CN103396450B - Fire retardant four (0,0-dibutyl phosphoryl) glycoluril compounds and preparation method thereof - Google Patents
Fire retardant four (0,0-dibutyl phosphoryl) glycoluril compounds and preparation method thereof Download PDFInfo
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- CN103396450B CN103396450B CN201310330596.7A CN201310330596A CN103396450B CN 103396450 B CN103396450 B CN 103396450B CN 201310330596 A CN201310330596 A CN 201310330596A CN 103396450 B CN103396450 B CN 103396450B
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- fire retardant
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- tributyl phosphate
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- dibutyl phosphoryl
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Abstract
The present invention relates to a kind of fire retardant four (0,0-dibutyl phosphoryl) glycoluril compounds and preparation method thereof, the structure of this compound is shown below:
Description
Technical field
The present invention relates to a kind of fire retardant four (0; 0-dibutyl phosphoryl) glycoluril compounds and preparation method thereof; this compound is the compound containing phosphorus, the two ignition-proof element of nitrogen, can be used as the fire retardant of polyester, polymeric amide, epoxy resin, unsaturated polyester, polyvinyl alcohol and coating etc.
Background technology
Along with synthetic materials is at electronic apparatus, communications and transportation, household furniture, the widespread use in the fields such as upholstery, the hidden danger of fire also gets more and more, therefore the fire-retardant major issue having become people and paid close attention to of material.At present, the trend of Fire Retardant Industry development is improving flame retardant properties while, more focus on environmental protection and ecological safety, and phosphorus flame retardant has efficiently, low toxicity, non-corrosiveness and with the advantage such as material compatibility is good, therefore there are good market outlook
Fire retardant four (0,0-dibutyl phosphoryl) glycoluril of the present invention belongs to many phosphorus structure, also containing cooperative flame retardant nitrogen element.P-N cooperative flame retardant has and promotes into carbon, and polyphosphoric acid covers, the functions such as anoxybiotic is heat insulation, expansions, from multiple fire retardant mechanism performance fire retardation, can produce excellent flame-retarded efficiency.This product structure has planar conjugate and symmetric stability, and decomposition temperature is high, good with macromolecular material consistency, the high temperature process of energy adaptation material, and basic material is cheap and easy to get, applied range, has market in urgent need, has well application and DEVELOPMENT PROSPECT.
Summary of the invention
An object of the present invention is to propose a kind of fire retardant four (0,0-dibutyl phosphoryl) glycoluril compounds, and its physical and chemical performance is stablized, and nontoxic, flame-retarded efficiency is high, good with macromolecular material consistency, can overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
A kind of fire retardant four (0,0-dibutyl phosphoryl) glycoluril, it is characterized in that, the structure of this compound is shown below:
Another object of the present invention is to the preparation method proposing a kind of fire retardant four (0,0-dibutyl phosphoryl) glycoluril, its technique is simple, and be easy to large-scale production, and cheaper starting materials is easy to get, facility investment is few, with low cost, and the method is:
Control tetrachloroglycine urea and the certain mol ratio of tributyl phosphate, tributyl phosphate is divided and is added drop-wise at different temperature for four times in the solution of the organic solvent of tetrachloroglycine urea, first, at 5 DEG C, the tributyl phosphate of tetrachloroglycine urea 1 times mole is dripped, stirring reaction 1h; Then be warming up to 40 DEG C, then drip the tributyl phosphate of 1 times mole, stirring reaction 1h; Be warming up to 70 DEG C again, then drip the tributyl phosphate of 1 times mole, stirring reaction 1h; Finally be warming up to 100 DEG C ~ 115 DEG C, then drip the tributyl phosphate of 1-3 times mole, insulation reaction 5 ~ 7h; Purified process, obtains white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.
The solution of the organic solvent of tetrachloroglycine urea as above is the quality grams of tetrachloroglycine urea is 1: 4 ~ 1: 6 with the ratio of the volume milliliter number of organic solvent.
Mol ratio certain is as above tetrachloroglycine urea: tributyl phosphate is 1: 4 ~ 1: 6.
Organic solvent as above is ethylene glycol diethyl ether, toluene, dimethyl formamide, dioxane or dimethylbenzene.
Purified process as above is that underpressure distillation goes out organic solvent and excessive tributyl phosphate (recycling); add the aqueous ethanolic solution of quality product grams 2 times of volume milliliter numbers again; and aqueous ethanolic solution is ethanol and water volume ratio 1: 1; stirring heating makes it dissolve, and cooling, makes product sufficient crystallising separate out; suction filtration; vacuum-drying, obtains white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.
Fire retardant four (0 of the present invention; 0-dibutyl phosphoryl) glycoluril is white needle-like crystals; product yield is 81.4% ~ 93.2%; decomposition temperature: 354 ± 2 DEG C; it is suitable for the fire retardant of polyester PBT, polyester PET, polyvinyl chloride, urethane, epoxy resin and unsaturated polyester etc.; preparation technology's principle of this fire retardant four (0,0-dibutyl phosphoryl) glycoluril is shown below:
Compared with prior art, usefulness of the present invention is:
1. fire retardant four (0 of the present invention, 0-dibutyl phosphoryl) structure of glycoluril has good symmetric characteristics, good with macromolecular material intermiscibility, stability high (decomposition temperature 354 ± 2 DEG C), can be applicable to the high temperature process of various engineering plastics, and nitrogen, phosphorus dual ignition-proof element cooperative flame retardant usefulness is high;
2. fire retardant four (0,0 dibutyl phosphoryl) glycoluril of the present invention is not halogen-containing, belongs to environmental friendliness fire retardant;
3. the preparation method of fire retardant four (0,0-dibutyl phosphoryl) glycoluril of the present invention is single step reaction, and technique is simple, and building-up process does not introduce impurity without the need to adding catalyzer; Equipment is simple, with low cost, is suitable for large-scale production, has good application and development prospect.
Accompanying drawing explanation
In order to the stuctures and properties spy further illustrating product provides following accompanying drawing.
1, the infrared spectrogram of fire retardant four (0,0-dibutyl phosphoryl) glycoluril, refers to Figure of description Fig. 1:
Fig. 1 shows, wherein 3052.6cm
-1and 2845.4cm
-1the absorption peak at place is-CH
2-and-CH
3absorption peak, 1750.3cm
-1for the absorption peak of C=O, 1254.5cm-1 is the absorption peak of P=O, 1182.2cm
-1for the absorption peak of P-O, 1113.3cm
-1and 1158.5cm
-1the absorption peak of C-O, 1012.5cm
-1for the absorption peak of P-N-C.
2, the nuclear magnetic spectrum figure of fire retardant four (0,0-dibutyl phosphoryl) glycoluril, refers to Figure of description Fig. 2:
Fig. 2 shows, deuterated water makees solvent, and δ 0.9 ~ 1.05 is-OCH
2cH
2cH
2cH
3on the methyl 3H peak that is connected with methylene radical; δ 1.35 ~ 1.55 is-OCH
2cH
2cH
2cH
3on the methylene radical 2H peak that is connected with methyl, δ 1.90 ~ 2.10 is-OCH
2cH
2cH
2cH
3on the methylene radical 2H peak that is connected with ethyl, δ 4.20 ~ 4.35 is-OCH
2cH
2cH
2cH
3on the methylene radical 2H peak that is connected with oxygen, δ 4.65 ~ 4.76 is the H peak of aqueous solvent proton exchange, and δ 6.80 ~ 6.90 is the C-H peak on glycoluril ring.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1 is in the 500mL there-necked flask that agitator, reflux condensing tube and thermometer are housed, the air in most bottle is caught up with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dimethyl formamide, stirring makes it dissolve, at 5 DEG C, drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Then raised temperature to 40 DEG C, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Raised temperature to 70 DEG C again, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Last raised temperature to 115 DEG C, then drip 25.0g (0.10mol) tributyl phosphate, insulation reaction 5h; after reaction terminates; underpressure distillation goes out dimethyl formamide (recycling), then adds the aqueous ethanolic solution that 182mL volume ratio is 1: 1, is heated with stirring to 80 DEG C and makes it dissolve; cooling; product sufficient crystallising is separated out, suction filtration, vacuum-drying; obtain white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.Its productive rate is 81.4%, and decomposition temperature is 354 ± 2 DEG C.
Embodiment 2 is in the 500mL there-necked flask that agitator, reflux condensing tube and thermometer are housed, the air in most bottle is caught up with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dimethylbenzene, stirring makes it dissolve, at 5 DEG C, drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Then raised temperature to 40 DEG C, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Raised temperature to 70 DEG C again, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Last raised temperature to 110 DEG C, then drip 37.5g (0.15mol) tributyl phosphate, insulation reaction 5h; after reaction terminates; underpressure distillation goes out dimethylbenzene and excessive tributyl phosphate (recycling), then adds the aqueous ethanolic solution that 182mL volume ratio is 1: 1, is heated with stirring to 80 DEG C and makes it dissolve; cooling; product sufficient crystallising is separated out, suction filtration, vacuum-drying; obtain white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.Its productive rate is 87.1%, and decomposition temperature is 354 ± 2 DEG C.
Embodiment 3 is in the 500mL there-necked flask that agitator, reflux condensing tube and thermometer are housed, the air in most bottle is caught up with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL toluene, stirring makes it dissolve, at 5 DEG C, drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Then raised temperature to 40 DEG C, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Raised temperature to 70 DEG C again, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Last raised temperature to 110 DEG C, then drip 50.0g (0.20mol) tributyl phosphate, insulation reaction 6h; after reaction terminates; underpressure distillation goes out toluene and excessive tributyl phosphate (recycling), then adds the aqueous ethanolic solution that 182mL volume ratio is 1: 1, is heated with stirring to 80 DEG C and makes it dissolve; cooling; product sufficient crystallising is separated out, suction filtration, vacuum-drying; obtain white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.Its productive rate is 90.5%, and decomposition temperature is 354 ± 2 DEG C.
Embodiment 4 is in the 500mL there-necked flask that agitator, reflux condensing tube and thermometer are housed, the air in most bottle is caught up with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL ethylene glycol diethyl ether, stirring makes it dissolve, at 5 DEG C, drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Then raised temperature to 40 DEG C, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Raised temperature to 70 DEG C again, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Last raised temperature to 105 DEG C, then drip 62.5g (0.25mol) tributyl phosphate, insulation reaction 6h; after reaction terminates; underpressure distillation goes out ethylene glycol diethyl ether and excessive tributyl phosphate (recycling), then adds the aqueous ethanolic solution that 182mL volume ratio is 1: 1, is heated with stirring to 80 DEG C and makes it dissolve; cooling; product sufficient crystallising is separated out, suction filtration, vacuum-drying; obtain white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.Its productive rate is 89.8%, and decomposition temperature is 354 ± 2 DEG C.
Embodiment 5 is in the 500mL there-necked flask that agitator, reflux condensing tube and thermometer are housed, the air in most bottle is caught up with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dioxane, stirring makes it dissolve, at 5 DEG C, drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Then raised temperature to 40 DEG C, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Raised temperature to 70 DEG C again, then drip 25.0g (0.10mol) tributyl phosphate, stirring reaction 1h; Last raised temperature to 100 DEG C, then drip 75.0g (0.30mol) tributyl phosphate, insulation reaction 7h; after reaction terminates; underpressure distillation goes out dioxane and excessive tributyl phosphate (recycling), then adds the aqueous ethanolic solution that 182mL volume ratio is 1: 1, is heated with stirring to 80 DEG C and makes it dissolve; cooling; product sufficient crystallising is separated out, suction filtration, vacuum-drying; obtain white needle-like crystals fire retardant four (0,0-dibutyl phosphoryl) glycoluril.Its productive rate is 93.2%, and decomposition temperature is 354 ± 2 DEG C.
Table 1 preparation example main technologic parameters
Inventor is also by the fire retardant four (0 of above-mentioned synthesis; 0-dibutyl phosphoryl) glycoluril is applied in PBT; the fire retardant four (0 of different ratios is added in PBT; 0-dibutyl phosphoryl) glycoluril; at 230 DEG C, batten is extruded respectively again with XJ-01 type forcing machine; batten is of a size of diameter 3mm, length 15mm.Then flame retardant properties mensuration is carried out to it, reference: the limiting oxygen index(LOI) of GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.Test-results is as shown in table 2:
Table 2 fire retardant four (0,0-dibutyl phosphoryl) glycoluril flame retardant properties in PBT
From above-mentioned table, fire retardant four (0,0-dibutyl phosphoryl) glycoluril has good flame retardant properties to PBT resin.
Claims (5)
1. fire retardant four (O, O-dibutyl phosphoryl) glycoluril compounds, it is characterized in that, the structure of this compound is shown below:
2. the preparation method of fire retardant four (O, O-dibutyl phosphoryl) glycoluril according to claim 1, it is characterized in that, the method is:
Control tetrachloroglycine urea and the certain mol ratio of tributyl phosphate, tributyl phosphate is divided and is added drop-wise at different temperature for four times in the solution of the organic solvent of tetrachloroglycine urea, first, at 5 DEG C, the tributyl phosphate of tetrachloroglycine urea 1 times mole is dripped, stirring reaction 1h; Then be warming up to 40 DEG C, then drip the tributyl phosphate of 1 times mole, stirring reaction 1h; Be warming up to 70 DEG C again, then drip the tributyl phosphate of 1 times mole, stirring reaction 1h; Finally be warming up to 100 DEG C ~ 115 DEG C, then drip the tributyl phosphate of 1-3 times mole, insulation reaction 5 ~ 7h; Purified process, obtains white needle-like crystals fire retardant four (O, O-dibutyl phosphoryl) glycoluril.
3. the preparation method of fire retardant four (O, O-dibutyl phosphoryl) glycoluril according to claim 2, is characterized in that: described organic solvent is ethylene glycol diethyl ether, toluene, dimethyl formamide, dioxane or dimethylbenzene.
4. fire retardant four (O according to claim 2; O-dibutyl phosphoryl) preparation method of glycoluril, it is characterized in that: the solution of the organic solvent of described tetrachloroglycine urea is the quality grams of tetrachloroglycine urea is 1: 4 ~ 1: 6 with the ratio of the volume milliliter number of organic solvent.
5. fire retardant four (O according to claim 2; O-dibutyl phosphoryl) preparation method of glycoluril; it is characterized in that: described purified process is that underpressure distillation goes out organic solvent and excessive tributyl phosphate; add the aqueous ethanolic solution of quality product grams 2 times of volume milliliter numbers again; and aqueous ethanolic solution is ethanol and water volume ratio 1: 1; stirring heating makes it dissolve; cooling; product sufficient crystallising is separated out; suction filtration; vacuum-drying, obtains white needle-like crystals fire retardant four (O, O-dibutyl phosphoryl) glycoluril.
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| CN104151794B (en) * | 2014-08-14 | 2016-05-18 | 苏州科技学院相城研究院 | Four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination and application process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457333A (en) * | 1965-10-23 | 1969-07-22 | Stauffer Chemical Co | Bis(hydroxypolyalkoxyalkyl)-n,n dihydroxyalkyl aminomethyl phosphonates |
| EP0413613A1 (en) * | 1989-08-18 | 1991-02-20 | Minnesota Mining And Manufacturing Company | Flame retardants |
| WO1994011425A1 (en) * | 1992-11-13 | 1994-05-26 | Minnesota Mining And Manufacturing Company | Flame retardants |
| CN102827369A (en) * | 2012-08-17 | 2012-12-19 | 沈阳化工大学 | Synthetic method of phosphorus-nitrogen intumescent flame retardant |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW476771B (en) * | 1999-11-05 | 2002-02-21 | Chang Chun Plastics Co Ltd | Nitrogen-containing and phosphorus-containing resin hardener and flame resistant resin composition containing the hardener |
| EP1563004A1 (en) * | 2002-11-21 | 2005-08-17 | Ciba SC Holding AG | Flame retardant composition comprising a phosphonic acid metal salt and a nitrogen-containing compound |
| US8138245B2 (en) * | 2006-04-04 | 2012-03-20 | Dsm Ip Assets B.V. | Halogen free flame retardant polyester composition |
| DE102006049519A1 (en) * | 2006-10-20 | 2008-04-24 | Lanxess Deutschland Gmbh | Flame retardant for curable molding materials comprises ethylenediamine phosphate, a halogen-free phosphorus compound and a halogen-free nitrogen compound |
| US10717929B2 (en) * | 2009-08-11 | 2020-07-21 | Ionic Flame Retardant Inc. | Ionic liquid flame retardants |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457333A (en) * | 1965-10-23 | 1969-07-22 | Stauffer Chemical Co | Bis(hydroxypolyalkoxyalkyl)-n,n dihydroxyalkyl aminomethyl phosphonates |
| EP0413613A1 (en) * | 1989-08-18 | 1991-02-20 | Minnesota Mining And Manufacturing Company | Flame retardants |
| WO1994011425A1 (en) * | 1992-11-13 | 1994-05-26 | Minnesota Mining And Manufacturing Company | Flame retardants |
| CN102827369A (en) * | 2012-08-17 | 2012-12-19 | 沈阳化工大学 | Synthetic method of phosphorus-nitrogen intumescent flame retardant |
Non-Patent Citations (1)
| Title |
|---|
| 王彦林 等.《无溶剂法合成2, 4, 6-三(O,O-二甲基磷酰基)-1,3,5-三嗪的研究》.《化学世界》.2010,(第5期), * |
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