CN1721423A - Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) - Google Patents
Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) Download PDFInfo
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- CN1721423A CN1721423A CN 200410069309 CN200410069309A CN1721423A CN 1721423 A CN1721423 A CN 1721423A CN 200410069309 CN200410069309 CN 200410069309 CN 200410069309 A CN200410069309 A CN 200410069309A CN 1721423 A CN1721423 A CN 1721423A
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- dihydrogen phosphate
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Abstract
The present invention relates to the synthesis process of pentaerythritol diphophate melamine as phosphorus-nitrogen expansion type fire retardant. The present invention features that pentaerythritol and polyphosphate in the molar ratio of 1 to 2 are dispersed in benzene solvent in the amount one 8-9 times the weight of pentaerythritol and reacted in the presence of p-toluenesulfonic acid or benzoic acid catalyst through heating to 80-144 deg.c for 7-10 hr before decompression distillation to recover solvent and obtain ropy intermediate product; water and melamine in the weight ratio of 1 to 7-10 and with melamine/pentaerythritol molar ratio of 1 to 2 are then added for reaction of 2 hr while heating to 100 deg.c; and through further cooling naturally to room temperature, filtering, washing, stoving and crushing, the target product is obtained. The process is simple and has less environmental pollution, and the product has excellent fire retarding effect and high heat stability.
Description
Technical field
The present invention relates to a kind of preparation method of phosphorus-nitrogen expansion type combustion inhibitor, specifically a kind of synthetic method of melamine salt of pentaerythritol bis (dihydrogen phosphate).
Background technology
Fire retardant can be divided into inorganic combustion inhibitor and organic fire-retardant, wherein organic fire-retardant comprises halogen containing flame-retardant, it represents brand is the bromobenzene ethers, as decabromodiphynly oxide, tetrabromo-bisphenol etc.,, keep the unmodified resin physicals substantially though brominated flame-retardant has satisfied the fire-retardant requirement of macromolecular material, but the toxic substance that brominated superpolymer produces when burning, very harmful, havoc ecology, contaminate environment.Along with the enhancing of environmental consciousness, halogenated flame retardant is faced with formidable challenges, for the development of expansion type flame retardant provides good opportunity.
Melamine salt of pentaerythritol bis (dihydrogen phosphate) belongs to phosphorus-nitrogen expansion type combustion inhibitor, is applicable to flame retardant of plastics such as polyethylene, polypropylene, polystyrene, polyoxymethylene.When the superpolymer that contains this fire retardant is heated, surface energy generates layer of even carbonaceous foam layer, this layer is heat insulation, oxygen barrier, press down cigarette, and can prevent molten drop, have advantages such as good flame retardancy, thermostability height, consistency be good, it meets the development trend of the few cigarette of present fire retardant, low toxicity, is a kind of fire retardant of environment-friendly type.
Melamine salt of pentaerythritol bis (dihydrogen phosphate) is a white crystalline powder, is insoluble to organic solvents such as alcohol, ketone, ether, hydrocarbon, halohydrocarbon, is slightly soluble in water, decomposition temperature is greater than 250 ℃, has the thermostability height, whiteness height, advantage such as consistency is good, durable, fast light, nontoxic.
Adopted different routes to synthesize this product both at home and abroad, existing abroad commodity come out, and mainly contain the series product such as CN-329 that Albright and Wilson company produces; The domestic no large-scale production equipment of this product.
The study on the synthesis [J] of fire retardant pentaerythrite diphosphate ester melamine salt. Anhui chemical industry, 1998, (4): 23-25; Synthetic and the flame retardant properties [J] of BACN CN-329. fire retardant material and technology, 2003, (5): 3-5; The performance of novel phosphorus-nitrogen expanding fire retardant, synthetic and application [J]. the Jiangsu chemical industry, 1998, (3): 6-11 etc. have disclosed phosphorus oxychloride method synthetic route.Its process be phosphorus oxychloride and tetramethylolmethane under the effect of catalyzer aluminum chloride, in 100 ℃ of reactions 10 hours, excessive phosphorus oxychloride was removed in underpressure distillation, with the ice-water bath cooling, filter, intermediate is with washed with dichloromethane for several times, in vacuum drier, be dried to constant weight, get white solid; The reaction of this white solid and trimeric cyanamide, water refluxed 1.5 hours, with the ice-water bath cooling, filtered, be washed till no chlorion with deionized water till, in vacuum drier, be dried to constant weight, must product.Discharge HCl gas in this reaction process, equipment is had corrosion, environment is also had pollution, in addition, the raw material phosphorus oxychloride is a fuming liquid, brings difficulty to operation.
Synthetic and the application in polypropylene [J] of expansion type flame retardant phosphoric acid-tetramethylolmethane-melamine polymers. chemistry world, 2001, (4): 184-186; The expansion effect of expansion type flame retardant and be applied to polyacrylic flame retardant effect [J]. University Of Hebei's journal, 2001, (2): 138-141 etc. disclose Vanadium Pentoxide in FLAKES method operational path.Its process be Vanadium Pentoxide in FLAKES and tetramethylolmethane under nitrogen protection, 130 ℃ of reactions 2 hours down, thickness reddish-brown liquid; Adding quantitative trimeric cyanamide then in this liquid, is under 200 ℃ in temperature, reacts 2-5 hour, gets product.Material viscosity is big in this reaction process, equipment is stirred require height, has hindered mass transfer, heat transfer, is not suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is to propose a kind of tetramethylolmethane and polyphosphoric acid reacts in the benzene series solvent, its product method that melamine salt of pentaerythritol bis (dihydrogen phosphate) is synthesized in reaction with trimeric cyanamide again, simplify technology, reduce and pollute, be convenient to operation, suitability for industrialized is produced, and product has good thermostability.
The objective of the invention is to be achieved by the following technical solutions:
With mol ratio 1: 2 tetramethylolmethane and polyphosphoric acid, being dispersed in consumption is in the 8-9 benzene series solvent doubly of tetramethylolmethane weight, with tosic acid or phenylformic acid is catalyzer, its consumption is the 2-4% of tetramethylolmethane weight, be heated to 80-144 ℃, react vacuum distillation recovered solvent after 7-10 hour, obtain thick intermediate product; In this intermediate product, add entry and trimeric cyanamide then, the mol ratio of trimeric cyanamide and tetramethylolmethane is 1: 2, water and trimeric cyanamide weight ratio are 1: 7～10, be warming up to 100 ℃, and after reacting 2 hours under this temperature, when reducing to room temperature naturally again, stop agitation and filtration, the collecting precipitation thing is through 80-100 ℃ of oven dry, pulverize the melamine salt of pentaerythritol bis (dihydrogen phosphate) product obtain.
Its benzene series organic solvent is benzene,toluene,xylene or ethylbenzene.
Synthetic method raw material of the present invention is easy to get, technical process is short, has especially selected solvent for use, makes the reaction conditions gentleness, the reaction solution viscosity is little, stirring pattern requirement to equipment is low, does not produce toxic gas in the reaction, and environmental pollution is little, be suitable for suitability for industrialized production, product yield 80-82.2%, phosphorus content 11-12%, the solvent toluene rate of recovery 96%.The fire retardant applicating evaluating: with the polypropylene is research object, and the melamine salt of pentaerythritol bis (dihydrogen phosphate) that the foregoing description is prepared carries out flame retardant properties and Mechanical Properties.
The flame retardant properties test is carried out vertical combustion mensuration according to U.S. UL94 standard, total Three Estate, and the highest requirement is the V-0 level: in a series of 5 samples, it is 10S that two after flame times are arranged, and total after flame time can not surpass 50S, and does not have low phenomenon.For the V-1 level, require total after flame time can not surpass 250S, do not have the sample after flame time to surpass 30S, and do not have low phenomenon.If low phenomenon takes place under V-1 level condition, then should be classified as the V-2 level.
Concrete prescription sees Table 1, and test result sees 2.
The basic recipe of table 1 polypropylene flame redardant
| Form | Formula rate | ||
| Polypropylene | 74.6 | 71.6 | 69.6 |
| Fire retardant | 25.0 | 28.0 | 30.0 |
| Antioxidant 1010 | 0.2 | 0.2 | 0.2 |
| Oxidation inhibitor 168 | 0.2 | 0.2 | 0.2 |
Sample making course: polypropylene that will accurately measure and various auxiliary agent; provide material according to table 1; the sequencing of auxiliary agent joins and makes its thorough mixing in the high-speed mixer; after treating that each section of twin-screw mixer machine temperature reaches the technique initialization value and stablizes half an hour; the slow speed of revolution starts screw rod; the material that mixes; enter the twin-screw mixer machine through feeding machine (control feed rate); through fully heating; after mixing; by die head extruded stock bar, after water quench, send into dicing machine; evenly be cut into particle; after drying by the injection moulding of relevant criterion condition, obtain the standard batten, and carry out flame retardant properties and Mechanics Performance Testing again according to standard.
The main operational condition of forcing machine:
The temperature 175-215 of heating zone ℃;
Rate of feeding 120-180kg/h;
Screw speed 200-400rpm.
The performance test data table of table 2 polypropylene flame redardant
| Project | Not fire-retardant PP | The flame retardant resistance that contains fire retardant different amounts of the present invention | The method of inspection | ||
| 25％ | 28％ | 30％ | |||
| Incendivity | Burning has cigarette, and molten drop is arranged | V-1 | V-0 | V-0 | The UL94 standard |
| Tensile strength (Mpa) | 36.0 | 35.2 | 34.2 | 32.3 | ASTM D638 |
| Melting index (g/10min) | 8.0 | 12.0 | 12.5 | 12.8 | ASTM D790 |
| Notched Izod impact strength (J/m) | 30 | 29.0 | 27.5 | 26.0 | ASTM D256 |
| Heat-drawn wire (0.046MPa)/℃ | 110 | 116 | 120 | 128 | ASTM D648 |
From test result, fire retardant of the present invention is when consumption 28%, and flame retardant rating reaches the UL94V-0 level, can satisfy the application performance requirement of fire-retardant PP.
Embodiment
Embodiment 1:
In the 2000mL four-hole bottle of being furnished with agitator, thermometer, water trap, condenser, add 184.5 gram polyphosphoric acid, 108.8 gram tetramethylolmethanes, catalyzer phenylformic acid 2.5 grams, 1000 milliliters of toluene are warming up to 100-115 ℃, react 9 hours.Under-0.095Mpa, steam solvent.Add 201.6 gram trimeric cyanamides in four-hole bottle, 2015 ml waters are warming up to 100 ℃, react 2 hours.After being cooled to room temperature, stop to stir, filter, wash, the product that will wet are in 80-100 ℃ of drying in oven, pulverizing, packing.Product yield 82.2%, phosphorus content 11.6%, the solvent toluene rate of recovery 96%.
Embodiment 2:
In the 2000mL four-hole bottle of being furnished with agitator, thermometer, water trap, condenser, add 184.5 gram polyphosphoric acid, 108.8 gram tetramethylolmethanes, catalyzer tosic acid 2.5 grams, 1000 milliliters of toluene are warming up to 100-115 ℃, react 9 hours.Afterwards, under-0.095Mpa, steam solvent.Add 201.6 gram trimeric cyanamides in four-hole bottle, 1400 ml waters are warming up to 100 ℃, reacts 2 hours, reduce to room temperature after, stop to stir, filter, wash, the product that will wet are in 80-100 ℃ of drying in oven, pulverizing, packing.Product yield 80.5%, phosphorus content 12.0%, solvent recovering rate 95%.
Embodiment 3:
In the 2000mL four-hole bottle of being furnished with agitator, thermometer, water trap, condenser, add 184.5 gram polyphosphoric acid, 108.8 gram tetramethylolmethanes, catalyzer tosic acid 2.5 grams, 1000 milliliters of dimethylbenzene are warming up to 130-144 ℃, react 7 hours.Under-0.095Mpa, steam solvent xylene.Add 201.6 gram trimeric cyanamides in four-hole bottle, 1400 ml waters are warming up to 100 ℃, react 2 hours.After reducing to room temperature, stop to stir, filter, wash, the product that will wet are in 80-100 ℃ of drying in oven, pulverizing, packing.Yield 81.5%, phosphorus content 11.8%, solvent recovering rate 95%.
Embodiment 4:
In the 2000mL four-hole bottle of being furnished with agitator, thermometer, water trap, condenser, add 184.5 gram polyphosphoric acid, 108.8 gram tetramethylolmethanes, catalyzer tosic acid 2.5 grams, 1000 milliliters of benzene are warming up to 70-80 ℃, react after 9 hours.Under-0.095Mpa, steam solvent.Add 201.6 gram trimeric cyanamides in four-hole bottle, 2015 ml waters are warming up to 100 ℃, reacts 2 hours, reduce to room temperature after, stop to stir, filter, wash, the product that will wet are in 80-100 ℃ of drying in oven, pulverizing, packing.Product yield 82.0%, phosphorus content 11.5%, solvent recovering rate 96%.
Embodiment 5:
In the 2000mL bottle of being furnished with agitator, thermometer, water trap, condenser, add 184.5 gram polyphosphoric acid, 108.8 gram tetramethylolmethanes, catalyzer tosic acid 2.5 grams, 1000 milliliters of ethylbenzene are warming up to 130-136 ℃, react after 9 hours.Under-0.095Mpa, steam solvent.Add 201.6 gram trimeric cyanamides in four-hole bottle, 1400 ml waters are warming up to 100 ℃, reacts 2 hours, reduce to room temperature after, stop to stir, filter, wash, the product that will wet are in 80-100 ℃ of drying in oven, pulverizing, packing.Product yield 80.0%, phosphorus content 11.8%, solvent recovering rate 96%.
Claims (2)
1. the synthetic method of a melamine salt of pentaerythritol bis (dihydrogen phosphate), it is characterized in that: the tetramethylolmethane and the polyphosphoric acid that with mol ratio are 1: 2, being dispersed in consumption is in the 8-9 benzene series solvent doubly of tetramethylolmethane weight, with tosic acid or phenylformic acid is catalyzer, catalyst levels is the 2-4% of tetramethylolmethane weight, be heated to 80-144 ℃, react vacuum distillation recovered solvent after 7-10 hour, obtain thick intermediate product; In this intermediate product, add entry and trimeric cyanamide then, the mol ratio of trimeric cyanamide and tetramethylolmethane is 1: 2, the weight ratio of water and trimeric cyanamide is 1: 7～10, be warming up to 100 ℃, and after reacting 2 hours under this temperature, when reducing to room temperature naturally again, stop agitation and filtration, the collecting precipitation thing is through 80-100 ℃ of oven dry, pulverize the melamine salt of pentaerythritol bis (dihydrogen phosphate) product obtain.
2. the synthetic method of melamine salt of pentaerythritol bis (dihydrogen phosphate) according to claim 1, it is characterized in that: described benzene series organic solvent is benzene,toluene,xylene or ethylbenzene.
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| CNB2004100693092A CN1298726C (en) | 2004-07-16 | 2004-07-16 | Process for synthesis of melamine salt of pentaerythritol bis (dihydrogen phosphate) |
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| CN1298726C CN1298726C (en) | 2007-02-07 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100564439C (en) * | 2006-07-07 | 2009-12-02 | 江苏技术师范学院 | Environment-friendly type flame-retardant plastic and preparation method thereof |
| CN101143947B (en) * | 2006-09-13 | 2010-05-12 | 中国石油天然气股份有限公司 | Halogen-free intumescent flame retardant for polypropylene |
| CN101570518B (en) * | 2009-06-12 | 2010-11-17 | 东华大学 | Preparation method for expansion type melamine hypophosphite fire retardant |
| CN101289465B (en) * | 2007-04-19 | 2011-08-03 | 长春人造树脂厂股份有限公司 | Process for preparing di(phosphoric acid pentaerythrite ester)phosphoric acid melamine salts |
| CN102171273A (en) * | 2008-10-06 | 2011-08-31 | 建筑研究和技术有限公司 | Method for producing phosphated polycondensation products and the use thereof |
| CN104327304A (en) * | 2014-10-27 | 2015-02-04 | 沈阳化工大学 | Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant |
| CN104389165A (en) * | 2014-10-23 | 2015-03-04 | 吉林化工学院 | Preparation method for multi-component intumescent flame retardant for acrylic fabric |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575351B (en) * | 2009-05-30 | 2012-02-01 | 山东天一化学股份有限公司 | Method for preparing phosphorus-nitrogen expanding fire retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1251154B (en) * | 1991-08-07 | 1995-05-04 | Enichem Sintesi | PENTAERITRIL PHOSPHONATES AND THEIR USE IN SELF-EXTINGUISHING THERMOPLASTIC POLYMER COMPOSITIONS |
| US5387655A (en) * | 1991-09-09 | 1995-02-07 | Chemische Fabrik Budenheim | Composition with integral intumescence properties |
| CN1158293C (en) * | 2002-09-26 | 2004-07-21 | 东北林业大学 | Sythetic method of pentaerythrite diphosphate ester diacid chlorine |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100564439C (en) * | 2006-07-07 | 2009-12-02 | 江苏技术师范学院 | Environment-friendly type flame-retardant plastic and preparation method thereof |
| CN101143947B (en) * | 2006-09-13 | 2010-05-12 | 中国石油天然气股份有限公司 | Halogen-free intumescent flame retardant for polypropylene |
| CN101289465B (en) * | 2007-04-19 | 2011-08-03 | 长春人造树脂厂股份有限公司 | Process for preparing di(phosphoric acid pentaerythrite ester)phosphoric acid melamine salts |
| CN102171273A (en) * | 2008-10-06 | 2011-08-31 | 建筑研究和技术有限公司 | Method for producing phosphated polycondensation products and the use thereof |
| CN102171273B (en) * | 2008-10-06 | 2014-10-22 | 建筑研究和技术有限公司 | Method for producing phosphated polycondensation products and the use thereof |
| CN101570518B (en) * | 2009-06-12 | 2010-11-17 | 东华大学 | Preparation method for expansion type melamine hypophosphite fire retardant |
| CN104389165A (en) * | 2014-10-23 | 2015-03-04 | 吉林化工学院 | Preparation method for multi-component intumescent flame retardant for acrylic fabric |
| CN104327304A (en) * | 2014-10-27 | 2015-02-04 | 沈阳化工大学 | Fire retardant for polyolefin high polymers and epoxy resin and preparation method of fire retardant |
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| CN1298726C (en) | 2007-02-07 |
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