CN101993456B - 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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- CN101993456B CN101993456B CN 201010505942 CN201010505942A CN101993456B CN 101993456 B CN101993456 B CN 101993456B CN 201010505942 CN201010505942 CN 201010505942 CN 201010505942 A CN201010505942 A CN 201010505942A CN 101993456 B CN101993456 B CN 101993456B
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- phosphaphenanthrene
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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 the 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 in recent years proposition of halogen-free flameproof 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 " the 8th phase in 2010 the 48th page of a kind of preparation method who has reported this compound, the method was 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 the method.Except 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: with six-(4-aldehyde radical-phenoxy group)-ring, three phosphonitriles, carry out the melting addition reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (being called for short DOPO) and obtain 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 lower frit reaction 1-60 hour; React and be cooled to 80-130 ℃ after complete, stir lower add cleaning solvent ethylene glycol, propyl alcohol, Virahol, isopropylcarbinol, butanone, toluene, dimethylbenzene, chlorobenzene etc., 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 Büchner funnel, 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, preparation efficiency is high, 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; React and be cooled to 120 ℃ after complete, stir the lower cleaning solvent 12g dimethylbenzene that adds, holding temperature is 100 ℃, stirs 3 hours, filters wherein white powder with Büchner funnel, 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; React and be cooled to 100 ℃ after complete, stir the lower cleaning solvent 24g toluene that adds, holding temperature is 100 ℃, stirs 3 hours, filters wherein white powder with Büchner funnel, 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; React and be cooled to 130 ℃ after complete, stir the lower cleaning solvent 180g chlorobenzene that adds, holding temperature is 110 ℃, stirs 1 hour, filters wherein white powder with Büchner funnel, 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; React and be cooled to 120 ℃ after complete, stir the lower cleaning solvent 100g isopropylcarbinol that adds, holding temperature is 80 ℃, stirs 3 hours, filters wherein white powder with Büchner funnel, 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; React and be cooled to 120 ℃ after complete, stir the lower cleaning solvent 90g propyl alcohol that adds, holding temperature is 90 ℃, stirs 2 hours, filters wherein white powder with Büchner funnel, 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; React and be cooled to 130 ℃ after complete, stir the lower cleaning solvent 800g dimethylbenzene that adds, holding temperature is 120 ℃, stirs 3 hours, filters wherein white powder with Büchner funnel, 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 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 melting 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 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 was 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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| CN 201010505942 CN101993456B (en) | 2010-10-14 | 2010-10-14 | Method for preparing phosphaphenanthrene and phosphazene halogen-free retardant agent |
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| CN101993456B true CN101993456B (en) | 2013-03-13 |
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Families Citing this family (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 |
| CN104877173A (en) * | 2014-09-11 | 2015-09-02 | 常州大学 | Hydroxyl-containing liquid phosphor-nitrogen fire retardant and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| CN114957794B (en) * | 2022-06-01 | 2023-03-24 | 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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2010
- 2010-10-14 CN CN 201010505942 patent/CN101993456B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| 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.》.2002,第40卷359-368. * |
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