) or to be distributed to concentration be in 80～90% the phosphoric acid solution, generate the phosphoric acid solution that contains dihydrogen phosphate; The second, water and described phosphoric acid solution and the trimeric cyanamide that contains dihydrogen phosphate were reacted in reactor or in the ball mill 1.5～2.5 hours, temperature of reaction is 30～100 ℃; Three, reacted product is taken out filtration, oven dry, pulverizing, obtain the modified phosphate melamine salt; Four, the modified phosphate melamine salt is heated under 260～330 ℃ of conditions, polyreaction 8～12 hours obtains metallic ion modified polyphosphoric acid melamine salt.This product oxygen level is 21～25%, carbon content is 15～18%, hydrogen richness is 1～3%, phosphorus content is 13-16%, and nitrogen content is 37-42%, and metal ion content is 0.2-6%, is the white powder solid.The invention has the beneficial effects as follows: the thermolysis stability that has improved metallic ion modified polyphosphoric acid melamine salt, initial heat decomposition temperature is 340～355 ℃, initial heat decomposition temperature than existing polyphosphoric acid melamine salt has improved 9～15%, reduced the acidity in water, in fire-retardant process, can form simultaneously fine and close hard carbon-coating, improved the flame retardant properties to engineering plastics such as nylon, flame retardant properties reaches the UL94V-0 level.
Embodiment:
Embodiment one: the metallic ion modified polyphosphoric acid melamine salt of present embodiment is made of by weight percentage following ingredients: oxygen: 21～25%, carbon: 15～18%, hydrogen: 1～3%, phosphorus: 13～16%, nitrogen: 37～42%, metal ion: 0.2～6%.
Embodiment two: the preparation method of the metallic ion modified polyphosphoric acid melamine salt of present embodiment is: the first, with metal hydroxides, oxide compound or dissolves carbonate (reaction) or to be distributed to concentration be in 80～90% the phosphoric acid solution, generate the phosphoric acid solution that contains dihydrogen phosphate; The second, water and described phosphoric acid solution and the trimeric cyanamide that contains dihydrogen phosphate were reacted in reactor or in the ball mill 1.5～2.5 hours, temperature of reaction is 30～100 ℃; Three, reacted product is taken out filtration, oven dry, pulverizing, obtain the modified phosphate melamine salt; Four, the modified phosphate melamine salt is heated under 260～330 ℃ of conditions, polyreaction 8～12 hours obtains metallic ion modified polyphosphoric acid melamine salt.Described metal hydroxides, oxide compound or carbonate and concentration are that the weight ratio of 80～90% phosphoric acid solutions is 1: 30～120.Described water and contain the phosphoric acid solution of dihydrogen phosphate and the weight ratio of trimeric cyanamide is 10～30: 1～2: 5～15.Described metal hydroxides is Mg (OH)
2, lanthanum hydroxide; Oxide compound is CuO, ZnO, TiO
2Carbonate is MgCO
3The concentration of phosphoric acid solution is 85% in the described step 1.
Embodiment three: the difference of present embodiment and embodiment two is that the reaction times in the step 2 is 2 hours, and temperature of reaction is 50～90 ℃.Other step is identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two is that the Heating temperature in the step 4 is 290～310 ℃, and polymerization reaction time is 10 hours.Other step is identical with embodiment two.
Embodiment five: the difference of present embodiment and embodiment two is that the temperature of reaction in the step 2 is 60 ℃.Other step is identical with embodiment two.
Embodiment six: the difference of present embodiment and embodiment two is that the Heating temperature in the step 4 is 300 ℃.Other step is identical with embodiment two.
Embodiment seven: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, the concentration that adds 3000ml water and be dissolved with 5.6gZnO is 85% phosphoric acid solution 232.1g, under agitation condition, be warming up to 60 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, the product taking-up is filtered and dried under 120 ℃ of conditions, pulverizes, obtain the modified phosphate melamine salt.With the polyreaction 10 hours in 300 ℃ reactor of the modified phosphate melamine salt after the oven dry, obtain the zine ion modified polyphosphoric acid melamine salt, productive rate is 89.3%, survey its concentration and be 10% turbid solution, the pH value is 5.0, and initial heat decomposition temperature is 350 ℃, and this product phosphorus content is 14.3% by analysis, nitrogen content is 40.2%, and zinc ion content is 0.9%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment eight: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, add 4000ml water and be dissolved with 5.3gMg (OH)
2Concentration be 85% phosphoric acid solution 232.1g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, product is taken out filters and oven dry under 120 ℃ of conditions, pulverize, obtain the modified phosphate melamine salt.With the polyreaction 12 hours in 310 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the magnesium ion modified polyphosphoric acid melamine salt, productive rate is 90.2%, surveys its concentration and be 10% turbid solution, the pH value is 5.1, and initial heat decomposition temperature is 350 ℃, and this product phosphorus content is 14.1% by analysis, nitrogen content is 40.4%, and magnesium ion content is 0.49%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment nine: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, add 3000ml water and be dissolved with 10.5g Mg (OH)
2Concentration be 85% phosphoric acid solution 234.8g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, product is taken out filters and oven dry under 120 ℃ of conditions, pulverize, obtain the modified phosphate melamine salt.With the polyreaction 10 hours in 310 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the magnesium ion modified polyphosphoric acid melamine salt, productive rate is 91.5%, surveys its concentration and be 10% turbid solution, and the pH value is 5.3, and initial heat decomposition temperature is 350 ℃, and this product phosphorus content is 14% by analysis, and nitrogen content is 40.5%, and magnesium ion content is 0.95%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment ten: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, add 3000ml water and be dissolved with 15.7gMg (OH)
2Concentration be 85% phosphoric acid solution 236.8g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, product is taken out filters and oven dry under 120 ℃ of conditions, pulverize, obtain the modified phosphate melamine salt.With the polyreaction 12 hours in 300 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the magnesium ion modified polyphosphoric acid melamine salt, productive rate is 90.7%, surveys its concentration and be 10% turbid solution, and the pH value is 5.8, and initial heat decomposition temperature is 355 ℃, and this product phosphorus content is 14% by analysis, and nitrogen content is 40.0%, and magnesium ion content is 1.40%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment 11: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, add 2500ml water and be dissolved with 7.4gTiO
2Concentration be 85% phosphoric acid solution 236.8g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, product is taken out filters and oven dry under 120 ℃ of conditions, pulverize, obtain the modified phosphate melamine salt.With the polyreaction 12 hours in 300 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the titanium modified polyphosphoric acid melamine salt, productive rate is 87.7%, surveys its concentration and be 10% turbid solution, and the pH value is 4.8, and initial heat decomposition temperature is 340 ℃, and this product phosphorus content is 14.7% by analysis, and nitrogen content is 39.6%, and titanium ion content is 0.91%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment 12: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, the concentration that adds 3000ml water and be dissolved with 5.6gCuO is 85% phosphoric acid solution 236.2g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, the product taking-up is filtered and dried under 120 ℃ of conditions, pulverizes, obtain the modified phosphate melamine salt.With the polyreaction 12 hours in 300 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the copper ion modified polyphosphoric acid melamine salt, productive rate is 88.4%, surveys its concentration and be 10% turbid solution, the pH value is 5.0, and initial heat decomposition temperature is 345 ℃, and this product phosphorus content is 14.8% by analysis, nitrogen content is 40.0%, and content of copper ion is 0.90%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment 13: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, add 3500ml water and be dissolved with 14.7gMgCO
3Concentration be 85% phosphoric acid solution 236.2g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, product is taken out filters and oven dry under 120 ℃ of conditions, pulverize, obtain the modified phosphate melamine salt.With the polyreaction 12 hours in 300 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the magnesium ion modified polyphosphoric acid melamine salt, productive rate is 89.4%, surveys its concentration and be 10% turbid solution, the pH value is 5.5, and initial heat decomposition temperature is 350 ℃, and this product phosphorus content is 14.6% by analysis, nitrogen content is 40.1%, and magnesium ion content is 0.93%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Embodiment 14: the preparation method of present embodiment is: in 10 liters of stainless steel cauldrons of agitator, thermometer and charging opening are housed, the concentration that adds 3500ml water and be dissolved with the 5.7g lanthanum hydroxide is 85% phosphoric acid solution 236.2g, under agitation condition, be warming up to 80 ℃, slowly add the 327.6g trimeric cyanamide again, continue reaction 2 hours, the product taking-up is filtered and dried under 120 ℃ of conditions, pulverizes, obtain the modified phosphate melamine salt.With the polyreaction 12 hours in 300 ℃ reactor of the modified phosphate melamine salt after the oven dry.Obtain the magnesium ion modified polyphosphoric acid melamine salt, productive rate is 87.4%, surveys its concentration and be 10% turbid solution, the pH value is 5.0, and initial heat decomposition temperature is 345 ℃, and this product phosphorus content is 14.8% by analysis, nitrogen content is 39.5%, and lanthanum ion content is 0.93%.This fire retardant is applied in the glass fiber enhanced nylon 66, obtains composition and be 25% fire retardant, 25% roving glass fiber, 49% nylon 66 and the halogen-free flame-retardant glass fiber reinforced materials of 1% auxiliary agent, flame retardant properties reaches the UL94V-0 level.
Claims (10)
1. metallic ion modified polyphosphoric acid melamine salt is characterized in that oxygen by weight percentage: 21～25%, carbon: 15～18%, hydrogen: 1～3%, phosphorus: 13～16%, nitrogen: 37～42% and metal ion: 0.2～6%.
2. according to the preparation method of the described metallic ion modified polyphosphoric acid melamine salt of claim 1, it is characterized in that first, with metal hydroxides, oxide compound or dissolves carbonate or to be distributed to concentration be in 80～90% the phosphoric acid solution, generate the phosphoric acid solution that contains dihydrogen phosphate; The second, water and described phosphoric acid solution and the trimeric cyanamide that contains dihydrogen phosphate were reacted in reactor or in the ball mill 1.5～2.5 hours, temperature of reaction is 30～100 ℃; Three, the reacted product of step 2 is taken out filtration, oven dry, pulverizes, obtain the modified phosphate melamine salt; Four, the modified phosphate melamine salt is heated under 260～330 ℃ of conditions, polyreaction 8～12 hours obtains metallic ion modified polyphosphoric acid melamine salt.
3. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that described metal hydroxides, oxide compound or carbonate and concentration are that the weight ratio of 80～90% phosphoric acid solutions is 1: 30～120.
4. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that described water and contains the phosphoric acid solution of dihydrogen phosphate and the weight ratio of trimeric cyanamide is 10～30: 1～2: 5～15.
5. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that described metal hydroxides is Mg (OH)
2, lanthanum hydroxide; Oxide compound is CuO, ZnO, TiO
2Carbonate is MgCO
3
6. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that the reaction times in the step 2 is 2 hours, and temperature of reaction is 50～90 ℃.
7. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2, the concentration that it is characterized in that phosphoric acid solution in the described step 1 is 85%.
8. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that the Heating temperature in the step 4 is 290～310 ℃.
9. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that the polymerization reaction time in the step 4 is 10 hours.
10. the preparation method of metallic ion modified polyphosphoric acid melamine salt according to claim 2 is characterized in that the temperature of reaction in the step 2 is 60 ℃.
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| CN100410324C (en) * | 2006-10-30 | 2008-08-13 | 东北林业大学 | Glass fibre reingorced no-halogen flame-retardant nylon 66 and its preparing method |
| CN102127230B (en) * | 2010-01-19 | 2012-11-28 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN102604220B (en) * | 2012-03-13 | 2013-08-21 | 金发科技股份有限公司 | High-oxygen-index low-gloss flame-retardant polypropylene composition, preparation method for same and application thereof |
| CN104131463A (en) * | 2014-07-18 | 2014-11-05 | 成都纺织高等专科学校 | Metal ion-modified ammonium polyphosphate and its preparation method and use |
| CN105037287A (en) * | 2015-07-08 | 2015-11-11 | 广东华南精细化工研究院有限公司 | Melamine polyphosphoric acid rare earth metal salt, synthetic method and application |
| CN105968060B (en) * | 2016-05-09 | 2019-02-26 | 东华大学 | A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution |
| CN106336424B (en) * | 2016-08-01 | 2018-11-20 | 重庆派昂科技发展有限公司 | Inorganic hybridization melamine methylol and preparation method thereof |
| CN106831625A (en) | 2016-12-22 | 2017-06-13 | 杭州捷尔思阻燃化工有限公司 | A kind of metal ion-modified melamine polyphosphate and preparation method thereof, application |
| CN107556255A (en) * | 2017-07-26 | 2018-01-09 | 东华大学 | A kind of organic amine modified melamine polyphosphate and preparation method thereof |
| CN110591267B (en) * | 2019-09-23 | 2022-04-19 | 聚石化学(苏州)有限公司 | Low-smoke environment-friendly 5 VA-grade flame-retardant ASA material with excellent weather resistance and preparation method thereof |
| CN110483941B (en) * | 2019-09-23 | 2022-04-19 | 聚石化学(苏州)有限公司 | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof |
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