CN101007953A - Triazine ring combustion inhibitor containing phosphorus and its preparing process - Google Patents
Triazine ring combustion inhibitor containing phosphorus and its preparing process Download PDFInfo
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Abstract
The invention discloses a phosphoric triazine radical containing fire retarding agent and the preparing method. The method comprises following steps: putting neopentyl glycol phosphite ester and cyanuric acid of same equivalent weight in organic solvent, reacting for 2- 10 hours at normal temperature to 140 Deg. C, getting 1, 3, 5- triazine neopentyl glycol phosphate; then putting got 1, 3, 5- triazine neopentyl glycol phosphate and diamine of same equivalent weight in inert liquid for replace reaction and getting phosphoric triazine radical containing fire retarding agent, the reacting temperature is from normal temperatur to 160 Deg. C, reacting time is 6- 72 hours. The number average molecular weight of product is 2000- 20000, and the decompostion temperature is 240- 400 Deg. C. The invention increases the fire retarding agent's decompostion temperature, which enables it not to decompose during macromolecular material processing; and the expanded fire retarding agent ploymer prepared in this invention contains P, N and C element, which is multifunctional.
Description
Technical field
The present invention relates to a kind of fire retardant, be specifically related to a kind of triazine ring combustion inhibitor containing phosphorus and preparation method thereof.
Background technology
The fire retardant mechanism of present employed expansion phosphorus-nitrogen containing 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 part one acid sources, carbon source, source of the gas.Acid source can generate the compound of mineral acid when being generally mineral acid or being heated to 100～250 ℃, as phosphoric acid, boric acid, various phosphoric acid salt, phosphoric acid ester etc.; Carbon source (char-forming agent) is the basis that forms the foam charring layer, is generally the poly-hydroxy based compound of rich carbon, as starch, tetramethylolmethane, glycerine and the organic ester etc. that contains polyol.Source of the gas (foaming source) is generally amine or amides, trimeric cyanamide, Dyhard RU 100, polyphosphonic acid ammonium etc.
The expanding fire retardant that is used for macromolecular material is generally by ammonium polyphosphate (acid source), tetramethylolmethane (carbon source), trimeric cyanamide (source of the gas) is a main component, perhaps add certain auxiliary agent by condensation phase mechanism to improve the flame retardant effect of fire retardant.It is generally acknowledged that the fire retardant mechanism of intumescent system is the ammonium polyphosphate decomposes, generate phosphoric acid or tetra-sodium, make the tetramethylolmethane esterification with strong dehydration, and then the dehydration carbonization.The ammonia that water that reaction generates and trimeric cyanamide reaction generate expands the charcoal layer, finally forms the microporous charcoal layer of one deck, thus secluding air and thermal conduction, and the protection polymer body reaches fire-retardant purpose.
As the novel char-forming agent in the expansion type flame retardant system, verified have significant synergistic effect to the fire retardation that improves expansion type flame retardant based on the nitrogenous compound of triazine ring derivatives.Its Halogen, low toxicity, the decomposition temperature height is fit to processing, and is little to the mechanical property influence, do not ooze out, and flame retardant properties is good.The initiator of synthetic this based flame retardant is active big, can with contain the synthetic multiple dystectic compound of not isoplastic compound reaction.It is expansion type flame retardant architectural study and hot of research and development.
Though the flame retardant properties of performance was very excellent when ammonium polyphosphate particularly mixed with tetramethylolmethane and trimeric cyanamide, but the ammonium polyphosphate decomposition temperature is low, in the course of processing, and degraded easily, make the high molecular polymer variable color, and this based flame retardant also needs compounded technology.
U.S. Pat 5296598, US5314937 discloses the synthetic trimeric cyanamide monomer-2 that contains phosphoric acid and ester thereof, 4-two amidos-1,3,5-triazines base-6-phosphoric acid (ester).Have P in this compound simultaneously, N is to be used as the interpolation fire retardant in the polymkeric substance.It has following structural formula:
Wherein R is methyl, ethyl, ring neopentyl glycol base.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.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, synthetic a kind of P, N of containing novel the time, the expansion type flame retardant polymkeric substance of C, make the thermostability of fire retardant higher, it has the multi-functional character of potion equally, to be applied to macromolecular material as flame retardant additives.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of triazine ring combustion inhibitor containing phosphorus comprises the steps and processing condition:
(1) preparation of 1,3,5-triazines ring neopentyl glycol phosphoric acid ester: in the presence of organic solvent, the neopentyl glycol phosphite of equivalent and Cynuric Chloride under ℃ temperature condition of room temperature～140, are reacted and generated 1,3,5-triazines ring neopentyl glycol phosphoric acid ester in 2～10 hours; The mass ratio of organic solvent and Cynuric Chloride is 10～30: 1;
(2) preparation of triazine ring combustion inhibitor containing phosphorus: with 1 of step (1) preparation, 3, diamines substitution reaction in inert solvent of 5-triazine ring neopentyl glycol phosphoric acid ester and equivalent makes triazine ring combustion inhibitor containing phosphorus, and temperature of reaction is room temperature～160 ℃, and the reaction times is 6～72 hours; The mass ratio of inert solvent and three (neopentyl glycol cyclic phosphate) is 2 ∽ 10: 1.
The organic solvent of described step (1) is selected from normal hexane, toluene, ethylbenzene, dimethylbenzene, N, one or more in dinethylformamide or the methyl-sulphoxide organic solvent.
The neopentyl glycol phosphite of described step (1) is methyl esters, ethyl ester, propyl ester or the isopropyl ester of neopentyl glycol phosphorous acid.
The reaction times of described step (1) is 3～4 hours; The temperature of reaction of described step (1) is 105～115 ℃.
Solvent in the described step (2) is a toluene, dimethylbenzene, methylene dichloride, chloroform, acetone, methyl alcohol, ethanol, tetrahydrofuran (THF), dioxane, N, dinethylformamide, organic solvents such as methyl-sulphoxide.The diamines of described step (2) is piperazine, quadrol, hexanediamine or aromatic diamines.The temperature of reaction of described step (2) is a room temperature, and the reaction times is 12～24 hours.
By a kind of triazine ring combustion inhibitor containing phosphorus of method for preparing, its structural formula is formula (1) or formula (2)
Wherein X is C
2～C
6Fatty group or C
6～C
8The fragrance phenyl ring, the number-average molecular weight of fire retardant is 2000～20000; Its decomposition temperature is 240～400 ℃, and decomposing residual volume is 20～60% (nitrogen), 5～30% (air).
The molecular structure of 1,3,5-triazines ring neopentyl glycol phosphoric acid ester is as follows among the present invention:
Below in conjunction with typical chemical equation principle of the present invention is done and to be described in further detail:
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) the synthetic fire retardant is a macromolecular compound, has improved the thermostability of fire retardant, makes the decomposition temperature of fire retardant increase, and fire retardant is not decomposed in the processing of high molecular material process;
(2) this expansion type flame retardant polymkeric substance contains P, N, C element simultaneously, and because of C can form thermofin, P can promote the generation of carbon, and N can foam carbon is expanded, so this fire retardant has the multi-functional character of potion.
Description of drawings
The infrared spectrum of the 1,3,5-triazines ring neopentyl glycol phosphoric acid ester of Fig. 1 embodiment 1 preparation;
The 1,3,5-triazines ring neopentyl glycol phosphoric acid ester of Fig. 2 embodiment 1 preparation
1H NMR spectrogram;
The 1,3,5-triazines ring neopentyl glycol phosphoric acid ester of Fig. 3 embodiment 1 preparation
31P NMR spectrogram;
The infrared spectrum of (the 2-piperazinyl-4-neopentyl glycol cyclic phosphate-1,3,5-triazines ring) of Fig. 4 embodiment 1 preparation;
The MAS-NMR of (the 2-piperazinyl-4-neopentyl glycol cyclic phosphate-1,3,5-triazines ring) of Fig. 5 embodiment 1 preparation
31P figure;
The thermogravimetric analysis figure of (the 2-piperazinyl-4-neopentyl glycol cyclic phosphate-1,3,5-triazines ring) of Fig. 6 embodiment 1 preparation, 20 ℃/min of warm speed (air, nitrogen).
Embodiment
In order better to understand the present invention, the invention will be further described below in conjunction with embodiment and accompanying drawing, but the scope of protection of present invention is not limited to the scope that embodiment represents.
(1) preparation of 1,3,5-triazines ring neopentyl glycol phosphoric acid ester: 36.9g (0.2mol) Cynuric Chloride and 600g toluene join a 1000mL and are equipped with in the four-hole boiling flask of magnetic agitation, prolong, constant voltage addition funnel and thermometer.Reaction system remains on room temperature with water-bath, and 103.3g (0.63mol) neopentyl glycol phosphorous acid ethyl ester is added drop-wise in the system about 2h.After dropwising, reaction system is heated to backflow 4h.In this process, when about backflow 10min, produce thick product solid.After reaction finished, mixture was cooled to room temperature.The thick product that produces filters, with toluene and normal hexane washing, 40～50 ℃ of vacuum-dryings.The thick product dehydrated alcohol recrystallization that obtains obtains 96.7g white crystal three (neopentyl glycol cyclic phosphate)-1,3,5-triazines ring, productive rate 92.2%.Infrared spectrum is seen Fig. 1 (KBr compressing tablet): 2902, and 2794cm
-1(CH
3-, CH
2-), 1502cm
-1(C=N in the triazine ring), 1275cm
-1(P=O), 1057,1007cm
-1(P-O-C);
1H NMR sees Fig. 2 (molten neat CDCl
3): 0.8ppm (CH
3-), 3.4ppm (CH
2-O);
31PNMR sees Fig. 3 (solvent C DCl
3): 5.1ppm (P=O).
(2) preparation of triazine ring combustion inhibitor containing phosphorus: magnetic agitation, reflux condensing tube and thermometer are installed at a 500mL four-hole boiling flask.52.5g (0.1mol) three (neopentyl glycol cyclic phosphate)-1,3,5-triazines rings and 200g dehydrated alcohol join in the flask, mix, and add 8.6g (0.1mol) Piperazine anhydrous.Reaction mixture slowly is heated to 70 ℃ under nitrogen protection, react 12h under this temperature.After reaction finished, mixture was cooled to the greenhouse.Sedimentation and filtration is used hot water and washing with acetone successively.Filter cake is 80 ℃ of dryings in vacuum drying oven, get 27.8g white powder poly-(2-piperazinyl-4-neopentyl glycol cyclic phosphate-1,3,5-triazines ring), productive rate 89.2%.This material number-average molecular weight is 12000; Infrared spectrum is seen Fig. 4 (KBr compressing tablet): 2970, and 2894cm
-1(CH
3-, CH
2-), 1555cm
-1(C (triazine)-N (piperazine)), 1451cm
-1(C=N in the triazine ring), 1277cm
-1(P=O), 1057,1008cm
-1(P-O-C); MAS-NMR
31The p spectrum is seen Fig. 5: 4.7ppm (P=O); Thermogravimetric analysis figure sees Fig. 6, and decomposition temperature is 318 ℃ (nitrogen), 325 ℃ (air), and decomposing residual volume is 40% (nitrogen), 9.8% (air).
(1) 1,3, the preparation of 5-triazine ring neopentyl glycol phosphoric acid ester: the mixing solutions of 36.9g (0.2mol) Cynuric Chloride and 300g dimethylbenzene and ethylbenzene joins a 1000mL and is equipped with in the four-hole boiling flask of magnetic agitation, prolong, constant voltage addition funnel and thermometer.Reaction system remains on room temperature with water-bath, and 94.8g (0.63mol) neopentyl glycol methyl phosphite is added drop-wise in the system about 3h.After dropwising, reaction system is heated to 140 ℃ of reaction 2h.In this process, when about backflow 5min, produce thick product solid.After reaction finished, mixture was cooled to room temperature.The thick product that produces filters, with dimethylbenzene and normal hexane washing, 40～50 ℃ of vacuum-dryings.The thick product dehydrated alcohol recrystallization that obtains obtains 88.7g light yellow crystal three (neopentyl glycol cyclic phosphate)-1,3,5-triazines ring, productive rate 84.6%.
(2) preparation of triazine ring combustion inhibitor containing phosphorus: magnetic agitation, reflux condensing tube and thermometer are installed at a 500mL four-hole boiling flask.52.5g (0.1mol) three (neopentyl glycol cyclic phosphate)-1,3,5-triazines ring and 5200g N, dinethylformamide joins in the flask, mixes, and adds 6.0g (0.1mol) quadrol.Reaction mixture is room temperature reaction 72h under nitrogen protection.After reaction finished, mixture filtered, and uses hot water and washing with acetone successively.Filter cake is 80 ℃ of dryings in vacuum drying oven, get 14.3g white powder poly-(2-quadrol base-4-neopentyl glycol cyclic phosphate-1,3,5-triazines ring), productive rate 46.8%.
(1) preparation of 1,3,5-triazines ring neopentyl glycol phosphoric acid ester: 36.9g (0.2mol) Cynuric Chloride and 900g N, dinethylformamide join a 1000mL and are equipped with in the four-hole boiling flask of magnetic agitation, constant voltage addition funnel and thermometer.Reaction system remains on room temperature with water-bath, and 112.1g (0.63mol) neopentyl glycol phosphorous acid isopropyl ester is added drop-wise in the system about 3h.After dropwising, reaction system is at 40 ℃ of reaction 10h.After reaction finished, mixture was cooled to room temperature.Product mixture underpressure distillation solvent, the thick product dehydrated alcohol recrystallization that obtains obtains 55.8g light yellow crystal three (neopentyl glycol cyclic phosphate)-1,3,5-triazines ring, productive rate 53.2%.
(2) preparation of triazine ring combustion inhibitor containing phosphorus: magnetic agitation, reflux condensing tube and thermometer are installed at a 500mL four-hole boiling flask.52.5g (0.1mol) three (neopentyl glycol cyclic phosphate)-1,3,5-triazines rings and 100g methyl-sulphoxide join in the flask, mix, and add 11.6g (0.1mol) hexanediamine.Reaction mixture is heated to 160 ℃ under nitrogen protection, reaction 6h.After reaction finished, mixture filtered, and uses hot water and washing with acetone successively.Filter cake is 80 ℃ of dryings in vacuum drying oven, get 23.7g white powder poly-(2-hexanediamine base-4-neopentyl glycol cyclic phosphate-1,3,5-triazines ring), productive rate 74.3%.
Claims (10)
1, a kind of preparation method of triazine ring combustion inhibitor containing phosphorus is characterized in that comprising the steps and processing condition:
(1) preparation of 1,3,5-triazines ring neopentyl glycol phosphoric acid ester: in the presence of organic solvent, the neopentyl glycol phosphite of equivalent and Cynuric Chloride under ℃ temperature condition of room temperature～140, are reacted and generated 1,3,5-triazines ring neopentyl glycol phosphoric acid ester in 2～10 hours; The mass ratio of organic solvent and Cynuric Chloride is 10～30: 1;
(2) preparation of triazine ring combustion inhibitor containing phosphorus: with 1 of step (1) preparation, 3, diamines substitution reaction in inert solvent of 5-triazine ring neopentyl glycol phosphoric acid ester and equivalent makes triazine ring combustion inhibitor containing phosphorus, and temperature of reaction is room temperature～160 ℃, and the reaction times is 6～72 hours; The mass ratio of inert solvent and three (neopentyl glycol cyclic phosphate) is 2 ∽ 10: 1.
2, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, the organic solvent that it is characterized in that described step (1) is selected from normal hexane, toluene, ethylbenzene, dimethylbenzene, N, one or more in dinethylformamide and the methyl-sulphoxide.
3, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, the neopentyl glycol phosphite that it is characterized in that described step (1) are methyl esters, ethyl ester, propyl ester or the isopropyl ester of neopentyl glycol phosphorous acid.
4, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, the reaction times that it is characterized in that described step (1) is 3～4 hours.
5, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, the temperature of reaction that it is characterized in that described step (1) is 105～115 ℃.
6, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, it is characterized in that the inert solvent in the described step (2) is toluene, dimethylbenzene, methylene dichloride, chloroform, acetone, methyl alcohol, ethanol, tetrahydrofuran (THF), dioxane, N, dinethylformamide or methyl-sulphoxide.
7, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, the diamines that it is characterized in that described step (2) is piperazine, quadrol, diamines or aromatic diamines.
8, the preparation method of a kind of triazine ring combustion inhibitor containing phosphorus according to claim 1, the temperature of reaction that it is characterized in that described step (2) is a room temperature, the reaction times is 12～24 hours.
9, by a kind of triazine ring combustion inhibitor containing phosphorus of any described method preparation of claim 1～8, the structural formula that it is characterized in that triazine ring combustion inhibitor containing phosphorus is formula (1) or formula (2);
Wherein X is C
2～C
6Fatty group or C
6～C
8Fragrant phenyl ring.
10, triazine ring combustion inhibitor containing phosphorus according to claim 1, the number-average molecular weight that it is characterized in that described triazine ring combustion inhibitor containing phosphorus is 2000～20000, decomposition temperature is 240～400 ℃.
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| JP4984385B2 (en) * | 2004-10-18 | 2012-07-25 | Ｄｉｃ株式会社 | Epoxy resin composition and cured product thereof |
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