CN101993456A - Method for preparing phosphaphenanthrene and phosphazene halogen-free retardant agent - Google Patents
Method for preparing phosphaphenanthrene and phosphazene halogen-free retardant agent Download PDFInfo
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- CN101993456A CN101993456A CN2010105059427A CN201010505942A CN101993456A CN 101993456 A CN101993456 A CN 101993456A CN 2010105059427 A CN2010105059427 A CN 2010105059427A CN 201010505942 A CN201010505942 A CN 201010505942A CN 101993456 A CN101993456 A CN 101993456A
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Abstract
The invention relates to a method for preparing a phosphaphenanthrene and phosphazene halogen-free retardant agent hexa-(phosphaphenanthrene-hydroxymethyl-phenoxyl)-cyclotriphosphazene. The structural formula of the hexa-(phosphaphenanthrene-hydroxymethyl-phenoxyl)-cyclotriphosphazene is shown in a figure 1. The hexa-(phosphaphenanthrene-hydroxymethyl-phenoxyl)-cyclotriphosphazene is prepared through a fusion addition reaction on hexa(4-formyl-phenoxyl)-cyclotriphosphazene and a compound of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and is purified by adopting an organic solvenet washing method to obtain the white powder of the hexa-(phosphaphenanthrene-hydroxymethyl-phenoxyl)-cyclotriphosphazene with high purity and high yield.
Description
(1) technical field
The technical field that to the invention belongs to a kind of phosphorus nitrogen be the preparation technology of additive flame retardant.Relate to a kind of preparation method with six of two kinds of ignition-proof elements of phosphorus nitrogen-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles.
(2) background technology
Six-(phospho hetero phenanthrene-methylol-phenoxy group)-ring, three phosphonitriles are as a kind of addition type phosphorus-nitrogen containing flame retardant, phosphorus content 12.93%, nitrogen content is 1.95%, can be used as flame-retardant additive and is used for macromolecular material, coating and special engineering plastics such as Resins, epoxy, polyester, polyolefine.
From the eighties in 20th century, the phosphazene derivative that abroad begun one's study is owing to the proposition of halogen-free flameproof in recent years develops rapidly.The Allcock of University of Pennsylvania professor has synthesized six (4-aldehyde radical phenoxy groups) ring, three phosphonitriles in 1981, and it has been carried out serial sign.Japan Maruzen Petrochemical Co., Ltd. company is in patent U.S.Pat.No.4,988,791, Ireland Loctite Ltd. company is at patent U.S.Pat.No.4, and 732,956 have also introduced the synthetic method of six-(4-aldehyde radical-phenoxy group)-ring, three phosphonitriles.Once in " New Chemical Materials " 2010 the 8th phases the 48th page of a kind of preparation method who has reported this compound, this method was a solvent method to the applicant, and preparation efficiency is on the low side, and the application's method is avoided the problem that exists in this method.Except that applicant's report, also not occurring both at home and abroad at present about phospho hetero phenanthrene base phosphazene derivative is the report of the synthetic and patent of six-(phospho hetero phenanthrene-methylol-phenoxy group)-ring, three phosphonitriles.
(3) summary of the invention
The invention provides a kind of preparation method with additive flame retardant of two kinds of elements of phosphorus nitrogen.
Technical scheme of the present invention is: and with six-(4-aldehyde radical-phenoxy group)-ring three phosphonitriles, with 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO) carries out the fusion addition reaction and obtains six-(phospho hetero phenanthrene-hydroxy methyl phenyloxy)-ring, three phosphonitrile C
114H
84O
24P
9N
3, and reaction mixture purified by organic solvent washing.
Six-(phospho hetero phenanthrene-methylol-phenoxy group)-ring, three phosphonitriles
Among the present invention, raw materials used is six-(4-aldehyde radical phenoxy group)-ring, three phosphonitriles and DOPO; Cleaning solvent adopts ethylene glycol, propyl alcohol, Virahol, isopropylcarbinol, butanone, toluene, dimethylbenzene, chlorobenzene.
Six-(4-aldehyde radical-phenoxy group)-ring, three phosphonitriles
The preparation method
DOPO is heated to 118-190 ℃, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitriles, the mass ratio of DOPO and six (4-aldehyde radical-phenoxy group)-ring three phosphonitriles is 1.5-10: 1, under the agitation condition, at 118-190 ℃ of following frit reaction 1-60 hour; After finishing, reaction is cooled to 80-130 ℃, stir and add cleaning solvent ethylene glycol, propyl alcohol, Virahol, isopropylcarbinol, butanone, toluene, dimethylbenzene, chlorobenzene etc. down, the cleaning solvent consumption is the 50%-500% of DOPO weight, holding temperature is 30-140 ℃, stirred 0.2-3 hour, filter wherein white powder with B, repeated washing 2-5 time, after getting white powder, 30-100 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are pulverulent solids, transformation efficiency＞98.0%, purity＞99.0%.
Effect of the present invention and benefit are: the present invention adopts six-(4-aldehyde radical-phenoxy group)-ring, three phosphonitriles and 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) prepared flame-retardant additive six-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles by the method for direct addition, be swift in response, the preparation efficiency height, and remove residual DOPO raw material by the method for high-temperature solvent washing product is purified, solvent of the present invention has the lower solubleness of prepared product is had higher solubleness to impurity, adopts method provided by the invention can obtain six of high purity and high yield-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitrile powder.
(4) description of drawings
(5) embodiment
Embodiment 1 is heated to 130 ℃ with 18gDOPO, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitrile 4g, frit reaction 10 hours; After finishing, reaction is cooled to 120 ℃, stir and add cleaning solvent 12g dimethylbenzene down, holding temperature is 100 ℃, stirs 3 hours, filters wherein white powder with B, add the same dimethylbenzene repeated washing of measuring 3 times, after getting white powder, 80 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are powder 11.88g, yield 99.0%, purity 99.2%.
Embodiment 2 is heated to 160 ℃ with 12gDOPO, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitrile 4g, frit reaction 5 hours; After finishing, reaction is cooled to 100 ℃, stir and add cleaning solvent 24g toluene down, holding temperature is 100 ℃, stirs 3 hours, filters wherein white powder with B, repeated washing 4 times, after getting white powder, 80 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are powder 11.82g, yield 98.5%, purity 99.1%.
Embodiment 3 is heated to 160 ℃ with 180gDOPO, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitrile 40g, frit reaction 12 hours; After finishing, reaction is cooled to 130 ℃, stir and add cleaning solvent 180g chlorobenzene down, holding temperature is 110 ℃, stirs 1 hour, filters wherein white powder with B, adopt the same procedure repeated washing 3 times, after getting white powder, 80 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are powder 119.04g, yield 99.2%, purity 99.3%.
Embodiment 4 is heated to 130 ℃ with 100gDOPO, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitrile 40g, frit reaction 20 hours; After finishing, reaction is cooled to 120 ℃, stir and add cleaning solvent 100g isopropylcarbinol down, holding temperature is 80 ℃, stirs 3 hours, filters wherein white powder with B, adopt the same way as repeated washing 3 times, after getting white powder, 80 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are powder 119.28g, yield 99.4%, purity 99.1%.
Embodiment 5 is heated to 160 ℃ with 180gDOPO, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitrile 40g, frit reaction 30 hours; After finishing, reaction is cooled to 120 ℃, stir and add cleaning solvent 90g propyl alcohol down, holding temperature is 90 ℃, stirs 2 hours, filters wherein white powder with B, adopt the same procedure repeated washing 3 times, after getting white powder, 80 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are powder 119.16g, yield 99.3%, purity 99.2%.
Embodiment 6 is heated to 150 ℃ with 150gDOPO, adds six (4-aldehyde radical-phenoxy groups)-ring three phosphonitrile 40g, frit reaction 15 hours; After finishing, reaction is cooled to 130 ℃, stir and add cleaning solvent 800g dimethylbenzene down, holding temperature is 120 ℃, stirs 3 hours, filters wherein white powder with B, adopt the same procedure repeated washing 3 times, after getting white powder, 80 ℃ of oven dry, the product six that obtains at last-(phospho hetero phenanthrene-methylol-phenoxy group)-ring three phosphonitriles are powder 119.00g, yield 99.2%, purity 99.1%.
Claims (3)
1. the preparation method of a phospho hetero phenanthrene phosphonitrile halogen-free flame retardants, it is characterized in that the present invention is with six-(4-aldehyde radical-phenoxy group)-ring, three phosphonitriles, with 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO) carries out the fusion addition reaction and obtains six-(phospho hetero phenanthrene-hydroxy methyl phenyloxy)-ring, three phosphonitriles, and reaction mixture is purified by organic solvent washing.
2. the preparation method of a kind of phospho hetero phenanthrene phosphonitrile halogen-free flame retardants according to claim 1, it is characterized in that the present invention with DOPO and six (4-aldehyde radical-phenoxy group)-ring three phosphonitriles at 118-190 ℃ of frit reaction 1-60 hour, the mass ratio of DOPO and six (4-aldehyde radical-phenoxy group)-ring three phosphonitriles is 1.5-10: 1.
3. the preparation method of a kind of phospho hetero phenanthrene phosphonitrile halogen-free flame retardants according to claim 1 is characterized in that cleaning solvent adopts a kind of in ethylene glycol, propyl alcohol, Virahol, isopropylcarbinol, butanone, toluene, dimethylbenzene, the chlorobenzene.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113410A (en) * | 2013-03-05 | 2013-05-22 | 上海交通大学 | High-temperature resistant polyphosphazene microsphere and preparation method thereof |
| CN103435652A (en) * | 2013-07-01 | 2013-12-11 | 北京化工大学 | Preparation method of novel high nitrogen content compounds containing phosphaphenanthrene and phosphazene double-effect functional group |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
| CN104877173A (en) * | 2014-09-11 | 2015-09-02 | 常州大学 | Hydroxyl-containing liquid phosphor-nitrogen fire retardant and preparation method thereof |
| CN105295093A (en) * | 2015-12-02 | 2016-02-03 | 厦门大学 | Ring phosphonitrile type additive flame retardant and preparation method thereof |
| TWI615396B (en) * | 2016-10-20 | 2018-02-21 | Shengyi Technology Co Ltd | Halogen-modified modified cyclotriphosphazene halogen-free flame retardant and preparation method and application thereof |
| CN109400651A (en) * | 2017-08-15 | 2019-03-01 | 中蓝晨光化工研究设计院有限公司 | A kind of fire retardant and preparation method thereof of the structure of-DOPO containing phosphonitrile |
| CN110438578A (en) * | 2019-07-30 | 2019-11-12 | 福建省百凯经编实业有限公司 | A kind of color-changing face fabric and its production method |
| CN112442212A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN114106538A (en) * | 2021-12-16 | 2022-03-01 | 东莞市百川新材料有限公司 | Fully-degradable plastic processing technology |
| CN114957794A (en) * | 2022-06-01 | 2022-08-30 | 山东甲子湖畔新材料科技有限公司 | Halogen-free flame retardant and preparation method thereof |
-
2010
- 2010-10-14 CN CN 201010505942 patent/CN101993456B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| YING LING LIU: "Epoxy Resins from Novel Monomers with a Bis-(9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl-)Substituent", 《J.POLYM.SCI.PART A: POLYM. CHEM.》 * |
| 钱立军等: "具有磷杂菲和磷腈双效官能团的新型阻燃助剂的合成及表征", 《化工新型材料》 * |
| 钱立军等: "基于磷杂菲基团化合物的构建与性能", 《化学进展》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113410A (en) * | 2013-03-05 | 2013-05-22 | 上海交通大学 | High-temperature resistant polyphosphazene microsphere and preparation method thereof |
| CN103435652A (en) * | 2013-07-01 | 2013-12-11 | 北京化工大学 | Preparation method of novel high nitrogen content compounds containing phosphaphenanthrene and phosphazene double-effect functional group |
| CN104877173A (en) * | 2014-09-11 | 2015-09-02 | 常州大学 | Hydroxyl-containing liquid phosphor-nitrogen fire retardant and preparation method thereof |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
| CN104403128B (en) * | 2014-10-30 | 2017-07-04 | 东北林业大学 | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO |
| CN105295093A (en) * | 2015-12-02 | 2016-02-03 | 厦门大学 | Ring phosphonitrile type additive flame retardant and preparation method thereof |
| CN107964117A (en) * | 2016-10-20 | 2018-04-27 | 广东生益科技股份有限公司 | A kind of three phosphonitrile halogen-free flame retardants of silicone-modified ring and its preparation method and application |
| EP3312186A1 (en) | 2016-10-20 | 2018-04-25 | Shengyi Technology Co., Ltd. | Siloxane-modified cyclotriphosphazene halogen-free flame retardant, preparation process and use thereof |
| TWI615396B (en) * | 2016-10-20 | 2018-02-21 | Shengyi Technology Co Ltd | Halogen-modified modified cyclotriphosphazene halogen-free flame retardant and preparation method and application thereof |
| CN107964117B (en) * | 2016-10-20 | 2019-07-26 | 广东生益科技股份有限公司 | A kind of three phosphonitrile halogen-free flame retardants of silicone-modified ring and its preparation method and application |
| US10400173B2 (en) | 2016-10-20 | 2019-09-03 | Shengyi Technology Co., Ltd. | Siloxane-modified cyclotriphosphazene halogen-free flame retardant, preparation process and use thereof |
| CN109400651A (en) * | 2017-08-15 | 2019-03-01 | 中蓝晨光化工研究设计院有限公司 | A kind of fire retardant and preparation method thereof of the structure of-DOPO containing phosphonitrile |
| CN110438578A (en) * | 2019-07-30 | 2019-11-12 | 福建省百凯经编实业有限公司 | A kind of color-changing face fabric and its production method |
| CN110438578B (en) * | 2019-07-30 | 2021-08-20 | 福建省百凯经编实业有限公司 | Color-changing fabric and production method thereof |
| CN112442212A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
| CN114106538A (en) * | 2021-12-16 | 2022-03-01 | 东莞市百川新材料有限公司 | Fully-degradable plastic processing technology |
| CN114957794A (en) * | 2022-06-01 | 2022-08-30 | 山东甲子湖畔新材料科技有限公司 | Halogen-free flame retardant and preparation method thereof |
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| CN101993456B (en) | 2013-03-13 |
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