CN102675371A - Cyclic phenyl phosphonate compound and method for preparing same - Google Patents
Cyclic phenyl phosphonate compound and method for preparing same Download PDFInfo
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- CN102675371A CN102675371A CN2012101243213A CN201210124321A CN102675371A CN 102675371 A CN102675371 A CN 102675371A CN 2012101243213 A CN2012101243213 A CN 2012101243213A CN 201210124321 A CN201210124321 A CN 201210124321A CN 102675371 A CN102675371 A CN 102675371A
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- LBYUDXQNXLOBHW-UHFFFAOYSA-N OCC(COP(c1ccccc1)(Oc1ccccc1)=O)(CO1)COP1(c1ccccc1)=O Chemical compound OCC(COP(c1ccccc1)(Oc1ccccc1)=O)(CO1)COP1(c1ccccc1)=O LBYUDXQNXLOBHW-UHFFFAOYSA-N 0.000 description 2
Abstract
The invention relates to a cyclic phenyl phosphonate compound and a method for preparing the same, and in particular relates to a cyclic phenyl phosphonate compound having high thermal stability and hydrolysis resistance and a method for preparing the same. The structure of the compound provided by the invention is as shown in the specification, wherein n=0 or 1. The method provided by the invention is to synthesize the compound by a two-step method from trimethylolpropane, trimethyl phosphite and phosphorous acid. The compound is high in phosphorus content, low in toxicity, free of pollution and the like. With a benzene ring and a cyclic structure in the molecular structure, the thermal stability and hydrolysis resistance of the compound are greatly improved; and simultaneously, with the structure of the cyclic phosphonate and high phosphorus content in the molecular structure, the compound shows excellent flame retardant efficiency and can be widely applied to most flame retardant high molecular materials. Furthermore, the compound is rich in synthesis raw material source, simple in production process, and easy for realizing industrial production and application.
Description
Technical field
The invention belongs to the technique for synthesizing compounds field; Relate to a kind of ring-type phenyl-phosphonic acid ester cpds and preparation method thereof, particularly a kind of ring-type phosphoric acid condenses that can be used for the fire-retardant novel cyclic phenyl-phosphonic acid ester cpds of polymkeric substance and preparation method thereof a kind of specifically C-P of containing key and phenyl ring and preparation method thereof.
Background technology
Since the fifties, the purposes of macromolecular material is increasingly extensive, and consumption increases sharply, and the fire hazard that brings thus is bigger, causes requiring increasingly high for the flame retardant properties of macromolecular material.In recent years, the increase of Along with people's environmental consciousness, halogen flame steps down from the stage of history gradually, and the non-halogen cry of fire retardant requires increasingly high, and phosphorus flame retardant receives very big favor.
Advantages such as the high and low cigarette of phosphorus flame retardant efficient, environmental protection, low halogen or Halogen, non-corrosiveness and consistency are good meet the fire retardant development trend.In organic phosphorus flame retardant, phosphate flame retardant is aboundresources not only, and is cheap, and its products of combustion generally all is nontoxic, less to health, environmental influence, and SULPHOSUCCINIC ACID ESTER has concurrently fire-retardant and the plasticising dual-use function simultaneously.Because the existence of C in the phosphate flame retardant, its chemicalstability strengthens, and have water-fast solvent resistance, thereby flame retardant properties is lasting.Chinese patent CN1888013A has described a kind of bicyclic phosphate fire retardant; It adopts tetramethylolmethane and dimethyl methyl phosphonate or methyl-phosphorous acid diethyl ester; Has higher phosphorus content in the product fire retardant; This fire retardant normal temperature is solid down, and thermally-stabilised ability is good and good with the consistency of superpolymer, but this fire retardant is soluble in water.Chinese patent number is main raw material synthetic annular phosphonate fire retardant for CN101230274A has described a kind of with TriMethylolPropane(TMP), methyl-phosphorous acid two formicesters, and this fire retardant can be applicable in the after-finishing flame resistant fabric of terylene, cotton, Zantrel and synthon.But this fire retardant thermostability is not high, soluble in water, has limited its expansion in Application Areass such as engineering plastics.The present invention is a raw material with TriMethylolPropane(TMP) and triphenyl phosphite, has synthesized a kind of ring-type phenyl-phosphonic acid ester cpds, and this compound has the phosphorus content height; Thermal stability is good, and anti-hydrolytic performance is good, Halogen; Characteristics such as low toxicity can be used as most of macromolecular material fire retardants and use.Simultaneously; The present invention has realized that through cycloaddition and rearrangement reaction the direct phosphorylated of aryl has generated the C-P key with aromatic base; And traditional method great majority adopt phosphorus trichloride and aromatic hydrocarbon reaction, all are to adopt this method preparation like Chinese invention patent application number 200510048704.7 with 201110162487.x, and follow-up method is owing to adopt the phosphorus trichloride reaction; Serious to equipment corrosion, by product has pollution to environment simultaneously.
Summary of the invention
The invention provides a kind of ring-type phenyl-phosphonic acid ester cpds and preparation method thereof, a kind of fire-retardant novel cyclic phenyl-phosphonic acid ester cpds of polymkeric substance and preparation method thereof that can be used for is provided especially.The present invention utilizes TriMethylolPropane(TMP) base cage shape phosphate compound and the triphenyl phosphite reaction that contains phenyl ring to form a kind of ring-type phenyl-phosphonic acid ester cpds; This compound has the phosphorus content height; Thermal stability is good, and anti-hydrolytic performance is good, Halogen; Characteristics such as low toxicity can be used as most of macromolecular material fire retardants and use.Owing to contain phenyl ring and ring texture simultaneously in the molecule, improve its thermal stability greatly.And the raw material sources of synthetic this fire retardant are abundant, and product price is cheap relatively, is easy to realize suitability for industrialized production and application.Because this compound contains phenyl ring and C-P key simultaneously; The carbon-forming performance and the flame retardant properties of flame-retardant system have been improved greatly; The adding of finding phenyl ring has simultaneously improved the fire retardation of phosphorus in condensed phase, shows the cooperative flame retardant effect between C-P key and the phenyl ring, has the good flame effect.Synthetic compound of the present invention can be used for the fire-retardant of synthetic materialss such as various fabrics, polyolefine, nylon and polyester.
A kind of ring-type phenyl-phosphonic acid ester cpds of the present invention, concrete structure is following:
N=0 or 1 wherein.
A kind of ring-type phenyl-phosphonic acid ester cpds of the present invention has the phosphorus content height, and thermal stability is good, and anti-hydrolytic performance is good, Halogen, characteristics such as low toxic and environment-friendly.Can be widely used in the fire-retardant of synthetic materialss such as various fabrics, polyolefine, nylon and polyester.
The present invention also provides a kind of preparation method of ring-type phenyl-phosphonic acid ester cpds, adopts the two-step approach reaction:
The first step: add TriMethylolPropane(TMP), trimethyl phosphite and catalyzer, stir and be warming up to 60～120 ℃, reacted 5～15 hours, after reaction finished, rectifying obtained midbody cage shape SULPHOSUCCINIC ACID ESTER; Wherein, TriMethylolPropane(TMP) is 1: 1～1.5 with the reaction molar weight ratio of trimethyl phosphite; Described catalyzer is tertiary amine, quaternary ammonium salt or aluminum trichloride (anhydrous), and its consumption is 0.5～5 gram/mole of trimethylol propane;
Second step: the midbody that above-mentioned reaction is obtained is warming up to 100～220 ℃, adds a certain amount of triphenyl phosphite, and stirring reaction 10～25 hours obtains final product ring-type phenyl-phosphonic acid ester cpds; Wherein the reaction mol ratio of midbody and triphenyl phosphite is: 1: 1～1.5.
A kind of ring-type phenyl-phosphonic acid ester cpds of the present invention is owing to contain phenyl ring and C-P key in the molecular structure; Improve the carbon-forming performance and the flame retardant properties of flame-retardant system greatly; The adding of finding phenyl ring has simultaneously improved the fire retardation of phosphorus in condensed phase; Show cooperative flame retardant effect between C-P key and the phenyl ring, have the good flame effect.
Beneficial effect:
1, the first step reaction is cyclization, the recyclable utilization of methyl alcohol of synthetic by-product.
2, second step reaction opening is simple for the requirement of reactions step and conversion unit, is fit to be applied to large batch of industrial production.
3, synthetic ring-type phenyl-phosphonic acid ester cpds of the present invention has the phosphorus content height, and thermal stability is good, and anti-hydrolytic performance is good, Halogen, characteristics such as low toxic and environment-friendly.Fire retardant of the present invention is owing to contain phenyl ring and C-P key in the molecular structure; Improve the carbon-forming performance and the flame retardant properties of flame-retardant system greatly; The adding of finding phenyl ring has simultaneously improved the fire retardation of phosphorus in condensed phase; Show cooperative flame retardant effect between C-P key and the phenyl ring, have the good flame effect.Can be widely used in the fire-retardant of synthetic materialss such as various fabrics, polyolefine, nylon and polyester.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Is being furnished with whisking appliance; Atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g, trimethyl phosphite 124.08g in the four neck flasks of TM, gas tube; Add the 2.5g triethylamine; Heated and stirred is warming up to 60 ℃, and after the reaction times was 8 hours, rectifying obtained 140.37g cage shape SULPHOSUCCINIC ACID ESTER midbody.Second step added the 293.67g triphenyl phosphite in midbody, and it is warming up to 150 ℃, reacted after 15 hours, obtained 376.60g ring-type phenyl-phosphonic acid ester cpds, and its reaction yield is 90%, obtain product structure as shown in the formula:
Embodiment 2
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Add trimethyl phosphite 136.49g, add tetramethyl ammonium chloride 0.8g, heated and stirred is warming up to 70 ℃; Reaction times is 8 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 143.49g. adding 300.19g triphenyl phosphite in midbody, and its temperature is risen to 160 ℃; After reaction times is 16 hours; Obtain 389.25g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 91%, and the chemical structural formula that obtains product is following;
Embodiment 3
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 148.90g adds the 2g aluminum trichloride (anhydrous), and heated and stirred is warming up to 80 ℃; Reaction times is 9 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 326.29g in midbody, and mixture is warming up to 170 ℃ together; Reaction times is 16 hours; Obtain 437.04g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 94%, and the chemical structure that obtains product is following:
Embodiment 4
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 161.30g adds the 3g Tributylamine, and heated and stirred is warming up to 90 ℃; Reaction times is 10 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 358.92g in midbody, and mixture is warming up to 180 ℃ together; Reaction times is 17 hours; Obtain 441.69g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 95%, and the chemical structure that obtains product is following:
Embodiment 5
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 161.30g adds the 1.5g aluminum trichloride (anhydrous), and heated and stirred is warming up to 100 ℃; Reaction times is 10 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 424.18g in midbody, and mixture is warming up to 190 ℃ together; Reaction times is 17 hours; Obtain 446.34g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 96%, and the chemical structure that obtains product is following:
Embodiment 6
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 161.30g adds N, N-dimethyl benzylamine 5.0g; Heated and stirred is warming up to 105 ℃, and the reaction times is 10 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 424.18g in midbody; And mixture is warming up to 180 ℃ together, the reaction times is 17 hours, obtains 437.04g ring-type phenyl-phosphonic acid ester cpds; Its productive rate is 94%, and the chemical structure that obtains product is following:
Embodiment 7
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 173.71g adds triethylamine 0.5g, and heated and stirred is warming up to 110 ℃; Reaction times is 11 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 456.81g in midbody, and mixture is warming up to 180 ℃ together; Reaction times is 18 hours; Obtain 446.34g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 96%, and the chemical structure that obtains product is following:
Embodiment 8
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 173.71g adds 4 bromide 5.0g, and heated and stirred is warming up to 115 ℃; Reaction times is 13 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 489.44g in midbody, and mixture is warming up to 190 ℃ together; Reaction times is 18 hours; Obtain 450.99g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 97%, and the chemical structure that obtains product is following:
Embodiment 9
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 161.30g adds benzyl trimethyl ammonium chloride 3.2g, and heated and stirred is warming up to 120 ℃; Reaction times is 15 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 489.44g in midbody, and mixture is warming up to 190 ℃ together; Reaction times is 18 hours; Obtain 455.64g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 98%, and the chemical structure that obtains product is following:
Embodiment 10
Be furnished with whisking appliance, atmospheric distillation plant adds TriMethylolPropane(TMP) 134.17g in the four neck flasks of TM, gas tube; Trimethyl phosphite 161.30g adds Tetrabutyl amonium bromide 3.3g, and heated and stirred is warming up to 115 ℃; Reaction times is 14 hours, and rectifying obtains second step of midbody cage shape SULPHOSUCCINIC ACID ESTER 155.97g. adding triphenyl phosphite 489.44g in midbody, and mixture is warming up to 200 ℃ together; Reaction times is 20 hours; Obtain 460.29g ring-type phenyl-phosphonic acid ester cpds, its productive rate is 99%, and the chemical structure that obtains product is following:
Claims (2)
1. ring-type phenyl-phosphonic acid ester cpds is characterized in that concrete structure is following:
N=0 or 1 wherein.
2. the preparation method of a kind of ring-type phenyl-phosphonic acid ester cpds as claimed in claim 1 is characterized in that adopting the two-step approach reaction:
The first step: add TriMethylolPropane(TMP), trimethyl phosphite and catalyzer, stir and be warming up to 60～120 ℃, reacted 5～15 hours, after reaction finished, rectifying obtained midbody cage shape SULPHOSUCCINIC ACID ESTER; Wherein, TriMethylolPropane(TMP) is 1: 1～1.5 with the reaction molar weight ratio of trimethyl phosphite; Described catalyzer is tertiary amine, quaternary ammonium salt or aluminum trichloride (anhydrous), and its consumption is 0.5～5 gram/mole of trimethylol propane;
Second step: the midbody that above-mentioned reaction is obtained is warming up to 100～220 ℃, adds a certain amount of triphenyl phosphite, and stirring reaction 10～25 hours obtains final product ring-type phenyl-phosphonic acid ester cpds; Wherein the reaction mol ratio of midbody and triphenyl phosphite is: 1: 1～1.5.
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| CN2012101243213A CN102675371A (en) | 2012-04-25 | 2012-04-25 | Cyclic phenyl phosphonate compound and method for preparing same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926875A (en) * | 2015-07-07 | 2015-09-23 | 苏州科技学院 | Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor |
| CN104926873A (en) * | 2015-07-07 | 2015-09-23 | 苏州凯马化学科技有限责任公司 | Fire retardant hydroxymethyl phosphonyl hybrid ring-shaped methylphosphonate compound and preparing method thereof |
| CN105001263A (en) * | 2015-07-07 | 2015-10-28 | 苏州凯马化学科技有限责任公司 | Flame retardant hydroxymethyl phosphine heterocyclic phenyl phosphonate compound and preparation method thereof |
| CN111377967A (en) * | 2020-02-26 | 2020-07-07 | 青岛长荣化工科技有限公司 | Preparation method of cyclic phosphonate flame retardant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833015A (en) * | 2003-08-01 | 2006-09-13 | 罗迪亚公司 | Flame retardant phosphonate additives for thermoplastics |
| WO2012040074A1 (en) * | 2010-09-23 | 2012-03-29 | Icl-Ip America Inc. | Monohydroxy cyclic phosphonate substantially free of polyhydoxy phosphonate, process for making same and flame retardant flexible polyurethane foam obtained therefrom |
-
2012
- 2012-04-25 CN CN2012101243213A patent/CN102675371A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1833015A (en) * | 2003-08-01 | 2006-09-13 | 罗迪亚公司 | Flame retardant phosphonate additives for thermoplastics |
| WO2012040074A1 (en) * | 2010-09-23 | 2012-03-29 | Icl-Ip America Inc. | Monohydroxy cyclic phosphonate substantially free of polyhydoxy phosphonate, process for making same and flame retardant flexible polyurethane foam obtained therefrom |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926875A (en) * | 2015-07-07 | 2015-09-23 | 苏州科技学院 | Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor |
| CN104926873A (en) * | 2015-07-07 | 2015-09-23 | 苏州凯马化学科技有限责任公司 | Fire retardant hydroxymethyl phosphonyl hybrid ring-shaped methylphosphonate compound and preparing method thereof |
| CN105001263A (en) * | 2015-07-07 | 2015-10-28 | 苏州凯马化学科技有限责任公司 | Flame retardant hydroxymethyl phosphine heterocyclic phenyl phosphonate compound and preparation method thereof |
| CN105001263B (en) * | 2015-07-07 | 2018-02-02 | 苏州凯马化学科技有限责任公司 | Miscellaneous cyclic phenyl phosphonate compound of fire retardant methylol phosphine and preparation method thereof |
| CN111377967A (en) * | 2020-02-26 | 2020-07-07 | 青岛长荣化工科技有限公司 | Preparation method of cyclic phosphonate flame retardant |
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Application publication date: 20120919 |