CN1086390C - Preparation method of pentaerythritol phosphate - Google Patents
Preparation method of pentaerythritol phosphate Download PDFInfo
- Publication number
- CN1086390C CN1086390C CN99115493A CN99115493A CN1086390C CN 1086390 C CN1086390 C CN 1086390C CN 99115493 A CN99115493 A CN 99115493A CN 99115493 A CN99115493 A CN 99115493A CN 1086390 C CN1086390 C CN 1086390C
- Authority
- CN
- China
- Prior art keywords
- tetramethylolmethane
- pepa
- phosphorus oxychloride
- dichloropropylene
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for using halogenated hydrocarbon with the boiling range of 96 DEG C to 140 DEG C as synthetic solvents to prepare 1-oxo-4-hydroxymethyl-1-phospha-2, 6, 7-tri-oxa double ring [2, 2, 2] octane by pentaerythritol reacting with phosphorus oxychloride. Used solvents can be obtained by distilling side products in the production of chloropropene. The reaction yield can be more than 96%; products in solvents form fine sand-shaped crystals for bringing convenience to production; the synthetic product can be used as carbon forming agents or intermediate bodies for synthesizing various intumescent flame retardants.
Description
The present invention relates to a kind of tetramethylolmethane and phosphorus oxychloride reaction and prepare 1-oxo-4-methylol-1-phospha-2,6, the method for 7-trioxa-l-phosphabicyclo [2,2,2] octanes (hereinafter to be referred as PEPA).
Purified PEPA is a white solid, 213 ℃-218 ℃ of fusing points.Structural formula is as follows:
United States Patent (USP) U.S.Pat.No.4,454,064 discloses the synthesis technique of making solvent with dioxane adds (the 1mol tetramethylolmethane adds dioxane 500ml) in the dioxane with tetramethylolmethane, under nitrogen protection, be warming up to 95 ℃, add half phosphorus oxychloride earlier, splash into second half phosphorus oxychloride (tetramethylolmethane and phosphorus oxychloride equivalent) again; Drip and finish, back flow reaction is not discharged to there being hydrogen chloride gas.Discharging, cooling is filtered, and with dioxane and normal hexane washing, uses the dehydrated alcohol crystallization, the dry finished product that gets.
Many patent disclosures before this correlation technique (referring to
U.S.Pat.No.3,155,703，U.S.Pat.No.3,189,633，
U.S.Pat.No.3,134,662，U.S.Pat.No.3,287,448，
U.S.Pat.No.3,293,327, U.S.Pat.No.3,342,903), but there is following shortcoming in these patented technologies: ratio defective product is on the low side, is not more than 90%; Long reaction time; Cold filtration, most of PEPA product can not form good xln, and forms a gel coat in solvent lower floor, brings difficulty for the product aftertreatment.
The objective of the invention is to improve the yield of PEPA, simplify aftertreatment technology, shorten the reaction times, improve the quality of products.
Technical scheme of the present invention is: adopt boiling range at 96 ℃-140 ℃ halohydrocarbon, as by season pentanediol synthesize the solvent of PEPA with phosphorus oxychloride reaction.
Wherein solvent is preferred 1,2-propylene dichloride, 1, and 2-dichloropropylene, 1,3-dichloropropylene, one or more in the glyceryl trichloride, the composition of mixture can be arbitrary ratios of above-mentioned several compounds.
Its most economical source of the mixture of chloropropane and propenyl chloride can obtain by simple distillation from the by product of propylene thermal chlorination production propenyl chloride, and according to the variation of thermal chlorination and separating technology, the composition of mixture is also changing.The propenyl chloride that contains 1-4% generally speaking in the thermal chlorination by product, 1,2 of the propylene dichloride of 50%-70%, the dichloropropylene of 20%-40% (containing two kinds of isomer), 1%-5%, 3-chloropropane, less water and carbon slag.Collect 96 ℃-120 ℃ fraction through simple distillation, the content of propylene dichloride is 60%-90% in the mixture of collection, and the content of dichloropropylene is 20%-40%, also may contain the glyceryl trichloride below 5%.This mixture promptly can be used as the solvent of synthetic PEPA, with this mixture by rectifying separation, can obtain highly purified 1,2-propylene dichloride, 1,2-dichloropropylene, 1,3-dichloropropylene and glyceryl trichloride all can be separately as the solvents that synthesizes PEPA.
If solvent is taken from the by product of propenyl chloride, then the preparation of PEPA comprises following two steps:
The first step: the separation of propenyl chloride by product.Get 1Kg propenyl chloride by product, add the sodium hydroxide solution washing of 50g1%, the separating oil water.Oil phase slowly heats up in the flask of band separator column, collects 96.8 ℃ of-120 ℃ of fractions, is the mixed solvent of synthetic PEPA.By rectifying separation, can obtain highly purifiedly 1 the mixture collected, 2-propylene dichloride, 1,2-dichloropropylene, 1,3-dichloropropylene and glyceryl trichloride, these four kinds of halohydrocarbon all can be separately as the solvents that synthesizes PEPA.
Second step: in the reactor of band thermometer, stirring, reflux exchanger, add solvent and the tetramethylolmethane that the first step is collected; be warming up to 95 ℃, under nitrogen protection, drip phosphorus oxychloride, drip and finish; back flow reaction is not emitted to there being hydrogen chloride gas, cooling discharging, washing, the dry product that gets.
If solvent is directly taken from existing commodity, then only need above-mentioned second step.
The present invention makes solvent by adopting halon, and the reaction yield of PEPA has been reached more than 95%; PEPA is the crystallization of fine sand shape in solvent, discharging can at room temperature be carried out, and makes operations such as discharging, filtration, recrystallization be easy to carry out; Reaction times also shortens than prior art.
Comparative example: in the 2000ml four-hole bottle of thermometer, stirring, reflux exchanger, dropping funnel is housed, add 1050ml dioxane and 210g tetramethylolmethane; stirring heating is warming up to 95 ℃ under nitrogen protection; add the 118g phosphorus oxychloride earlier, in 1-1.5 hour, splash into the 118g phosphorus oxychloride then.Drip and finish, slowly be warming up to 102 ℃ of-104 ℃ of back flow reaction 7 hours, do not emit to there being hydrogenchloride.Discharging is cooled to room temperature, and PEPA forms the gel coat of a densification in the dioxane bottom, filters, and with 150ml dioxane wash crystallization, washes twice with the 300ml normal hexane again, gets white solid, yield 89.6% after the vacuum-drying.
Embodiment 1: get 20Kg propenyl chloride by product, add the sodium hydroxide solution washing of 1000g1%, the separating oil water.Oil phase slowly heats up in the flask of band separator column, collects 96.8 ℃ of-120 ℃ of fractions as the mixed solvent that synthesizes PEPA, the consisting of of mixture: propylene dichloride 65.2%, dichloropropylene are 34.4%, trichloropropane is 0.4%.Add 1200g mixed solvent and 408g tetramethylolmethane in the 2000ml four-hole bottle of thermometer, stirring, reflux exchanger, dropping funnel is housed, stirring heating is warming up to 95 ℃ under nitrogen protection, splashes into the 461g phosphorus oxychloride in 1-1.5 hour.Drip and finish, slowly heat up, back flow reaction 5 hours, no hydrogenchloride is emitted.Be cooled to room temperature, PEPA forms a fine sand layer in the solvent bottom, filters, and does the mixed solvent washing, uses the dehydrated alcohol recrystallization, gets white solid after the vacuum-drying, and yield 96% confirms that through IR, HPLC, NMR and ultimate analysis product is PEPA.
Embodiment 2: other foreshortens to 15 minutes with embodiment one with the phosphorus oxychloride dropping time, and reaction yield is 96.5%.
Embodiment 3: other all is controlled at 85 ℃ with embodiment two with dropping temperature and temperature of reaction, and reaction yield is 95.2%, and the reaction times also extends to 10 hours just not to be had hydrogenchloride and emit.
Embodiment 4: other is used propylene dichloride instead and makes solvent with embodiment one, and reaction yield is 96.1%, but reflux time has extended to 6 hours.
Embodiment 5: other is used dichloropropylene instead and makes solvent with embodiment one, and reaction yield is 97%.
Claims (3)
1, a kind of method for preparing tetramethylolmethane phosphoric acid fat by tetramethylolmethane and phosphorus oxychloride reaction: it is characterized in that with the halohydrocarbon of boiling range, as the solvent of synthetic PEPA at 96 ℃-140 ℃.
2, according to the described method for preparing tetramethylolmethane phosphoric acid fat of claim 1, it is characterized in that said halohydrocarbon is 1,2-propylene dichloride, 2,2-dichloropropylene, 1,3-dichloropropylene, 1,2, one or more in the 3-trichloropropane, the composition of mixture can be arbitrary ratios of above-mentioned several compounds.
3,, it is characterized in that said halohydrocarbon is to obtain by simple distillation from the by product of propylene thermal chlorination production propenyl chloride according to the described method for preparing tetramethylolmethane phosphoric acid fat of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115493A CN1086390C (en) | 1999-07-22 | 1999-07-22 | Preparation method of pentaerythritol phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115493A CN1086390C (en) | 1999-07-22 | 1999-07-22 | Preparation method of pentaerythritol phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1281861A CN1281861A (en) | 2001-01-31 |
| CN1086390C true CN1086390C (en) | 2002-06-19 |
Family
ID=5278439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99115493A Expired - Fee Related CN1086390C (en) | 1999-07-22 | 1999-07-22 | Preparation method of pentaerythritol phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1086390C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455722B1 (en) * | 2001-06-29 | 2002-09-24 | Pabu Services, Inc. | Process for the production of pentaerythritol phosphate alcohol |
| CN100345939C (en) * | 2006-04-05 | 2007-10-31 | 浙江大学 | Preparation technology of phosphorus nitrogen series expansion type fire retardant |
| CN101328269B (en) * | 2008-07-20 | 2011-08-24 | 大连理工大学 | Preparation of polyphosphate flame retardant having dicyclic phosphoric acid ester structure |
| CN101921407B (en) * | 2010-08-17 | 2012-08-29 | 东华大学 | Bromine-containing pentaerythritol phosphoester retardant and preparation method thereof |
| CN104725667A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Novel phosphorus and silicon flame retardant with double caged phosphate structure as well as preparation method and application of novel flame retardant |
| CN104725668A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Fluorophenyl and phosphate structure-containing novel phosphorus-silicon flame retardant and preparation method and application thereof |
| CN105504354B (en) * | 2015-12-22 | 2018-09-18 | 湖南美莱珀科技发展有限公司 | A kind of pressure sensitive adhesive efficient halogen-free element fire retardant combination and preparation method thereof |
| CN109401224A (en) * | 2018-10-08 | 2019-03-01 | 东莞市创之源新材料科技有限公司 | A kind of halogen-free expansion fire retardant and preparation method thereof |
| CN109988335B (en) * | 2019-04-12 | 2021-03-23 | 深圳市通产丽星股份有限公司 | Ferrocenyl Schiff base and preparation method and application thereof |
| CN114284634B (en) * | 2021-12-28 | 2023-09-01 | 江苏厚生新能源科技有限公司 | Safe flame-retardant polyimide diaphragm and preparation method thereof |
| CN114478633A (en) * | 2022-02-25 | 2022-05-13 | 青岛长荣化工科技有限公司 | Preparation method of pentaerythritol phosphate PEPA |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454064A (en) * | 1982-10-29 | 1984-06-12 | Borg-Warner Corporation | Process for preparing pentaerythritol phosphate |
-
1999
- 1999-07-22 CN CN99115493A patent/CN1086390C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454064A (en) * | 1982-10-29 | 1984-06-12 | Borg-Warner Corporation | Process for preparing pentaerythritol phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1281861A (en) | 2001-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rieger et al. | Unsymmetric ansa-zirconocene complexes with chiral ethylene bridges: influence of bridge conformation and monomer concentration on the stereoselectivity of the propene polymerization reaction | |
| CN1086390C (en) | Preparation method of pentaerythritol phosphate | |
| CN1968924B (en) | Pyrrolidin-3-yl compounds useful as beta-secretase inhibitors for the treatment of alzheimer's disease | |
| CN100519561C (en) | Method for the preparation of hexahydro-furo-[2,3-b]furan-3-ol | |
| JPH0320290A (en) | 2,2'-bis(di(m-tolyl)phosphino)-1,1'-binaphthyl | |
| US5399722A (en) | Process for preparing tert-butyl (3R,5S)-6-hydroxy-3,5--O--isopropylidene-3,5-dihydroxyhexanoate | |
| US5534635A (en) | Process for preparing pyridine-2-carboxamides | |
| CN113354586B (en) | Preparation method of trifluoromethyl-containing pyrazolone compound | |
| Clear et al. | Isolation, structure, chemistry, and photochemistry of cis-bis (2, 2′-bipyridyl) carbonylchlororuthenium (II) perchlorate | |
| JPH01160965A (en) | Isoquinoline derivative | |
| SU873883A3 (en) | Method of preparing hexahydro-gamma-carbolins or their salts | |
| Erker et al. | Metallacyclic metaloxycarbene complexes from 1, 2-didehydrobenzene Group 4 metallocenes and metal carbonyls | |
| CN102001920B (en) | Preparation method of medicine intermediate | |
| CN102344431A (en) | Method for preparing nebivolol hydrochloride | |
| CN110437277B (en) | Synthetic method of phosphoalkenyl ester compound | |
| CN102321067A (en) | Preparation method of articaine hydrochloride | |
| WO2021044230A1 (en) | Process for the synthesis of the sodium salt of 4-[[(lr)-2-[5-(2-fluoro-3-methoxyphenyl)-3-[[2-fluoro-6-(trifluoromethyl)-phenyl]methyl]-3,6-dihydro-4-methyl-2,6-dioxo-l(2h)-pyrimidinyl]-l- phenylethyl]amino]-butanoic acid (elagolix sodium salt) and intermediates of said process | |
| JP4540197B2 (en) | (E) Process for producing 3-methyl-2-cyclopentadecenone | |
| HU215133B (en) | Process for the preparation of 1-(3-trialkylsilylphenyl)-2,2,2-trifluoromethyl ethanone derivatives | |
| Lam et al. | Restricted internal rotations in some ortho-substituted diaryl sulfides and sulfones | |
| Eliel et al. | Conformational analysis. 44. 1, 1, 2-Trimethylcyclohexane | |
| CN112851619B (en) | Synthesis method of selenium-containing heterochroman compound | |
| CN108503586A (en) | The method for preparing high-purity tolvaptan intermediate | |
| JP2005529865A (en) | Method for producing indene substituted product | |
| US6313364B1 (en) | Synthesis of cyclopropaneacetylene using a catalytic decarboxylation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BALING PETROCHEMICAL CO., LTD., SINOPEC Free format text: FORMER OWNER: YUEYANG PETROLEUM CHEMICAL ENGINEERING CORPORATION RESEARCH INSTITUTE Effective date: 20030404 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20030404 Patentee after: Baling Petrochemical Co., Ltd., SINOPEC Patentee before: Inst. of Yueyang Petro-Chemical General Plant |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |