CN105566386B - Phenylphosphonothioic acid two（Tribromo phenyl）Ester compounds and preparation method thereof - Google Patents
Phenylphosphonothioic acid two（Tribromo phenyl）Ester compounds and preparation method thereof Download PDFInfo
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- CN105566386B CN105566386B CN201610037030.9A CN201610037030A CN105566386B CN 105566386 B CN105566386 B CN 105566386B CN 201610037030 A CN201610037030 A CN 201610037030A CN 105566386 B CN105566386 B CN 105566386B
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- phenylphosphonothioic
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- tribromo phenyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5398—Phosphorus bound to sulfur
Abstract
The present invention relates to a kind of fire retardant phenylphosphonothioic acids two（Tribromo phenyl）The structure of ester compounds and preparation method thereof, the compound is shown below：
Description
Technical field
The present invention relates to a kind of phenylphosphonothioic acid two (tribromo phenyl) ester compounds and preparation method thereof, which contains
There are three kinds of phosphorus, sulphur, bromine ignition-proof elements, cooperative flame retardant effect is good, is suitable as polyester PBT, polyester PET, polypropylene PP, polyurethane
The fire retardant of equal materials.
Background technique
The continuous development of science and technology enables high molecular material to be widely applied, and brings greatly just to people's lives
Benefit, but its inflammable disadvantage often causes fire, causes serious threat to the security of the lives and property of people, thus promote
The fast development of fire-retardant science and technology.Due to the enhancing of people's safety and environmental protection consciousness, halogenated flame retardant receives in some aspects
Certain limitation, organic phosphorus flame retardant low smoke and non-toxic, promise well, at the same to the exploitation of multielement synergy fire retardant by
To attention.While halogenated flame retardant Arrested Development, since its flame-retarded efficiency is high, applied widely, comprehensive cost performance is excellent,
The ideal substitute of halogenated flame retardant is also difficult to find that at present, it is generally desirable that compounding or designing intramolecular by a variety of fire retardants
More ignition-proof element collaborations, to reduce the additive amount of fire retardant in the material, reduce the danger generated when burning to improve flame-retarded efficiency
Evil.
The invention discloses a kind of phenylphosphonothioic acid two (tribromo phenyl) ester compounds and preparation method thereof, the compounds
Containing three kinds of phosphorus, sulphur, bromine ignition-proof elements, cooperative flame retardant effect is good, and decomposition temperature is high, and aromatic ring in molecule and polyester structure can
It is a kind of fire retardant that comprehensive cost performance is excellent to increase the compatibility of product and substrate, and simple process, it is easy to operate, if
Standby small investment, it is environmental-friendly, there is preferable application and development prospect.
Summary of the invention
It, should it is an object of the present invention to proposing a kind of fire retardant phenylphosphonothioic acid two (tribromo phenyl) ester compounds
Compound contains three kinds of phosphorus, sulphur, bromine ignition-proof elements, and cooperative flame retardant efficiency is high, and heat-resistant stability is good, can effectively overcome existing skill
Deficiency in art.
For achieving the above object, present invention employs following technical solutions：
A kind of phenylphosphonothioic acid two (tribromo phenyl) ester compounds, which is characterized in that the structure of the compound such as following formula
It is shown：
Another object of the present invention is to propose a kind of preparation of phenylphosphonothioic acid as described above two (tribromo phenyl) ester
Method, simple process are easy to large-scale production, and this method is：
Equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading access one can extremely stretch it is swollen
In the reactor of swollen soft seal set, nitrogen displaces air, and tribromphenol, organic solvent is added, and under stirring, is added certain mole
The phenylphosphonothioic dichloride of ratio, and ammonia is continually fed on liquid level into reaction flask, keep soft seal set micro- to be passed through speed
Rise constancy of volume, after 30-50 DEG C of insulation reaction 3-4h, purified processing obtains two (tribromo-benzene of white solid phenylphosphonothioic acid
Base) ester.
This method can also be：
With nitrogen displace equipped with blender, thermometer, high performance reflux condenser reaction flask in air, be added magnesium
Bits, methanol are warming up to 40 DEG C, and stirring to magnesium chips disappears, and the tribromphenol of 2 times of moles of magnesium chips is added, and heating steams methanol,
Organic solvent is added, the phenylphosphonothioic dichloride of certain mol proportion is added dropwise in reaction system, process control temp is added dropwise
Not higher than 40 DEG C, after dripping off, after 40-50 DEG C of reaction 4-6h, purified processing obtains white solid phenylphosphonothioic acid two (three
Bromophenyl) ester.
Organic solvent as described above is methylene chloride, dichloroethanes, dioxane or chloroform, dosage volume ml
It is 3-8 times of the quality grams of tribromphenol.
Purification process as described above is that vacuum distillation removes organic solvent (recycling uses) and a small amount of low boilers, adds water
Agitator treating is dispersed in water solid product, filters, and elutes, drying.
Purification process as described above can remove organic solvent (recycling uses) and a small amount of low boilers also for vacuum distillation,
The acetonitrile of 4-10 times of volume ml of quality grams of tribromphenol is added, is filtered while hot after being heated to acetonitrile boiling, filtrate is cold
But it crystallizes, filters, it is dry.
The phenylphosphonothioic dichloride of certain mol proportion as described above is phenylphosphonothioic dichloride: tribromphenol=1:
2-1∶2.5。
Methanol as described above is anhydrous methanol, and dosage volume ml is 3-5 times of tribromphenol quality grams.
(tribromo phenyl) ester of phenylphosphonothioic acid two of the invention is white powdery solids, fusing point：254 ± 2 DEG C, point
Solve temperature：285±5℃；Yield is 86.5%-93.1%, is suitable as the materials such as polyester PBT, polyester PET, polypropylene (PP)
The fire retardant of material is used.
Inventor the study found that phenylphosphonothioic dichloride reacts very active with tribromphenol under the conditions of the present invention,
Reaction temperature cannot be excessively high, slightly at a high temperature of, reaction system is easy blackening, and yield and purity can be lower.
The preparation process principle of phenylphosphonothioic acid two (tribromo phenyl) ester is shown below：
Compared with prior art, innovation of the invention is：
1. the structural symmetry of phenylphosphonothioic acid two (tribromo phenyl) ester of the present invention is good, physical and chemical performance is stablized,
Heat-resistant stability is good, and the aromatic ring and polyester structure in molecule can increase the compatibility of product and substrate, and experiment discovery is used for PVC
The compatibility of chlorinated paraffin and substrate can also be improved, introduce ignition-proof element sulphur, the effectively fire-retardant member of intramolecular again in molecular structure
Cellulose content is up to 67.88%, and three element cooperative flame retardant efficiency are high.
2. the preparation method reaction time of the present invention is short, mild condition, good reaction selectivity, yield is high, without hydrogen chloride dirt
Dye does not generate corrosivity to equipment.
3. the method that preparation method of the present invention mutually ties up acid using ammonia, ammonia is inexpensive nontoxic, the hydrogen chloride released with system
Reaction generates ammonium chloride on material liquid surface, can effectively facilitate the evolution of hydrogen chloride, and ammonia not with acyl chloride reaction, ammonium chloride with have
Machine object is immiscible, can be easily separated, and the Fertilizer application after can recycling as plant.
4. preparation method of the present invention is reacted with phenyl phosphonyl chloride again after first generating phenol magnesium with magnesium using tribromphenol, and three
Bromophenol magnesium itself has catalytic action, and tribromphenol magnesium and phenylphosphonothioic dichloride have preferable intersolubility, so that reaction is more
Add and be easy progress, react more complete, and reacts the MgCl generated2It is easier to remove.
5. the brominated amount of the raw materials used in the present invention tribromphenol is high itself to have preferable anti-flammability, but its easily distillation, Yi Yi
Out, there is biggish irritation taste, reacted with phenylphosphonothioic dichloride after generating ester, overcome its above-mentioned deficiency, and
It is embedded in two highly effective flame-retardant elements of sulphur phosphorus again, has also invested the phosphate ester structure of good dispersion, has also improved the processing of material
Performance.
6. preparation method simple process of the present invention, raw material is cheap and easy to get, and equipment investment is few, is easy to large-scale production.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the infrared spectrogram of phenylphosphonothioic acid two (tribromo phenyl) ester；Fig. 1 shows：749.6cm-1Place is P=S
The stretching vibration peak of key；1060.4cm-1Place is the stretching vibration peak of Ar-Br key；1120.2cm-1Place is the stretching vibration of P-O key
Peak；1240.6cm-1Place is the stretching vibration peak of Ar-O key；1434.4cm-1Place is the skeleton stretching vibration peak of phenyl ring；
3068.9cm-1Place is the stretching vibration peak of c h bond on phenyl ring.
Fig. 2 is the nuclear magnetic spectrum figure of phenylphosphonothioic acid two (tribromo phenyl) ester；Fig. 2 shows：With CDCl3For solvent, δ3：
8.15-8.26 (q, 2H)；δ4：7.61-7.68 (s, 4H)；δ1：7.52-7.59 (t, 1H)；δ2：7.40-7.49 (q, 2H).
Fig. 3 is the thermogravimetric spectrogram of phenylphosphonothioic acid two (tribromo phenyl) ester；Fig. 3 shows：The fusing point of product is 254 DEG C,
285 DEG C of beginnings are weightless；When weight-loss ratio is 5%, temperature is 324 DEG C；When weight-loss ratio is 50%, temperature is 393 DEG C.
Specific embodiment
Technical solution of the present invention is described further below in conjunction with specific embodiment.
Embodiment 1 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to one can extremely
In the 100mL four-hole boiling flask of flexible expansion soft seal set, leads to the air in nitrogen displacement bottle falling, be added 6.62g (0.020mol)
Under stirring, 2.11g (0.01mol) phenylphosphonothioic dichloride is added, and into reaction flask in tribromphenol and 30mL methylene chloride
It is continually fed into ammonia on liquid level, keeps soft seal set to rise slightly constancy of volume to be passed through speed, after being warming up to 30 DEG C of insulation reaction 4h,
Methylene chloride (recycling uses) and a small amount of low boilers are distilled off, adds 20mL water agitator treating, solid product is made to be scattered in water
In, it filters, elutes, drying obtains white solid phenylphosphonothioic acid two (tribromo phenyl) ester, yield 86.5%, fusing point：254
± 2 DEG C, decomposition temperature：285±5℃.
Embodiment 2 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to one can extremely
In the 100mL four-hole boiling flask of flexible expansion soft seal set, leads to the air in nitrogen displacement bottle falling, be added 7.28g (0.022mol)
Under stirring, 2.11g (0.01mol) phenylphosphonothioic dichloride is added, and into reaction flask in tribromphenol and 30mL dioxane
It is continually fed into ammonia on liquid level, keeps soft seal set to rise slightly constancy of volume to be passed through speed, after being warming up to 45 DEG C of insulation reaction 3h,
Vacuum distillation removes dioxane (recycling uses) and a small amount of low boilers, adds 20mL water agitator treating, disperses solid product
Yu Shuizhong is filtered, and is eluted, and drying obtains white solid phenylphosphonothioic acid two (tribromo phenyl) ester, yield 89.3%, fusing point：
254 ± 2 DEG C, decomposition temperature：285±5℃.
Embodiment 3 equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading be connected to one can extremely
In the 100mL four-hole boiling flask of flexible expansion soft seal set, leads to the air in nitrogen displacement bottle falling, be added 7.61g (0.023mol)
Under stirring, 2.11g (0.01mol) phenylphosphonothioic dichloride, and the liquid level into reaction flask is added in tribromphenol and 30mL chloroform
On be continually fed into ammonia, keep soft seal set to rise slightly constancy of volume to be passed through speed, after being warming up to 50 DEG C of insulation reaction 3h, decompression
Chloroform (recycling uses) and a small amount of low boilers are distilled off, acetonitrile 50mL is added later, are taken out while hot after being heated to acetonitrile boiling
Filter, filtrate crystallisation by cooling obtain white solid phenylphosphonothioic acid two (tribromo phenyl) ester, yield 93.1%, fusing point：254±2
DEG C, decomposition temperature：285±5℃.
Under 4 nitrogen protection of embodiment, in the 100mL four-hole boiling flask for having blender, thermometer, high performance reflux condenser,
0.252g (0.0105mol) magnesium chips, 30mL anhydrous methanol is added, is warming up to 40 DEG C, stirring to magnesium chips disappears, and 6.95g is added
(0.021mol) tribromphenol, stirring heating steam methanol, 30mL dichloroethanes are added, by 2.11g (0.01mol) in 1h
Phenylphosphonothioic dichloride is added dropwise in reaction system, and process control temp is added dropwise and is not higher than 40 DEG C, after dripping off, 40 DEG C of heat preservations are anti-
After answering 6h, vacuum distillation removes dichloroethanes (recycling uses) and a small amount of low boilers, adds 20mL water agitator treating, produces solid
Product are dispersed in water, and are filtered, and are eluted, and drying obtains white solid phenylphosphonothioic acid two (tribromo phenyl) ester, yield is
88.3%, fusing point：254 ± 2 DEG C, decomposition temperature：285±5℃.
Under 5 nitrogen protection of embodiment, in the 100mL four-hole boiling flask for having blender, thermometer, high performance reflux condenser,
0.29g (0.012mol) magnesium chips, 30mL anhydrous methanol is added, is warming up to 40 DEG C, stirring to magnesium chips disappears, and 7.94g is added
(0.024mol) tribromphenol, stirring heating steam methanol, 30mL dioxane are added, by 2.11g (0.01mol) in 1h
Phenylphosphonothioic dichloride is added dropwise in reaction system, and process control temp is added dropwise and is not higher than 40 DEG C, after dripping off, is warming up to 40 DEG C
After reacting 5h, vacuum distillation removes dioxane (recycling uses) and a small amount of low boilers, adds 20mL water agitator treating, makes solid
Product is dispersed in water, and is filtered, and is eluted, and drying obtains white solid phenylphosphonothioic acid two (tribromo phenyl) ester, yield is
91.2%, fusing point：254 ± 2 DEG C, decomposition temperature：285±5℃.
Under 6 nitrogen protection of embodiment, in the 100mL four-hole boiling flask for having blender, thermometer, high performance reflux condenser,
0.30g (0.0125mol) magnesium chips, 30mL anhydrous methanol is added, is warming up to 40 DEG C, stirring to magnesium chips disappears, and 8.27g is added
(0.025mol) tribromphenol, stirring heating steam methanol, 30mL dichloroethanes are added, by 2.11g (0.01mol) in 1h
Phenylphosphonothioic dichloride is added dropwise in reaction system, and process control temp is added dropwise and is not higher than 40 DEG C, after dripping off, is warming up to 50 DEG C
After reacting 4h, vacuum distillation removes dichloroethanes (recycling uses) and a small amount of low boilers, adds 20mL water agitator treating, makes solid
Product is dispersed in water, and is filtered, and is eluted, and drying obtains white solid phenylphosphonothioic acid two (tribromo phenyl) ester, yield is
92.7%, fusing point：254 ± 2 DEG C, decomposition temperature：285±5℃.
1 preparation example main technologic parameters of table
The phenylphosphonothioic acid two of above-mentioned preparation (tribromo phenyl) ester is also applied in polyester PBT by inventor.Ginseng
According to：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limit oxygen index of sample.Take product phosphorus sulphur
Halogen synergistic fire retardant phenylphosphonothioic acid two (tribromo phenyl) ester, synergistic flame retardant antimony oxide and PBT are mixed in varing proportions
It after closing uniformly, is squeezed out with extruder, diameter is made and is the batten of 3mm, and its flame retardant property is tested, part test knot
Fruit is as shown in table 2：
2 phenylphosphonothioic acid of table, two (tribromo phenyl) ester is used for the flame retardant property data of PBT
Table 2 shows (tribromo phenyl) ester of phenylphosphonothioic acid two for PBT, and when additive amount 20%, limit oxygen index can
Up to 30%, illustrate that it has preferable flame retardant property.
Claims (2)
1. a kind of preparation method of fire retardant phenylphosphonothioic acid two (tribromo phenyl) ester compounds, which is characterized in that this method
For：
Equipped with blender, thermometer, high performance reflux condenser and condenser pipe it is suitable for reading access one can extremely stretch expand it is soft
In the reactor of sealing shroud, nitrogen displaces air, and tribromphenol, organic solvent is added, under stirring, certain mol proportion is added
Phenylphosphonothioic dichloride, and be continually fed into ammonia on liquid level into reaction flask keeps soft seal set to rise slightly body to be passed through rate
Product is constant, and after being warming up to 30-50 DEG C of insulation reaction 3-4h, purified processing obtains two (tribromo-benzene of white solid phenylphosphonothioic acid
Base) ester, the structure of the compound is shown below：
The purified processing is that vacuum distillation removes organic solvent and a small amount of low boilers, adds water and stirs washing, makes solid
Product is dispersed in water, and is filtered, and is eluted, drying；Or vacuum distillation removes organic solvent and a small amount of low boilers, and tribromo-benzene is added
The acetonitrile of phenol quality 4-10 times of volume ml of grams is heated to boiling and filters while hot, and filtrate crystallisation by cooling filters, dry.
2. a kind of preparation method of fire retardant phenylphosphonothioic acid two (tribromo phenyl) ester compounds as described in claim 1,
It is characterized in that：The organic solvent is methylene chloride, dichloroethanes, dioxane or chloroform, and dosage volume ml is three
3-8 times of the quality grams of bromophenol.
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| CN112442213A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with halogen atoms and preparation method and application thereof |
| CN114516889A (en) * | 2022-03-10 | 2022-05-20 | 长春市兆兴新材料技术有限责任公司 | 4,4' -biphenyl bis (diphenyl phosphonate) flame retardant and preparation method thereof |
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| GB705646A (en) * | 1952-06-26 | 1954-03-17 | Dow Chemical Co | O,o-di(polyhalophenyl) n-substituted amidothiophosphates |
| CN101967162A (en) * | 2010-08-24 | 2011-02-09 | 苏州科技学院 | Synergetic flame retardant compound containing four elements of P, N, S and Br and preparation method thereof |
| CN102250357A (en) * | 2011-06-09 | 2011-11-23 | 苏州科技学院 | polyphenyl thiophosphonic gylcol ester compound and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5269958A (en) * | 1975-12-09 | 1977-06-10 | Kanebo Ltd | Polyester composition |
| JPS5377042A (en) * | 1976-12-20 | 1978-07-08 | Sumitomo Chem Co Ltd | Preparation of optically active organic thiophosphotic acid |
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- 2016-01-19 CN CN201610037030.9A patent/CN105566386B/en active Active
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|---|---|---|---|---|
| GB705646A (en) * | 1952-06-26 | 1954-03-17 | Dow Chemical Co | O,o-di(polyhalophenyl) n-substituted amidothiophosphates |
| CN101967162A (en) * | 2010-08-24 | 2011-02-09 | 苏州科技学院 | Synergetic flame retardant compound containing four elements of P, N, S and Br and preparation method thereof |
| CN102250357A (en) * | 2011-06-09 | 2011-11-23 | 苏州科技学院 | polyphenyl thiophosphonic gylcol ester compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Direct Conversion of Phosphonates to Phosphine Oxides: An Improved Synthetic Route to Phosphines Including the First Synthesis of Methyl JohnPhos;Alexander J. Kendall et al.;《Organometallics》;20141022;第33卷;第6171-6178页 * |
| Synthesizing of salicylealdehyde using magnesium phenoxide and its mass analyzing characterization;Mandana Nejati Bor Bor et al.;《Chemical Technology: An Indian Journal》;20131231;第8卷;第36-40页 * |
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