CN105254678A - Preparation method for fire retardant high in phosphorus content - Google Patents
Preparation method for fire retardant high in phosphorus content Download PDFInfo
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- CN105254678A CN105254678A CN201510809636.5A CN201510809636A CN105254678A CN 105254678 A CN105254678 A CN 105254678A CN 201510809636 A CN201510809636 A CN 201510809636A CN 105254678 A CN105254678 A CN 105254678A
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Abstract
The invention relates to a preparation method for a fire retardant high in phosphorus content. The formula for synthesizing the fire retardant high in phosphorus content comprises the following components by weight percent: 9.87%-11.22% of 6-(hydroxymethyl)dibenzo[c,e][1,2]oxygen phosphor hexane heterocycle-6-oxide, 10.11%-10.54% of phosphorus oxychloride, 4.38%-4.72% of triethylamine and 74.22%-78.37% of methylene dichloride. The preparation method comprises the following steps: adding methylene dichloride and 6-(hydroxymethyl)dibenzo[c,e][1,2]oxygen phosphor hexane heterocycle-6-oxide which are at the formula ratio into a reactor and stirring for 30min at 25 DEG C; reducing the temperature of the system to -8 DEG C; adding triethylamine at the formula ratio and keeping low-temperature stirring for 30min; adding phosphorus oxychloride into the system, after ending the adding, keeping the temperature for 2h; lastly, increasing the temperature of the system to 25 DEG C, stirring for 6h and then stopping reaction; removing the solvent from the system and acquiring the yellow solid products; crystallizing and then acquiring the colorless solid.
Description
Technical field
The present invention relates to phosphonium flame retardant and preparation method thereof, belong to the technical field of polymer chemistry and polymer technology.
Background technology
Polymer materials is applied very extensive in all trades and professions with the performance of its excellence, but there is inflammable defect in most polymers, very easily big fire is caused under high temperature or Fire Conditions, can cause very large life and property loss, in polymkeric substance, add fire retardant is improve the conventional means of macromolecular material flame retardant properties.
Find in research in the past, while halogen containing flame-retardant flame-retardant polymer, self thermolysis can discharge poisonous gas, and the developed country of European Union and the U.S. has prohibited use halogen containing flame-retardant.Develop the emphasis that other ignition-proof elements become research.
Phosphoric has plurality of advantages as ignition-proof element, and it can play fire-retardant effect simultaneously in gas phase and condensed phase.Can not discharge virulent gas in thermal decomposition process, these features make phosphorus containg substances become Green Flammability agent.
CN102898677A discloses with DOPO and Benzyl Chloride as main raw material reacts the luxuriant and rich with fragrance oxa-fire retardant of the addition type phosphorus made in the presence of a catalyst.But reaction conditions is not gentle, and use catalyzer to increase production cost, main ignition-proof element is relatively low simultaneously, and the present invention will overcome these defects.
Summary of the invention
The object of the invention is to provide a kind of preparation method of high phosphorus content fire retardant.
The present invention is a kind of preparation method of high phosphorus content fire retardant, its high phosphorus content fire retardant is three ((6-oxo-6H-dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-base) methyl) method for production of phosphate salt, by mass percentage, the formula synthesizing high phosphonium flame retardant is: 6-(methylol) dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-oxide compound 9.87% ~ 11.22%, phosphorus oxychloride 10.11% ~ 10.54%, triethylamine 4.38% ~ 4.72%, methylene dichloride 74.22% ~ 78.37%;
The preparation method of high phosphonium flame retardant, by above-mentioned synthesis, raw materials used and proportioning is prepared burden, and its preparation process is:
In the reactor that agitator, thermometer are housed, add methylene dichloride and the 6-(methylol of formula ratio) the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound, stirs 30min at 25 DEG C; Then system temperature is reduced to-8 DEG C, adds the triethylamine of formula ratio, keep low temperature to stir 30min, then in system, drip phosphorus oxychloride, drip and terminate rear maintenance temperature 2h, finally system is warming up to 25 DEG C, stopped reaction after continuation stirring 6h; System internal solvent is removed, obtains yellow solid product, after crystallization, obtain colorless solid.
Usefulness of the present invention is: the fire retardant synthesizing new high content of phosphorus, and synthesis technique is simple, stable performance.
Embodiment
The present invention is a kind of preparation method of high phosphorus content fire retardant, its high phosphorus content fire retardant is three ((6-oxo-6H-dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-base) methyl) method for production of phosphate salt, by mass percentage, the formula synthesizing high phosphonium flame retardant is: 6-(methylol) dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-oxide compound 9.87% ~ 11.22%, phosphorus oxychloride 10.11% ~ 10.54%, triethylamine 4.38% ~ 4.72%, methylene dichloride 74.22% ~ 78.37%;
The preparation method of high phosphonium flame retardant, by above-mentioned synthesis, raw materials used and proportioning is prepared burden, and its preparation process is:
In the reactor that agitator, thermometer are housed, add methylene dichloride and the 6-(methylol of formula ratio) the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound, stirs 30min at 25 DEG C; Then system temperature is reduced to-8 DEG C, adds the triethylamine of formula ratio, keep low temperature to stir 30min, then in system, drip phosphorus oxychloride, drip and terminate rear maintenance temperature 2h, finally system is warming up to 25 DEG C, stopped reaction after continuation stirring 6h; System internal solvent is removed, obtains yellow solid product, after crystallization, obtain colorless solid.
According to the preparation method of above high phosphorus content fire retardant, by mass percentage, 6-(methylol is synthesized) formula of the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound is:
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 36.24% ~ 36.61%, paraformaldehyde 5.08% ~ 6.04%, dimethylbenzene 57.72% ~ 58.31%;
Its preparation process is:
In the reactor that agitator, thermometer, reflux condensing tube are housed, add dimethylbenzene and the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide stirring heating of formula ratio; When temperature is 85 DEG C, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide dissolves completely; The paraformaldehyde of formula ratio is added in batches in 2h; Being warming up to 120 DEG C after reinforced, there is backflow in system, and system changes muddiness into by limpid simultaneously; Discharging after insulation reaction 6h; Use a large amount of dimethylbenzene washing precipitate while hot, suction filtration; At 120 DEG C, be incubated 48h, obtain white powder 6-(methylol) the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound.
First the present invention adopts 9, assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy and paraformaldehyde (PFA) are obtained by reacting 6-(methylol with the ratio of the amount of substance of 1:1) dibenzo [c, e] [1,2] oxygen phospha own ring-6-oxide compound (HDOPO).Then HDOPO and phosphorus oxychloride are obtained by reacting three ((the own ring of 6-oxo-6H-dibenzo [c, e] [1,2] oxygen phospha-6-base) methyl) phosphoric acid salt (TOPMP) with the amount of substance of 3:1.
Phosphonium flame retardant TOPMP synthesis route is as follows:
Based on the total mass preparing phosphonium flame retardant TOPMP, by mass percentage, intermediate HDOPO formula is:
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) 36.61% ~ 36.24%, paraformaldehyde 5.08% ~ 6.04%, dimethylbenzene 57.72% ~ 58.31%.
The preparation process of HDOPO is:
In the reaction vessel that agitator, thermometer and Glass tubing are housed, add DOPO and the dimethylbenzene of formula ratio, stir 30min at 90 DEG C, DOPO dissolves completely in dimethylbenzene.Keep temperature, in two hours in batches, add the paraformaldehyde of formula ratio.Then be warming up to backflow, insulation 6h, discharging, washs while hot with a large amount of dimethylbenzene, obtains product after oven dry.
Based on the total mass preparing phosphonium flame retardant TOPMP, by mass percentage, its formula is:
HDOPO9.87% ~ 11.22%, phosphorus oxychloride 10.11% ~ 10.54%, triethylamine 4.38% ~ 4.72%, methylene dichloride 74.22% ~ 78.37%.
The preparation process of TOPMP is:
Methylene dichloride and the HDOPO of formula ratio is added in the reaction vessel that agitator, thermometer and Glass tubing are housed, stirred at ambient temperature 30min, then system temperature is reduced ester-8 DEG C, add the triethylamine of formula ratio, keep low temperature to stir 30min, then in system, drip phosphorus oxychloride, drip and terminate rear maintenance temperature 2h, then system be warming up to 25 DEG C and continue to stir 6h, reaction terminates.System internal solvent is removed, obtains yellow product, after crystallization, obtain clean product.
Be below embodiments of the invention, but the present invention is not limited in the following example.
Embodiment 1.
In the reactor that agitator, thermometer, reflux condensing tube are housed, add 51.60kg dimethylbenzene and 32.4kgDOPO stirring heating.When temperature is 85 DEG C, DOPO dissolves completely.Keep same temperature, in 2h, add 4.5kg paraformaldehyde in batches.Being warming up to 120 DEG C after reinforced, there is backflow in system, and system changes muddiness into by limpid simultaneously.Then 6h is incubated, discharging.Use a large amount of dimethylbenzene washing precipitate while hot, suction filtration.Then 48h is incubated at being placed on 120 DEG C.Obtain white powder HDOPO.
Embodiment 2.
The HDOPO of 7.95kg is added, the dichloromethane solution of 46.40kg, stirred at ambient temperature 30min in the there-necked flask of 250ml.System temperature is reduced to-8 DEG C, adds 3.55kg triethylamine, stir and be incubated 30min.Then start to drip 8.25kg phosphorus oxychloride and 13.25kg methylene dichloride mixing solutions.After dropwising, keep low temperature 2h, be then warming up to 25 DEG C, stir 6h.Discharging, by the solvent in system and triethylamine evaporation.By product recrystallization, obtain clean product TOPMP.
Claims (2)
1. the preparation method of one kind high phosphorus content fire retardant, its high phosphorus content fire retardant is three ((6-oxo-6H-dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-base) methyl) method for production of phosphate salt, by mass percentage, the formula synthesizing high phosphonium flame retardant is: 6-(methylol) dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-oxide compound 9.87% ~ 11.22%, phosphorus oxychloride 10.11% ~ 10.54%, triethylamine 4.38% ~ 4.72%, methylene dichloride 74.22% ~ 78.37%;
The preparation method of high phosphonium flame retardant, by above-mentioned synthesis, raw materials used and proportioning is prepared burden, and its preparation process is:
In the reactor that agitator, thermometer are housed, add methylene dichloride and the 6-(methylol of formula ratio) the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound, stirs 30min at 25 DEG C; Then system temperature is reduced to-8 DEG C, adds the triethylamine of formula ratio, keep low temperature to stir 30min, then in system, drip phosphorus oxychloride, drip and terminate rear maintenance temperature 2h, finally system is warming up to 25 DEG C, stopped reaction after continuation stirring 6h; System internal solvent is removed, obtains yellow solid product, after crystallization, obtain colorless solid.
2. the preparation method of high phosphorus content fire retardant according to claim 1, is characterized in that: by mass percentage, synthesis 6-(methylol) formula of the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound is:
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 36.24% ~ 36.61%, paraformaldehyde 5.08% ~ 6.04%, dimethylbenzene 57.72% ~ 58.31%;
Its preparation process is:
In the reactor that agitator, thermometer, reflux condensing tube are housed, add dimethylbenzene and the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide stirring heating of formula ratio; When temperature is 85 DEG C, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide dissolves completely; The paraformaldehyde of formula ratio is added in batches in 2h; Being warming up to 120 DEG C after reinforced, there is backflow in system, and system changes muddiness into by limpid simultaneously; Discharging after insulation reaction 6h; Use a large amount of dimethylbenzene washing precipitate while hot, suction filtration; At 120 DEG C, be incubated 48h, obtain white powder 6-(methylol) the own ring of dibenzo [c, e] [1,2] oxygen phospha-6-oxide compound.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905561A (en) * | 2017-03-02 | 2017-06-30 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-containing DOPO derivative flame retardants and preparation method thereof |
| WO2017193463A1 (en) * | 2016-05-10 | 2017-11-16 | 淮安领创新材料有限公司 | Composite phosphorus flame retardant comprising cyclic organophosphate with multiple dopo moieties, and manufacturing method thereof |
| EP3540000A1 (en) | 2018-03-16 | 2019-09-18 | Stutz, Felix Benjamin | Flame retardant polyamide 6 master batch and fibers made thereof |
| CN110981912A (en) * | 2019-12-16 | 2020-04-10 | 寿光卫东化工有限公司 | Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof |
Citations (4)
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| JPH0753582A (en) * | 1993-08-12 | 1995-02-28 | Sanko Chem Co Ltd | Organic phosphorous compound and its production |
| CN1580108A (en) * | 2003-08-08 | 2005-02-16 | 长春人造树脂厂股份有限公司 | Phosphorous compound |
| CN101838538A (en) * | 2009-07-17 | 2010-09-22 | 大连理工大学 | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof |
| CN102757579A (en) * | 2012-07-19 | 2012-10-31 | 三峡大学 | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof |
-
2015
- 2015-11-23 CN CN201510809636.5A patent/CN105254678A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753582A (en) * | 1993-08-12 | 1995-02-28 | Sanko Chem Co Ltd | Organic phosphorous compound and its production |
| CN1580108A (en) * | 2003-08-08 | 2005-02-16 | 长春人造树脂厂股份有限公司 | Phosphorous compound |
| CN101838538A (en) * | 2009-07-17 | 2010-09-22 | 大连理工大学 | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof |
| CN102757579A (en) * | 2012-07-19 | 2012-10-31 | 三峡大学 | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017193463A1 (en) * | 2016-05-10 | 2017-11-16 | 淮安领创新材料有限公司 | Composite phosphorus flame retardant comprising cyclic organophosphate with multiple dopo moieties, and manufacturing method thereof |
| CN106905561A (en) * | 2017-03-02 | 2017-06-30 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-containing DOPO derivative flame retardants and preparation method thereof |
| CN106905561B (en) * | 2017-03-02 | 2019-08-23 | 张家港市山牧新材料技术开发有限公司 | A kind of fluorine-containing DOPO derivative flame retardant and preparation method thereof |
| EP3540000A1 (en) | 2018-03-16 | 2019-09-18 | Stutz, Felix Benjamin | Flame retardant polyamide 6 master batch and fibers made thereof |
| WO2019175421A1 (en) | 2018-03-16 | 2019-09-19 | Stutz Felix Benjamin | Flame retardant master batch for polyamide 6 and fibers made thereof |
| CN110981912A (en) * | 2019-12-16 | 2020-04-10 | 寿光卫东化工有限公司 | Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof |
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Application publication date: 20160120 |