CN103360625A - Flame retardant tetra (O-methyl-phenyl phosphinic) glycoluril compound and preparation method therefor - Google Patents
Flame retardant tetra (O-methyl-phenyl phosphinic) glycoluril compound and preparation method therefor Download PDFInfo
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- CN103360625A CN103360625A CN2013103305859A CN201310330585A CN103360625A CN 103360625 A CN103360625 A CN 103360625A CN 2013103305859 A CN2013103305859 A CN 2013103305859A CN 201310330585 A CN201310330585 A CN 201310330585A CN 103360625 A CN103360625 A CN 103360625A
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Abstract
The invention relates to a flame retardant tetra (O-methyl-phenyl phosphinic) glycoluril compound and a preparation method therefor. The structural formula of the compound is as follows:. The preparation method is as follows: the molar ratio of tetrachloro glycoluril to phenyl phosphonic acid dimethyl is controlled at 1:4-1:6; phenyl phosphonic acid dimethyl is added dropwisely into the solution of the organic solvent of tetrachloro glycoluril by four times; the mixture is reacted for 5-7 h at the temperature of 95 DEG C-105 DEG C, and subjected to purification processing to obtain tetra (O-methyl-phenyl phosphinic) glycoluril product. The compound is a good halogen-free phosphorus-nitrogen synergistic flame retardant, and can be used for flame retarding of polyester PBT, polyester PET, polyvinyl chloride, polyurethane, epoxy resin, unsaturated resin and the like. The compound has advantages of simple technology and small device investment, and is easy to realize industrialized production.
Description
Technical field
The present invention relates to a kind of fire retardant four (0-methyl-phenyl time phosphono) glycoluril compounds and preparation method thereof; this compound is the compound that contains phosphorus, the two ignition-proof elements of nitrogen, can be used as the fire retardant of polyester, polymeric amide, Resins, epoxy, unsaturated polyester, polyvinyl alcohol and coating etc.
Background technology
Development along with polymer material science, synthesized polymer material is used more and more extensive in daily life, yet, the inflammableness of macromolecular material often causes fire, bring threat also often for people's lives and properties, therefore to the flame-retardant modified major issue that has become people's concern of macromolecular material, fire retardant industry has obtained rapidly development, and flame retardant regulation has also obtained constantly replenishing and be perfect.At present, the trend of fire retardant material and fire retardant researchdevelopment is when improving flame retardant properties, more pay attention to environmental protection and ecological safety, and phosphorus-nitrogen containing flame retardant has efficiently, low toxicity, non-corrosiveness and with the advantages such as material compatibility is good, so phosphorus-nitrogen containing flame retardant has become the emphasis of research and development.
Fire retardant four of the present invention (0-methyl-phenyl time phosphono) glycoluril belongs to many phosphorus structure, also contains cooperative flame retardant nitrogen element.The P-N cooperative flame retardant has and promotes into carbon, and polyphosphoric acid covers, and anoxybiotic is heat insulation, and the multiple fire retardations such as expansion can produce good flame-retarded efficiency.This product structure has good symmetry, planar conjugate stability, also contain stable fragrant C-P key, decomposition temperature is high, owing to contain the polydirectional phenyl ring of electronic structure with macromolecular material has good 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, and good application and DEVELOPMENT PROSPECT are arranged.
Summary of the invention
One of purpose of the present invention is to propose a kind of fire retardant four (0-methyl-phenyl time phosphono) glycoluril compounds, and its physical and chemical performance is stable, and is nontoxic, and flame-retarded efficiency is high, and is good with the macromolecular material consistency, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of fire retardant four (0-methyl-phenyl time phosphono) glycoluril is characterized in that the structure of this compound is shown below:
Another object of the present invention is to propose the preparation method of a kind of fire retardant four (0-methyl-phenyl time phosphono) glycoluril compounds, its technique is simple, is easy to large-scale production, and raw material is cheap and easy to get, and facility investment is few, and is with low cost, and the method is:
Control tetrachloroglycine urea and the certain mol ratio of phenyl phosphinic acid dimethyl ester, the phenyl phosphinic acid dimethyl ester is divided in the solution of the organic solvent that under different temperature, is added drop-wise to tetrachloroglycine urea for four times, at first under 5 ℃, drip the phenyl phosphinic acid dimethyl ester of 1 times of mole of tetrachloroglycine urea, stirring reaction 1h; Then be warming up to 40 ℃, drip again the phenyl phosphinic acid dimethyl ester of 1 times of mole, stirring reaction 1h; Be warming up to again 70 ℃, drip again the phenyl phosphinic acid dimethyl ester of 1 times of mole, stirring reaction 1h; Be warming up at last 80 ℃～100 ℃, drip again the doubly phenyl phosphinic acid dimethyl ester of mole of 1-3, insulation reaction 5～7h; Purified processing gets white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril.
The solution of the organic solvent of aforesaid tetrachloroglycine urea is that the ratio of quality grams and the volume milliliter number of organic solvent of tetrachloroglycine urea is 1: 4～1: 6.
Aforesaid certain mol ratio is tetrachloroglycine urea: the phenyl phosphinic acid dimethyl ester is 1: 4～1: 6.
Aforesaid organic solvent is acetonitrile, toluene, dimethyl formamide, dioxane or dimethylbenzene.
Aforesaidly purifiedly be treated to underpressure distillation and go out organic solvent and excessive phenyl phosphinic acid dimethyl ester (recycling); the aqueous ethanolic solution that adds again 2 times of volume milliliters of quality product grams number; and aqueous ethanolic solution is ethanol and water volume ratio 1: 1; stirring heating makes its dissolving; cooling makes the product sufficient crystallising separate out suction filtration; vacuum-drying gets white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril.
Fire retardant four of the present invention (0-methyl-phenyl time phosphono) glycoluril is white needle-like crystals; the product yield is 82.2%～95.3%; decomposition temperature: (380 ± 2 ℃); it is suitable as the fire retardant of polyester PBT, polyester PET, polyvinyl chloride, urethane, Resins, epoxy, unsaturated polyester and polyvinyl alcohol etc., and the synthesis technique principle of this fire retardant four (0-methyl-phenyl time phosphono) glycoluril is shown below:
Compared with prior art, usefulness of the present invention is:
1. fire retardant four of the present invention (0-methyl-phenyl time phosphono) glycoluril novel structure, symmetrical configuration is good, stability high (380 ± 2 ℃ of decomposition temperatures) can be applicable to the high temperature process of various engineering plastics, and nitrogen, the dual ignition-proof element cooperative flame retardant of phosphorus usefulness are high;
2. fire retardant four of the present invention (0-methyl-phenyl time phosphono) glycoluril is not halogen-containing, belongs to the environmental friendliness fire retardant;
3. the preparation method of fire retardant four of the present invention (0-methyl-phenyl time phosphono) glycoluril is single step reaction, and technique is simple, and building-up process need not to add catalyzer and do not introduce impurity; Equipment is simple, and is with low cost, is suitable for large-scale production, and good application and development prospect is arranged.
Description of drawings
For structure and the performance spy who further specifies product provides following accompanying drawing.
1, the infrared spectrogram of fire retardant four (0-methyl-phenyl time phosphono) glycoluril, see Figure of description Fig. 1 for details:
Fig. 1 shows, wherein 3023.3cm
-1The absorption peak at place is the absorption peak on the phenyl ring, 2806.6cm
-1The absorption peak at place is-CH
3Absorption peak, 1750.3cm
-1Be the absorption peak of C=0,1400.5cm
-1Be the absorption peak of P=0,1312.5cm
-1Be the absorption peak of P-0,1151.3cm
-1And 1248.5cm
-1Be the absorption peak of C-0,1021.8cm
-1Absorption peak for P-N-C.
2, the nuclear magnetic spectrum figure of fire retardant four (0-methyl-phenyl time phosphono) glycoluril, see Figure of description Fig. 2 for details:
Fig. 2 shows that deuterochloroform is made solvent, and chemical shift δ 3.35-3.42 place is-OCH
3On methyl 3H peak; δ 6.50-6.60 is the C-H peak on the glycoluril ring; δ 7.20-7.30 is the proton H peak of deuterochloroform exchange of solvent; δ 7.30-7.75 is P-C
6H
5On phenyl ring 5H peak.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment 2 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, catch up with the interior air of most bottle with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL toluene, stirring makes its dissolving, under 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; The temperature that raises again drips 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h again to 40 ℃; Be warming up to again 70 ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up at last 90 ℃; drip again 25.5g (0.15mol) phenyl phosphinic acid dimethyl ester; insulation reaction 6h; after reaction finishes; underpressure distillation goes out toluene and excessive phenyl phosphinic acid dimethyl ester (recycling); add again the 152mL volume ratio and be 1: 1 aqueous ethanolic solution; be heated with stirring to 80 ℃ and make its dissolving; cooling makes the product sufficient crystallising separate out suction filtration; vacuum-drying; white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 88.4%, decomposition temperature is (380 ± 2) ℃.
Embodiment 3 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, catch up with the interior air of most bottle with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dioxane, stirring makes its dissolving, under 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 40 ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 70 ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up at last 95 ℃; 34.0g (0.20mol) the phenyl phosphinic acid dimethyl ester that drips again; insulation 6h; after reaction finishes; underpressure distillation goes out dioxane and excessive phenyl phosphinic acid dimethyl ester (recycling); add again the 152mL volume ratio and be 1: 1 aqueous ethanolic solution; be heated with stirring to 80 ℃ and make its dissolving; cooling makes the product sufficient crystallising separate out suction filtration; vacuum-drying; white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 95.3%, decomposition temperature is (380 ± 2) ℃.
Embodiment 4 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, catch up with the interior air of most bottle with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dimethylbenzene, stirring makes its dissolving, under 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 40 ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 70 ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up at last 95 ℃; drip again 42.5g (0.25mol) phenyl phosphinic acid dimethyl ester; insulation reaction 5h; after reaction finishes; underpressure distillation goes out dimethylbenzene and excessive phenyl phosphinic acid dimethyl ester (recycling); add again the 152mL volume ratio and be 1: 1 aqueous ethanolic solution; be heated with stirring to 80 ℃ and make its dissolving; cooling makes the product sufficient crystallising separate out suction filtration; vacuum-drying; white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 89.5%, decomposition temperature is (380 ± 2) ℃.
Embodiment 5 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, catch up with the interior air of most bottle with nitrogen, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL methane amide, stirring makes its dissolving, under 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Between the temperature to 40 that then raises ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Increase the temperature to again 70 ℃, drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up at last 100 ℃; drip again 25.5g (0.30mol) phenyl phosphinic acid dimethyl ester; insulation reaction 5h; after reaction finishes; underpressure distillation goes out dimethyl formamide and excessive phenyl phosphinic acid dimethyl ester (recycling); add again the 152mL volume ratio and be 1: 1 aqueous ethanolic solution; be heated with stirring to 80 ℃ and make its dissolving; cooling makes the product sufficient crystallising separate out suction filtration; vacuum-drying; white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 91.1%, decomposition temperature is (380 ± 2) ℃.
Table 1 preparation example main technologic parameters
This case contriver also is applied to above-mentioned synthetic fire retardant four (0-methyl-phenyl time phosphono) glycoluril among the PET; fire retardant four (0-methyl-phenyl time phosphono) glycoluril that in PET, adds different ratios; under 245 ℃, extrude batten respectively with XJ-01 type forcing machine again; batten is of a size of diameter 3mm, length 15mm.Then it is carried out flame retardant properties and measure the limiting oxygen index(LOI) of reference: 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-methyl-phenyl time phosphono) glycoluril flame retardant properties in PET
By above-mentioned table as can be known, fire retardant four (0-methyl-phenyl time phosphono) glycoluril has preferably flame retardant properties to the PET resin.
Claims (6)
1. the present invention relates to a kind of fire retardant four (0-methyl-phenyl time phosphono) glycoluril compounds, it is characterized in that the structure of this compound is shown below:
2. the preparation method of fire retardant four according to claim 1 (0-methyl-phenyl time phosphono) glycoluril is characterized in that the method is:
Control tetrachloroglycine urea and the certain mol ratio of phenyl phosphinic acid dimethyl ester, the phenyl phosphinic acid dimethyl ester is divided in the solution of the organic solvent that under different temperature, is added drop-wise to tetrachloroglycine urea for four times, at first under 5 ℃, drip the phenyl phosphinic acid dimethyl ester of 1 times of mole of tetrachloroglycine urea, stirring reaction 1h; Then be warming up to 40 ℃, drip again the phenyl phosphinic acid dimethyl ester of 1 times of mole, stirring reaction 1h; Be warming up to again 70 ℃, drip again the phenyl phosphinic acid dimethyl ester of 1 times of mole, stirring reaction 1h; Be warming up at last 80 ℃～100 ℃, drip again the doubly phenyl phosphinic acid dimethyl ester of mole of 1-3, insulation reaction 5～7h; Purified processing gets white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril.
3. the preparation method of fire retardant four according to claim 2 (0-methyl-phenyl time phosphono) glycoluril, it is characterized in that: described certain mol proportion is tetrachloroglycine urea: the phenyl phosphinic acid dimethyl ester is 1: 4～1: 6.
4. the preparation method of fire retardant four according to claim 2 (0-methyl-phenyl time phosphono) glycoluril, it is characterized in that: described organic solvent is acetonitrile, toluene, dimethyl formamide, dioxane or dimethylbenzene.
5. the preparation method of fire retardant four according to claim 2 (0-methyl-phenyl time phosphono) glycoluril is characterized in that: the solution of the organic solvent of described tetrachloroglycine urea is that the ratio of quality grams and the volume milliliter number of organic solvent of tetrachloroglycine urea is 1: 4～1: 6.
6. the preparation method of fire retardant four according to claim 2 (0-methyl-phenyl time phosphono) glycoluril; it is characterized in that: describedly purifiedly be treated to underpressure distillation and go out organic solvent and excessive phenyl phosphinic acid dimethyl ester; the aqueous ethanolic solution that adds again 2 times of volume milliliters of quality product grams number; and aqueous ethanolic solution is ethanol and water volume ratio 1: 1; stirring heating makes its dissolving; cooling; the product sufficient crystallising is separated out; suction filtration; vacuum-drying gets white needle-like crystals four (0-methyl-phenyl time phosphono) glycoluril.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194041A (en) * | 2014-08-14 | 2014-12-10 | 苏州科技学院相城研究院 | Tetra(0-methyl-phenylphosphinyl)glycoluril (TMPG) flame retardant composition and application method thereof |
| CN108164534A (en) * | 2013-11-25 | 2018-06-15 | 四国化成工业株式会社 | Glycoluril class and its utilization with functional group |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1714120A (en) * | 2002-11-21 | 2005-12-28 | 西巴特殊化学品控股有限公司 | Flame retardant composition comprising a phosphonic acid metal salt and a nitrogen-containing compound |
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- 2013-08-01 CN CN201310330585.9A patent/CN103360625B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1714120A (en) * | 2002-11-21 | 2005-12-28 | 西巴特殊化学品控股有限公司 | Flame retardant composition comprising a phosphonic acid metal salt and a nitrogen-containing compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164534A (en) * | 2013-11-25 | 2018-06-15 | 四国化成工业株式会社 | Glycoluril class and its utilization with functional group |
| CN104194041A (en) * | 2014-08-14 | 2014-12-10 | 苏州科技学院相城研究院 | Tetra(0-methyl-phenylphosphinyl)glycoluril (TMPG) flame retardant composition and application method thereof |
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