CN103204879A - Synthesis process of phosphate flame retardant - Google Patents
Synthesis process of phosphate flame retardant Download PDFInfo
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- CN103204879A CN103204879A CN2013100559478A CN201310055947A CN103204879A CN 103204879 A CN103204879 A CN 103204879A CN 2013100559478 A CN2013100559478 A CN 2013100559478A CN 201310055947 A CN201310055947 A CN 201310055947A CN 103204879 A CN103204879 A CN 103204879A
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- flame retardant
- phosphorus oxychloride
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Abstract
The present invention relates to a synthesis process of a phosphate flame retardant. The flame retardant has a molecular formula of C15H24016P4 and a structure as below, and is named as tri (2, 6, 7-trioxa-1-phenoxy Phosphabicyclo [2, 2, 2] octane-4-methylene) phosphate, and has a commodity name of Trimer. The manufacturing method is as below: dissolving the pentaerythritol in a solvent; and slowly and dropwise adding phosphorus oxychloride with mole number 4 / 3 times of pentaerythritol under a reflux temperature in a stirring device with nitrogen flow protection; after addition, continuing a reflux reaction; after the reaction, filtering the solvent; and washing and drying the product to obtain the phosphate ester flame retardant Trimer. The invention adopts a one-pot synthesis technology, has a simple manufacturing process, and is convenient for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic manufacture method of phosphate flame retardant.
Background technology
Nineteen sixty Verdade has synthesized 1-oxygen base phospha-4-methylol-2,6, the two octanes of 7-trioxa (be bicyclo cage shaped phosphoric acid ester, PEPA), its structure is as follows:
US Patent No. 4454064 has been invented the method for the higher bicyclo cage shaped phosphoric acid ester of preparation (PEPA) of productive rate.The molecular structure of PEPA is the rigidity cage structure, and Heat stability is good, intramolecularly have acid source and charcoal source concurrently.By the PEPA multiple fire retardant for thermoset and thermoplastic macromolecule material of having derived.
US Patent No. 3883478 has been invented fire retardant (PEPA) the alkoxyl group phosphoric acid ester that is used for trevira, and structural formula is
US Patent No. 5536863 has been invented fire retardant PEPA and has been encircled new penta phosphorous acid ester and PEPA ring neopentyl glycol phosphoric acid ester, and structure is as follows:
Li Xin, Ou Yuxiang, Zhang Yunhong (Li Xin, Ou Yuxiang, Zhang Yunhong: three (1-oxos-2; 6; 7-trioxa-l-phosphabicyclo [2; 2; 2] octane)-synthetic, crystalline structure and the thermal characteristics of 4-methylene radical phosphoric acid ester; SCI, the 4th phases 23 in 2002 volume, 695～699 pages) synthesized three (PEPA) phosphoric acid ester (Trimer), structural formula is:
Summary of the invention
The invention provides the method for a kind of synthetic manufacturing Trimer.The present invention is on the basis of U.S. patent US4464064, behind the PEPA end of synthesis, does not separate and purified product, and directly drops into the second step reaction mass phosphorus oxychloride in reaction system, continues reaction and makes Trimer.
The method difference that method provided by the invention and Li Xin etc. provide is: the present invention is starting raw material with tetramethylolmethane and phosphorus oxychloride, finishes the synthetic of Trimer in a reactor, and does not separate and purification intermediate product PEPA.
For realizing the object of the invention, a kind of synthetic method of phosphate flame retardant is provided, this flame retardant molecule formula is C
15H
240
16P
4, structural formula is:
Comprise the steps:
(1) tetramethylolmethane is dissolved in the solvent, and under the inert atmosphere, drips the phosphorus oxychloride of equimolar amount under 20-105 ℃ of temperature, reaction is not discharged to there being obvious hydrogen chloride gas;
(2) continue to drip the phosphorus oxychloride of tetramethylolmethane 1/3 molar weight, and reaction is not till have obvious hydrogen chloride gas and discharge;
(3) filter then, washing, recrystallization, drying, obtain above-mentioned fire retardant.
Wherein, described solvent is a kind of in dioxane, tetrahydrofuran (THF), the ethylene dichloride or their mixture.
Wherein, the molar mass of described tetramethylolmethane, phosphorus oxychloride is than being 3:4.
Preferably, filtrate is used repeatedly through the distillating recovering solvent circulation.
Preferably, after (1) reactions steps, reaction system is cooled to normal temperature, adds appropriate amount of catalysts then.
Wherein, described catalyzer is DMAP.
More particularly, building-up reactions adopts following processing step:
1, to reflux exchanger being housed and having in the stirred vessel that feeds nitrogen protection gas, drops into an amount of solvent and tetramethylolmethane;
2, as the described method of U.S. patent US4464064, drip the phosphorus oxychloride of the tetramethylolmethane equimolar amount that drops into;
3, be added dropwise to complete after, continuing to the reactor heating and continuing to feed under the drying nitrogen condition, carry out back flow reaction, until no obvious hydrogen chloride gas discharge, about 12 hours of this process;
4, continue under reflux state, drip the phosphorus oxychloride of the institute's tetramethylolmethane that drops into 1/3 molar weight, control the rate of addition of this process, dropping end in about 6～8 hours.
5, keep reflux state, discharge until no obvious hydrogen chloride gas, about 12 hours of this process, reaction finishes;
6, product postprocessing: will react the material filtering desolventizing after finishing, and be washed to no chlorion, oven dry namely gets target product Trimer of the present invention then.
Be to realize the object of the invention, building-up reactions can be selected following reaction solvent: a kind of in dioxane, tetrahydrofuran (THF), the acetonitrile, and preferred dioxane is solvent;
Preferably, after first reactions steps, need reaction system is cooled to normal temperature, add an amount of acylation catalyst then, as DMAP etc., temperature rising reflux is proceeded the reaction of back then.
Embodiment 1
In the there-necked flask that has stirring, thermometer, reflux condensing tube and the protection of dry nitrogen air-flow, add 275ml dioxane and 54.4g(0.4mol) tetramethylolmethane.Be warming up to 95 ℃, add the 30.6g phosphorus oxychloride, this moment, visible reflux condensing tube had liquid return.Thereafter slowly drip the 30.6g phosphorus oxychloride, dripped off in 3 hours.Refluxed 12 hours.
Continue to drip dioxane (100ml) solution that contains the 20.4g phosphorus oxychloride, dripped off in 6 hours.After being added dropwise to complete, kept 12 hours under the reflux state, do not had obvious hydrogen chloride gas in the nitrogen gas stream this moment.
The gained material is filtered in cooling, and the washing filter cake, oven dry gets white powder solid product (Trimer) 25.2g, fusing point〉300 ℃, calculated yield is 32.3%.
Embodiment 2
Preceding as example 1, in this omission.
After once insulation refluxed 12 hours and before dripping last 20.4g phosphorus oxychloride dioxane solution, system is cooled to normal temperature, adds the dioxane mixing solutions of 3gDMAP and 20ml, be warming up to backflow then.
Next step reaction is continued, in this omission as example 1 in the back.
The gained material is filtered in cooling at last, and the washing filter cake, oven dry gets white powder solid product (Trimer) 50.7g, fusing point〉300 ℃, calculated yield is 32.3%.Finally obtain white powder solid product (Trimer) 25.2g, calculated yield is 65.0%.
Example 3
In the there-necked flask that has stirring, thermometer, reflux condensing tube and the protection of dry nitrogen air-flow, add 200ml acetonitrile and 54.4g(0.4mol) tetramethylolmethane.Be warming up to 85 ℃, add the 30.6g phosphorus oxychloride, this moment, visible reflux condensing tube had liquid return, and tetramethylolmethane is partly dissolved.Thereafter continue slowly to drip the 30.6g phosphorus oxychloride, dripped off in 8 hours.Refluxed 12 hours.
Continue to drip acetonitrile (100ml) solution that contains the 20.4g phosphorus oxychloride, dripped off in 6 hours.After being added dropwise to complete, kept 12 hours under the reflux state, do not had obvious hydrogen chloride gas in the nitrogen gas stream this moment.
The gained material is filtered in cooling, and the washing filter cake, oven dry gets white powder solid product (Trimer) 6.5g, fusing point〉300 ℃, calculated yield is 8.3%.
Embodiment 4
Preceding as example 3, in this omission.
After once insulation refluxed 12 hours and before dripping last 20.4g phosphorus oxychloride acetonitrile solution, system is cooled to normal temperature, adds the acetonitrile mixing solutions of 3gDMAP and 20ml, be warming up to backflow then.
Next step reaction is continued, in this omission as example 1 in the back.
The gained material is filtered in cooling at last, the washing filter cake, and oven dry gets white powder solid product (Trimer) 40.0g, and calculated yield is 51.3%.
Embodiment 5
In the there-necked flask that has stirring, thermometer, reflux condensing tube and the protection of dry nitrogen air-flow, add 300ml tetrahydrofuran (THF) and 54.4g(0.4mol) tetramethylolmethane.Be warming up to 65 ℃, add the 30.6g phosphorus oxychloride, this moment, visible reflux condensing tube had liquid return, and tetramethylolmethane is partly dissolved.Thereafter continue slowly to drip the 30.6g phosphorus oxychloride, dripped off in 8 hours.Refluxed 12 hours.
Cooling, the tetrahydrofuran (THF) mixing solutions of adding 3gDMAP and 20ml is warming up to backflow then.
Continue to drip tetrahydrofuran (THF) (100ml) solution that contains the 20.4g phosphorus oxychloride, dripped off in 6 hours.After being added dropwise to complete, kept 12 hours under the reflux state, do not had obvious hydrogen chloride gas in the nitrogen gas stream this moment.
The gained material is filtered in cooling, and the washing filter cake, oven dry gets white powder solid product (Trimer) 20.8g, fusing point〉300 ℃, calculated yield is 26.7%.
Although it is pointed out that the present invention elaborates by above-described embodiment.But those of ordinary skills should be understood that under the prerequisite of spirit of the present invention, improvement and change that the present invention is made include in protection scope of the present invention, and protection scope of the present invention is as the criterion with the content of appended claims.
Claims (6)
1. the synthetic method of a phosphate flame retardant, this flame retardant molecule formula is C
15H
240
16P
4, structural formula is:
Comprise the steps:
(1) tetramethylolmethane is dissolved in the solvent, and under the inert atmosphere, drips the phosphorus oxychloride of equimolar amount under 20-105 ℃ of temperature, reaction is not discharged to there being obvious hydrogen chloride gas;
(2) continue to drip the phosphorus oxychloride of tetramethylolmethane 1/3 molar weight, and reaction is not till have obvious hydrogen chloride gas and discharge;
(3) filter then, washing, recrystallization, drying, obtain above-mentioned fire retardant.
2. synthetic method as claimed in claim 1, wherein said solvent are a kind of in dioxane, tetrahydrofuran (THF), the ethylene dichloride or their mixture.
3. synthetic method as claimed in claim 1, wherein, the molar mass of described tetramethylolmethane, phosphorus oxychloride is than being 3:4.
4. as each described synthetic method of claim 1-3, filtrate is used repeatedly through the distillating recovering solvent circulation.
5. as each described synthetic method of claim 1-3, after (1) reactions steps, reaction system is cooled to normal temperature, adds appropriate amount of catalysts then.
6. synthetic method as claimed in claim 5, described catalyzer is DMAP.
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| CN2013100559478A CN103204879A (en) | 2013-02-21 | 2013-02-21 | Synthesis process of phosphate flame retardant |
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| CN2013100559478A CN103204879A (en) | 2013-02-21 | 2013-02-21 | Synthesis process of phosphate flame retardant |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004024A (en) * | 2014-06-11 | 2014-08-27 | 苏州科技学院相城研究院 | Method for preparing caged tetracyclic phosphate siloxane flame-retardant charring agent |
| CN106211777A (en) * | 2014-03-27 | 2016-12-07 | 巴斯夫欧洲公司 | The seven phosphorus derivative compounds as fire retardant |
| CN109180733A (en) * | 2018-09-18 | 2019-01-11 | 苏州科技大学 | Fire retardant phosphorous acyl-(N, N ', N ＂-three cage phosphate) triamine compound and preparation method thereof |
| CN109232978A (en) * | 2018-09-18 | 2019-01-18 | 苏州科技大学 | Fire retardant thiophosphoryl-(N, N ' ,-three young laying ducks in cage of N ") triamine compound and preparation method thereof |
| CN109504350A (en) * | 2018-12-20 | 2019-03-22 | 昆明理工大学 | A kind of natural phase-change material of body flame and preparation method thereof |
| CN116496753A (en) * | 2023-06-29 | 2023-07-28 | 广州以恒有机硅有限公司 | High-performance organic silicon sealant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206234A (en) * | 2007-10-26 | 2011-10-05 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol diphosphite antioxidant |
| CN102268043A (en) * | 2011-06-09 | 2011-12-07 | 苏州科技学院 | Sulfur-containing organic phosphine double-cage cyclic ester compound and preparation method thereof |
-
2013
- 2013-02-21 CN CN2013100559478A patent/CN103204879A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206234A (en) * | 2007-10-26 | 2011-10-05 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol diphosphite antioxidant |
| CN102268043A (en) * | 2011-06-09 | 2011-12-07 | 苏州科技学院 | Sulfur-containing organic phosphine double-cage cyclic ester compound and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEIYI XING ET AL.: "Flame retardancy and thermal degradation of intumescent flame retardant polypropylene with MP/TPMP", 《POLYM. ADV. TECHNOL.》, vol. 20, 21 November 2008 (2008-11-21) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106211777A (en) * | 2014-03-27 | 2016-12-07 | 巴斯夫欧洲公司 | The seven phosphorus derivative compounds as fire retardant |
| CN106211777B (en) * | 2014-03-27 | 2019-06-18 | 巴斯夫欧洲公司 | The seven phosphorus derivative compounds as fire retardant |
| CN104004024A (en) * | 2014-06-11 | 2014-08-27 | 苏州科技学院相城研究院 | Method for preparing caged tetracyclic phosphate siloxane flame-retardant charring agent |
| CN104004024B (en) * | 2014-06-11 | 2016-05-18 | 苏州科技学院相城研究院 | The preparation method of the fire-retardant carbon forming agent of four cage cyclic phosphate siloxanes |
| CN109180733A (en) * | 2018-09-18 | 2019-01-11 | 苏州科技大学 | Fire retardant phosphorous acyl-(N, N ', N ＂-three cage phosphate) triamine compound and preparation method thereof |
| CN109232978A (en) * | 2018-09-18 | 2019-01-18 | 苏州科技大学 | Fire retardant thiophosphoryl-(N, N ' ,-three young laying ducks in cage of N ") triamine compound and preparation method thereof |
| CN109504350A (en) * | 2018-12-20 | 2019-03-22 | 昆明理工大学 | A kind of natural phase-change material of body flame and preparation method thereof |
| CN116496753A (en) * | 2023-06-29 | 2023-07-28 | 广州以恒有机硅有限公司 | High-performance organic silicon sealant and preparation method thereof |
| CN116496753B (en) * | 2023-06-29 | 2023-08-25 | 广州以恒有机硅有限公司 | High-performance organic silicon sealant and preparation method thereof |
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Application publication date: 20130717 |