CN103360625B - 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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- CN103360625B CN103360625B CN201310330585.9A CN201310330585A CN103360625B CN 103360625 B CN103360625 B CN 103360625B CN 201310330585 A CN201310330585 A CN 201310330585A CN 103360625 B CN103360625 B CN 103360625B
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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 shown in the specification. The preparation method comprise that: 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, epoxy resin, unsaturated polyester, polyvinyl alcohol and coating etc.
Background technology
Development along with polymer material science, synthesized polymer material is applied more and more extensive in daily life, yet, the inflammableness of macromolecular material often causes fire, bring threat also often to people's lives and properties, so the flame-retardant modified major issue that has become people's concern to macromolecular material, fire retardant industry has obtained development rapidly, and flame retardant regulation has also obtained constantly supplementing and is perfect.At present, the trend of fire retardant material and fire retardant researchdevelopment is when improving flame retardant properties, more focus on environmental protection and ecological safety, and phosphorus-nitrogen containing flame retardant has efficiently, low toxicity, non-corrosiveness and with the advantage 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 multiple fire retardations such as P-N cooperative flame retardant has and promotes into carbon, and polyphosphoric acid covers, and anoxybiotic is heat insulation, 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 containing the polydirectional phenyl ring of electronic structure and 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, has good application and DEVELOPMENT PROSPECT.
Summary of the invention
One of object 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 nontoxic, flame-retarded efficiency is high, good with macromolecular material consistency, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
Fire retardant four (0-methyl-phenyl time phosphono) glycoluril, is characterized in that, the structure of this compound is shown below:
The preparation method who another object of the present invention is to propose 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, with low cost, and the method is:
Control tetrachloroglycine urea and the certain mol ratio of phenyl phosphinic acid dimethyl ester, phenyl phosphinic acid dimethyl ester is divided in the solution of the organic solvent that is added drop-wise to tetrachloroglycine urea for four times at different temperature, first at 5 ℃, drip the phenyl phosphinic acid dimethyl ester of 1 times mole of tetrachloroglycine urea, stirring reaction 1h; Then be warming up to 40 ℃, then drip the phenyl phosphinic acid dimethyl ester of 1 times mole, stirring reaction 1h; Be warming up to again 70 ℃, then drip the phenyl phosphinic acid dimethyl ester of 1 times mole, stirring reaction 1h; Finally be warming up to 80 ℃～100 ℃, then drip the phenyl phosphinic acid dimethyl ester of 1-3 times mole, insulation reaction 5～7h; Purified processing, obtains white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril.
The solution of the organic solvent of tetrachloroglycine urea as above is that the ratio of the quality grams of tetrachloroglycine urea and the volume milliliter number of organic solvent is 1: 4～1: 6.
Certain mol ratio as above is tetrachloroglycine urea: phenyl phosphinic acid dimethyl ester is 1: 4～1: 6.
Organic solvent as above is acetonitrile, toluene, dimethyl formamide, dioxane or dimethylbenzene.
As abovely 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 milliliter numbers of quality product grams; and aqueous ethanolic solution is ethanol and water volume ratio 1: 1; stirring heating makes its dissolving; cooling, product sufficient crystallising is separated out, suction filtration; vacuum-drying, obtains 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; 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, epoxy resin, 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 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 is not introduced impurity without 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 further illustrate structure and the performance spy of product, provide following accompanying drawing.
1, the infrared spectrogram of fire retardant four (0-methyl-phenyl time phosphono) glycoluril, refers to Figure of description Fig. 1:
Fig. 1 shows, wherein 3023.3cm
-1the absorption peak at place is the absorption peak on phenyl ring, 2806.6cm
-1the absorption peak at place is-CH
3absorption peak, 1750.3cm
-1for the absorption peak of C=0,1400.5cm
-1for the absorption peak of P=0,1312.5cm
-1for the absorption peak of P-0,1151.3cm
-1and 1248.5cm
-1for 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, refers to Figure of description Fig. 2:
Fig. 2 shows, 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 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 1 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, with nitrogen, catch up with the air in most bottle, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL acetonitrile, stirring makes its dissolving, at 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; The temperature to 40 ℃ that raises again, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; The temperature to 70 ℃ that raises again, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Temperature to 80 ℃ finally raises; drip again 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester; insulation reaction 7h; after reaction finishes; underpressure distillation goes out acetonitrile (recycling); adding 152mL volume ratio is the aqueous ethanolic solution of 1: 1 again. be heated with stirring to 80 ℃ and make its dissolving; cooling; product sufficient crystallising is separated out; suction filtration, vacuum-drying, obtains white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril; its productive rate is 82.2%, and decomposition temperature is (380 ± 2) ℃.
Embodiment 2 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, with nitrogen, catch up with the air in most bottle, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL toluene, stirring makes its dissolving, at 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Raise again warm to 40 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 70 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Finally be warming up to 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); adding 152mL volume ratio is the aqueous ethanolic solution of 1: 1 again; be heated with stirring to 80 ℃ and make its dissolving; cooling, product sufficient crystallising is separated out, suction filtration; vacuum-drying; obtain white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 88.4%, and decomposition temperature is (380 ± 2) ℃.
Embodiment 3 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, with nitrogen, catch up with the air in most bottle, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dioxane, stirring makes its dissolving, at 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 40 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 70 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Finally be warming up to 95 ℃; 34.0g (0.20mol) the phenyl phosphinic acid dimethyl ester dripping again; insulation 6h; after reaction finishes; underpressure distillation goes out dioxane and excessive phenyl phosphinic acid dimethyl ester (recycling); adding 152mL volume ratio is the aqueous ethanolic solution of 1: 1 again; be heated with stirring to 80 ℃ and make its dissolving; cooling, product sufficient crystallising is separated out, suction filtration; vacuum-drying; obtain white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 95.3%, and decomposition temperature is (380 ± 2) ℃.
Embodiment 4 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, with nitrogen, catch up with the air in most bottle, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL dimethylbenzene, stirring makes its dissolving, at 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 40 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Be warming up to again 70 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Finally be warming up to 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); adding 152mL volume ratio is the aqueous ethanolic solution of 1: 1 again; be heated with stirring to 80 ℃ and make its dissolving; cooling, product sufficient crystallising is separated out, suction filtration; vacuum-drying; obtain white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 89.5%, and decomposition temperature is (380 ± 2) ℃.
Embodiment 5 is in being equipped with the 500mL there-necked flask of agitator, reflux condensing tube and thermometer, with nitrogen, catch up with the air in most bottle, add 28.0g (0.10mol) tetrachloroglycine urea and 150mL methane amide, stirring makes its dissolving, at 5 ℃, drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Between the temperature to 40 that then raises ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Increase the temperature to again 70 ℃, then drip 17.0g (0.10mol) phenyl phosphinic acid dimethyl ester, stirring reaction 1h; Finally be warming up to 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); adding 152mL volume ratio is the aqueous ethanolic solution of 1: 1 again; be heated with stirring to 80 ℃ and make its dissolving; cooling, product sufficient crystallising is separated out, suction filtration; vacuum-drying; obtain white needle-like crystals fire retardant four (0-methyl-phenyl time phosphono) glycoluril, its productive rate is 91.1%, and decomposition temperature is (380 ± 2) ℃.
Table 1 preparation example main technologic parameters
This case contriver is also applied to above-mentioned synthetic fire retardant four (0-methyl-phenyl time phosphono) glycoluril in PET; fire retardant four (0-methyl-phenyl time phosphono) glycoluril that adds different ratios in PET; with XJ-01 type forcing machine, at 245 ℃, extrude batten respectively again; batten is of a size of diameter 3mm, length 15mm.Then it is carried out to flame retardant properties mensuration, 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-methyl-phenyl time phosphono) glycoluril flame retardant properties in PET
From above-mentioned table, fire retardant four (0-methyl-phenyl time phosphono) glycoluril has good flame retardant properties to PET resin.
Claims (6)
1. fire retardant four (O-methyl-phenyl time phosphono) glycoluril compounds, is characterized in that, the structure of this compound is shown below:
2. the preparation method of fire retardant four according to claim 1 (O-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, phenyl phosphinic acid dimethyl ester is divided in the solution of the organic solvent that is added drop-wise to tetrachloroglycine urea for four times at different temperature, first at 5 ℃, drip the phenyl phosphinic acid dimethyl ester of 1 times mole of tetrachloroglycine urea, stirring reaction 1h; Then be warming up to 40 ℃, then drip the phenyl phosphinic acid dimethyl ester of 1 times mole, stirring reaction 1h; Be warming up to again 70 ℃, then drip the phenyl phosphinic acid dimethyl ester of 1 times mole, stirring reaction 1h; Finally be warming up to 80 ℃～100 ℃, then drip the phenyl phosphinic acid dimethyl ester of 1-3 times mole, insulation reaction 5～7h; Purified processing, obtains white needle-like crystals fire retardant four (O-methyl-phenyl time phosphono) glycoluril.
3. the preparation method of fire retardant four according to claim 2 (O-methyl-phenyl time phosphono) glycoluril, is characterized in that: described certain mol proportion is tetrachloroglycine urea: phenyl phosphinic acid dimethyl ester is 1: 4～1: 6.
4. the preparation method of fire retardant four according to claim 2 (O-methyl-phenyl time phosphono) glycoluril, 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 (O-methyl-phenyl time phosphono) glycoluril, is characterized in that: the quality grams that the solution of the organic solvent of described tetrachloroglycine urea is tetrachloroglycine urea is 1: 4～1: 6 with the ratio of the volume milliliter number of organic solvent.
6. the preparation method of fire retardant four according to claim 2 (O-methyl-phenyl time phosphono) glycoluril; it is characterized in that: described be purifiedly 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 milliliter numbers of quality product grams; and aqueous ethanolic solution is ethanol and water volume ratio 1: 1; stirring heating makes its dissolving; cooling; product sufficient crystallising is separated out; suction filtration; vacuum-drying, obtains white needle-like crystals four (O-methyl-phenyl time phosphono) glycoluril.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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Effective date of registration: 20191204 Address after: 215000 Jiangsu city of Suzhou province Wuzhong District Su Li Road No. 63 Patentee after: SUZHOU ZHONGTUO PATENT OPERATIONS MANAGEMENT CO., LTD. Address before: 215131, 959 yuan and building 610, Jia Yuan Road, Xiangcheng District, Jiangsu, Suzhou Patentee before: Xiangcheng Institute of Suzhou University of Science and Technology |