CN101429438A - Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same - Google Patents
Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same Download PDFInfo
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Abstract
The invention discloses a phosphorus-nitrogen swelling type fire retardant and a method for preparing the same. The chemical name of the fire retardant is 5, 5-dimethyl-4-p-chlorophenyl-1, 3, 2-dioxaphosphorinane phosphonate melamine salt. The preparation method comprises the following steps: (1) p-chlorobenzaldehyde and iso-butyraldehyde react with alkali ethanol solution, are cooled down and filtered to obtain an intermediate product (I); (2) the intermediate product (I) and phosphoric acid are added to solvent, and added with paratoluenesulfonic acid or benzoic acid or sodium salt of benzoic acid; and the mixing solution is distilled after reaction to reclaim the solvent to obtain an intermediate product(II); and (3) melamine and the intermediate product(II) are added to water for reaction, cooled down and filtered to obtain a filter cake; and the filter cake is dried to obtain phosphorus-nitrogen swelling type fire retardant. The phosphorus-nitrogen swelling type fire retardant has the advantages of high thermal stability, good compatibility, no halogen, less smoke and environmental protection. The preparation method has the advantages of materials available, simple process, mild reaction conditions, small viscosity of reaction liquid, low requirement on equipment and little environmental pollution.
Description
Technical field
The present invention relates to a kind of phosphor-nitrogen expansion type combustion inhibitor and preparation method thereof, specifically a kind of BACN 5,5-dimethyl-4-rubigan-1,3,2-dioxaphosphorinane phosphoric melamine salt and preparation method thereof.
Background technology
In recent years, in the development and application of fire retardant, phosphorus-nitrogen containing flame retardant is a dark horse, because synergy and synergy between phosphorus nitrogen make this compounds have good flame retardancy, and the amount of being fuming are little, Poisonous Gas is few, becomes a direction of fire retardant exploitation from now on.Also have an expansion type fire retardant in the phosphorus-nitrogen containing flame retardant, surface energy generated layer of even carbonaceous foam layer when the superpolymer that has added this based flame retardant was heated, this layer oxygen barrier, heat insulation, press down cigarette, and can prevent molten drop, have bright development prospect.
The fire retardant mechanism of present employed expansion type flame retardant is by thermolysis, discharges phosphoric acid and non-flammable gases, the oxygen in latter's diluent air.Nitrogenous compound plays a part whipping agent and coke toughener, and phosphoric acid then is pyrogenic catalyzer, impels burning surface to form one deck porousness coking protective membrane, plays heat insulation and the oxygen barrier effect, can interrupt the incendiary chain reaction.
Based on the requirement that low cigarette, corrodibility are little, toxicity is little to flame retardant materials, the important substitute that develops into traditional halogen flame of expansion type flame retardant.Expansion type flame-retarding system main component can be divided into three parts: acid source, carbon source, source of the gas.Acid source is generally mineral acid or is heated to the compound that can generate mineral acid more than 100 ℃, as phosphoric acid, phosphorus oxychloride, phosphoric acid ester etc.; Carbon source (char-forming agent) is the basis that forms the foam charring layer, is generally the polyol of rich carbon, as tetramethylolmethane, hot pentanediol and contain the organic ester etc. of polyol.Source of the gas (foaming source) is generally amine or amides, trimeric cyanamide, Dyhard RU 100 etc.
Nitrogenous compound based on triazine ring derivatives has multiple reaction (addition, replacement, condensation), excellent thermostability, weather resistance and weathering resistance, good with material compatibility, and its Halogen, low toxicity, be fit to processing, little to the mechanical property influence, do not ooze out, advantages such as flame retardant properties is good, in the exploitation of expansion type flame retardant, compound in triazine class, trimeric cyanamide particularly, obtained widespread use, the expansion type flame retardant Char-Guard CN-329 of U.S. Great Lakes company exploitation for example, the domestic no large-scale production equipment of this product.U.S. Pat 5296598 discloses the trimeric cyanamide monomer-2 that contains phosphoric acid and ester thereof, 4-two amidos-1,3,5-triazinyl-6-phosphoric acid ester.In this compound, have P, N simultaneously to be used as the interpolation fire retardant in the polymkeric substance.But the thermostability of this compound is not too high, decomposes easily in the high molecular fire retardant course of processing, has limited its application in polymeric material field.
With 1,3,2-dioxaphosphorinane structure is incorporated in the triazines fire retardant, can obtain collecting carbon source, the gentle expansion type flame retardant that comes from one of acid source.We further investigate this compounds, have synthesized phosphorus-nitrogen expanding fire retardant, 5,5-dimethyl-4-rubigan-1,3,2-dioxaphosphorinane phosphoric melamine salt.
Summary of the invention
First purpose of the present invention provides a kind of phosphor-nitrogen expansion type combustion inhibitor, and its structural formula is:
Second purpose of the present invention provides the preparation method of above-mentioned phosphor-nitrogen expansion type combustion inhibitor.
The present invention adopts the preparation method who comprises following steps to reach two purposes of the present invention:
(1) be the 4-chloro-benzaldehyde and the isobutyric aldehyde of 1:2～2.5 with mol ratio, with the ethanolic soln of alkali, stir and 50～60 ℃ of temperature condition under, reaction 4～6h, after reaction is finished, cooling, after resultant of reaction is separated out, filter, obtaining white crystal shape filter cake is intermediate product (I);
(2) with mol ratio be the intermediate product (I) and the phosphoric acid of 1:1～2, join 4～6 times in the benzene series solvent of intermediate product (I) weight, and add 1～3% times of tosic acid or phenylformic acid or its sodium salt to intermediate product (I) weight, stir and 50～60 ℃ of temperature condition under, reaction 8～10h, after reaction finished, vacuum distillation recovered solvent obtained thick intermediate product (II);
(3) with mol ratio be the trimeric cyanamide and the intermediate product (II) of 1:1～1.2, join 6～10 times in the water of trimeric cyanamide weight, stir and 90～110 ℃ of temperature condition under, with trimeric cyanamide reaction 4～6h, react finish after, cooling, after resultant of reaction is separated out, filter, get filter cake, the oven dry filter cake gets white crystal shape phosphor-nitrogen expansion type combustion inhibitor.
The ethanolic soln of the alkali described in the step (1) comprises dehydrated alcohol and alkali, and wherein alkali is sodium hydroxide or potassium hydroxide, and the proportioning of alkali and dehydrated alcohol is 0.1mol:90～120ml, and the mol ratio of alkali and 4-chloro-benzaldehyde is 1～1.4:1.
Benzene series solvent described in the step (1) is benzene,toluene,xylene or ethylbenzene.
In the step (1), after filtration obtained filter cake, filter cake also will after the washing, obtain intermediate product (I) through the straight-chain paraffin liquid scrubbing, and all the other are identical with step (1).
Described straight-chain paraffin liquid is normal heptane or normal hexane.
In the described step (3), after filtration obtained filter cake, filter cake also will be dried after water washing again, and all the other are identical with step (3).
Chemical equation of the present invention is as follows:
This structural formula is
The material that is characterized is phosphor-nitrogen expansion type combustion inhibitor of the present invention, and its chemical name is: 5,5-dimethyl-4-rubigan-1,3,2-dioxaphosphorinane phosphoric melamine salt.
This phosphor-nitrogen expansion type combustion inhibitor lenticular that is white in color, molecular weight is 401～403,222～224 ℃ of fusing points, be insoluble to organic solvents such as alcohol, ether, ketone, hydrocarbon, be slightly soluble in water, because it contains P, N, three kinds of elements of C, thermostability height simultaneously, consistency is good, belongs to Halogen, low cigarette, environment friendly flame retardant efficiently.
Preparation method's raw material of the present invention is easy to get, and technology is simple, the reaction conditions gentleness, and reaction solution viscosity is little, lower to equipment requirements, do not produce toxic gas in the reaction, environmental pollution is little, be suitable for suitability for industrialized production, product yield 80%～85%, P content 7.50%～8.00%.
Description of drawings
Fig. 1 is 5, the 5-dimethyl-4-rubigan-1,3 of embodiment 1 preparation, the infrared spectrum of 2-dioxaphosphorinane phosphoric melamine salt.
Embodiment
Further specify the preparation method of phosphor-nitrogen expansion type combustion inhibitor by the following examples, these embodiment only are used to the present invention is described and to the present invention without limits.
Embodiment 1
4-chloro-benzaldehyde 0.1mol, isobutyric aldehyde 0.2mol mixing is placed the 250ml four-hole boiling flask that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed.Potassium hydroxide 0.1mol is dissolved in the 90ml dehydrated alcohol, slowly splashes into four-hole boiling flask with constant pressure funnel.Exothermic heat of reaction, at 50 ℃, stirring reaction 4h is after reaction finishes with the water-bath controlled temperature, naturally cooling carries out suction filtration after the question response resultant is separated out, and filter cake with the normal heptane washing for several times, obtaining the 19.70g white crystal is intermediate product (I), yield 91.84%, 99～100 ℃ of fusing points.
In the 250ml four-hole bottle that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed, add intermediate product (I) 0.1mol, phosphoric acid 0.1mol, tosic acid 0.22g, 85.8g toluene, stir and 50 ℃ of temperature condition under, reaction 8h is after reaction finishes, under-0.09Mpa pressure condition, solvent toluene is removed in distillation, obtain thick intermediate product (II) 25.80g, yield 93.31%, 216～218 ℃ of fusing points.
Intermediate product (II) 0.1mol, trimeric cyanamide 0.1mol, distilled water 76ml are placed the 250ml four-hole bottle that thermometer, reflux condensing tube, magnetic stirring apparatus are housed, stir and 90 ℃ of temperature condition under, reaction 4h, after reaction finished, naturally cooling carried out suction filtration after resultant of reaction is separated out, suction filtration is dried after water washing, obtain the 34.50g white crystal, yield 85.71%, 222～223 ℃ of fusing points;
Embodiment 2
4-chloro-benzaldehyde 0.1mol, isobutyric aldehyde 0.22mol mixing is placed the 250ml four-hole boiling flask that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed.Potassium hydroxide 0.12mol is dissolved in the 120ml dehydrated alcohol, slowly splashes into four-hole boiling flask with constant pressure funnel.Exothermic heat of reaction, at 54 ℃, stirring reaction 5h is after reaction finishes with the water-bath controlled temperature, naturally cooling carries out suction filtration after the question response resultant is separated out, and filter cake with the normal heptane washing for several times, obtaining the 19.75g white crystal is intermediate product (I), yield 92.07%, 98～99.5 ℃ of fusing points.
In the 250ml four-hole bottle that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed, add intermediate product (I) 0.1mol, phosphoric acid 0.12mol, phenylformic acid 0.43g, 108g benzene, stir and 54 ℃ of temperature condition under, reaction 8.6h is after reaction finishes, under-0.09Mpa pressure condition, solvent benzol is removed in distillation, obtain thick intermediate product (II) 25.22g, yield 91.21%, 215～217 ℃ of fusing points.
Intermediate product (II) 0.105mol, trimeric cyanamide 0.1mol, distilled water 95ml are placed the 250ml four-hole bottle that thermometer, reflux condensing tube, magnetic stirring apparatus are housed, stir and 96 ℃ of temperature condition under, reaction 4.6h, after reaction finished, naturally cooling carried out suction filtration after resultant of reaction is separated out, suction filtration is dried after water washing, obtain the 33.81g white crystal, yield 84.00%, 222.5～224 ℃ of fusing points.
Embodiment 3
4-chloro-benzaldehyde 0.1mol, isobutyric aldehyde 0.23mol mixing is placed the 250ml four-hole boiling flask that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed.Sodium hydroxide 0.13mol is dissolved in the 143ml dehydrated alcohol, slowly splashes into four-hole boiling flask with constant pressure funnel.Exothermic heat of reaction, at 57 ℃, stirring reaction 5.5h is after reaction finishes with the water-bath controlled temperature, naturally cooling carries out suction filtration after the question response resultant is separated out, and filter cake with the normal hexane washing for several times, obtaining the 18.90g white crystal is intermediate product (I), yield 88.11%, 97～99.5 ℃ of fusing points.
In the 250ml four-hole bottle that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed, add intermediate product (I) 0.1mol, phosphoric acid 0.16mol, paratoluenesulfonic acid sodium salt 0.53g, 118g dimethylbenzene, stir and 57 ℃ of temperature condition under, reaction 9.2h is after reaction finishes, under-0.09Mpa pressure condition, solvent xylene is removed in distillation, obtain thick intermediate product (II) 25.10g, yield 90.78%, 215.5～217 ℃ of fusing points.
Intermediate product (II) 0.11mol, trimeric cyanamide 0.1mol, distilled water 110ml are placed the 250ml four-hole bottle that thermometer, reflux condensing tube, magnetic stirring apparatus are housed, stir and 102 ℃ of temperature condition under, reaction 5.5h, after reaction finished, naturally cooling carried out suction filtration after resultant of reaction is separated out, suction filtration is dried after water washing, obtain the 32.20g white crystal, yield 80.00%, 222～223.5 ℃ of fusing points.
Embodiment 4
4-chloro-benzaldehyde 0.1mol, isobutyric aldehyde 0.25mol mixing is placed the 250ml four-hole boiling flask that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed.Sodium hydroxide 0.14mol is dissolved in the 168ml dehydrated alcohol, slowly splashes into four-hole boiling flask with constant pressure funnel.Exothermic heat of reaction, at 60 ℃, stirring reaction 6h is after reaction finishes with the water-bath controlled temperature, naturally cooling carries out suction filtration after the question response resultant is separated out, and filter cake with the normal hexane washing for several times, obtaining the 18.55g white crystal is intermediate product (I), yield 86.48%, 97.5～99.5 ℃ of fusing points.
In the 250ml four-hole bottle that thermometer, magnetic stirring apparatus, reflux condensing tube, constant pressure funnel are housed, add intermediate product (I) 0.1mol, phosphoric acid 0.2mol, Sodium Benzoate 0.64g, 129g ethylbenzene, stir and 60 ℃ of temperature condition under, reaction 10h is after reaction finishes, under-0.09Mpa pressure condition, distillation removes the ethylbenzene that desolvates, obtain thick intermediate product (II) 25.88g, yield 93.60%, 216～217 ℃ of fusing points.
Intermediate product (II) 0.12mol, trimeric cyanamide 0.1mol, distilled water 126ml are placed the 250ml four-hole bottle that thermometer, reflux condensing tube, magnetic stirring apparatus are housed, stir and 110 ℃ of temperature condition under, reaction 6h, after reaction finished, naturally cooling carried out suction filtration after resultant of reaction is separated out, suction filtration is dried after water washing, obtain the 32.61g white crystal, yield 81.02%, 222～224 ℃ of fusing points.
Among the embodiment 1-4, the refrigerative mode has only exemplified natural cooling cooling, and the types of cooling such as spray water cooling certainly, ice-water bath cooling and freezing salt solution cooling are suitable for the present invention too.
The quality examination of the phosphor-nitrogen expansion type combustion inhibitor that embodiment 1-4 makes the results are shown in Table 1.
Table 1 quality product detected result table
Annotate: 1. the .P element adopts the wet oxidation quantitative analysis, and other elements adopt elemental analyser to detect.Flash EAm2 elemental analyser (U.S. Finnigan) is measured Elements C, H, N, 0 etc., measurement range 0.01%～100%, analysis time 5～10min, sample size 0.01～100mg.
2.. fusing point adopts the fusing point instrument to measure.
WRS-2A numeral fusing point instrument, useful range room temperature to 300 ℃, 5 ℃/min of temperature rise rate.
This fire retardant contains P, N element, and surface energy generated layer of even carbonaceous foam layer when the superpolymer that has added this based flame retardant was heated, this layer oxygen barrier, heat insulation, press down cigarette, nontoxic, and can prevent molten drop, thermostability is strong.
Fig. 1 is the infrared spectrum (KBr compressing tablet) of the fire retardant of embodiment 1 preparation: at 3400～3100cm
-1Have primary amine salt and-NH
2Absorption peak, 2900～3030cm
-1C-H is arranged, CH
2-and CH
3-structure absorption peak is at 1570cm
-1And 1340cm
-1NH is arranged
3 +Unsymmetrically and symmetric vibration absorption peak, at 1690cm
-1The place is a phenyl ring skeleton C=C vibration absorption peak, 1670cm
-1The C=N vibration absorption peak is arranged, the existence of provable thus melamine salt structure; At 1207cm
-1The two key stretching vibration peaks of P=0 are arranged, 1110cm
-1Be P-0 singly-bound stretching vibration absorption peak, hence one can see that, on spectrogram, show as, P=0 double bond absorption peak intensity a little less than, P-0 singly-bound absorption peak strength is stronger; 1110cm
-1And 1026cm
-1P-0-C vibration absorption peak is arranged, 850cm
-1The place is C-C1 vibration absorption peak.
The results of elemental analyses of embodiment 1 is: C 41.91%, and H 4.72%, and P 7.80%, and N 20.70%, and theoretical value is: C 41.74%, and H 4.97%, and P 7.70%, and N 20.87%, and the content and the theoretical value of each element are more identical; 1 examination of infrared spectrum result has in conjunction with the embodiments proved the exactness of this compound structure.
In order further to verify the flame retardant properties of fire retardant of the present invention, be research object with polyethylene (PE), the fire retardant for preparing is carried out the flame retardant properties test.
Fire retardant is added in the polyethylene by different ratios, make standard model, test its combustionproperty and mechanical property then.The making processes of standard model: polyethylene is plastified the mixing 5～10min in back on 160 ℃ duplex roller, add the mixing 10～15min of fire retardant again, 190 ℃ of shaped by fluid pressures on thermocompressor are made the thick standard model of 3.2mm with omnipotent sampling machine then.The combustionproperty and the measuring mechanical property of sample the results are shown in Table 2.
The The performance test results of table 2 flame-proof polyethylene
To annotate: 1.. the flame retardant properties test is carried out the vertical combustion experiment according to U.S. UL94 standard, measures according to ASTM D635, total Three Estate, the highest requirement is the V-0 level, is the V-1 level secondly, the V-2 level.
2.. melting index is measured according to ASTM D790 according to U.S. UL94 standard.
3.. shock strength is measured according to ASTM D256 according to U.S. UL94 standard.
4.. tensile strength is measured according to ASTM D638 according to U.S. UL94 standard.
5.. equipment: microcomputer control electronics universal testing machine RG2000-10.
As shown in Table 2, institute's synthetic fire retardant is 30% o'clock at consumption, and flame retardant rating reaches UL94-0, can be compatible well with polyethylene, can satisfy the application performance requirement of fire-retardant PE.
Claims (7)
1. a structural formula is
2. the preparation method of the described phosphor-nitrogen expansion type combustion inhibitor of claim 1, it is characterized in that: this method may further comprise the steps:
(1) be the 4-chloro-benzaldehyde and the isobutyric aldehyde of 1:2～2.5 with mol ratio, with the ethanolic soln of alkali, stir and 50～60 ℃ of temperature condition under, reaction 4～6h, after reaction is finished, cooling, after resultant of reaction is separated out, filter, obtaining white crystal shape filter cake is intermediate product (I);
(2) with mol ratio be the intermediate product (I) and the phosphoric acid of 1:1～2, join 4～6 times in the benzene series solvent of intermediate product (I) weight, and add 1～3% times of tosic acid or phenylformic acid or its sodium salt to intermediate product (I) weight, stir and 50～60 ℃ of temperature condition under, reaction 8～10h, after reaction finished, the benzene series solvent was removed in underpressure distillation, obtains thick intermediate product (II);
(3) with mol ratio be the trimeric cyanamide and the intermediate product (II) of 1:1～1.2, join 6～10 times in the water of trimeric cyanamide weight, stir and 90～110 ℃ of temperature condition under, with trimeric cyanamide reaction 4～6h, react finish after, cooling, after resultant of reaction is separated out, filter, get filter cake, the oven dry filter cake gets white crystal shape phosphor-nitrogen expansion type combustion inhibitor.
2. the preparation method of phosphor-nitrogen expansion type combustion inhibitor according to claim 2, it is characterized in that: the ethanolic soln of the alkali described in the step (1), comprise dehydrated alcohol and alkali, wherein alkali is sodium hydroxide or potassium hydroxide, the proportioning of alkali and dehydrated alcohol is 0.1mol:90～120ml, and the mol ratio of alkali and 4-chloro-benzaldehyde is 1～1.4:1.
3. the preparation method of phosphor-nitrogen expansion type combustion inhibitor according to claim 2, it is characterized in that: the benzene series solvent described in the step (1) is benzene,toluene,xylene or ethylbenzene.
4. the preparation method of phosphor-nitrogen expansion type combustion inhibitor according to claim 2 is characterized in that: in the step (1), filter obtain filter cake after, filter cake also will after the washing, obtain intermediate product (I) through the straight-chain paraffin liquid scrubbing, all the other are identical with step (1).
5. the preparation method of phosphor-nitrogen expansion type combustion inhibitor according to claim 4, it is characterized in that: described straight-chain paraffin liquid is normal heptane or normal hexane.
6. the preparation method of phosphor-nitrogen expansion type combustion inhibitor according to claim 2 is characterized in that: in the described step (3), filter obtain filter cake after, filter cake also will be dried through water washing again, all the other are identical with step (3).
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| CN108117668A (en) * | 2018-01-15 | 2018-06-05 | 三峡大学 | The fire retardant of one kind structure containing melamine, preparation method and applications |
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