DE19546833A1 - Halogen-free cyclic phosphate ester(s) useful as flame retardants - Google Patents
Halogen-free cyclic phosphate ester(s) useful as flame retardantsInfo
- Publication number
- DE19546833A1 DE19546833A1 DE1995146833 DE19546833A DE19546833A1 DE 19546833 A1 DE19546833 A1 DE 19546833A1 DE 1995146833 DE1995146833 DE 1995146833 DE 19546833 A DE19546833 A DE 19546833A DE 19546833 A1 DE19546833 A1 DE 19546833A1
- Authority
- DE
- Germany
- Prior art keywords
- halogen
- phosphoric acid
- dimethylphenyl
- free cyclic
- methylphenyl
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Abstract
Description
Die Erfindung betrifft halogenfreie cyclische Phosphorsäureester, ein Verfahren zu ihrer Herstellung und ihre Verwendung.The invention relates to halogen-free cyclic phosphoric acid esters, a process for their Production and its use.
Einige cyclische Phosphorsäureester sind bereits in der Literatur beschrieben. So findet sich im Chemical Abstracts 93, 133266 (1980) ein Hinweis auf verschiedene Halogenalkylester von cyclischen Phosphorsäureestern. Ferner wurden von R. M. Mc Connell und H. W. Coover jr. [J. Org. Chem 24 630-635 (1959)] weitere cyclische Phosphorsäureester syn thetisiert und charakterisiert.Some cyclic phosphoric acid esters have already been described in the literature. That's how it is in Chemical Abstracts 93, 133266 (1980) an indication of various haloalkyl esters of cyclic phosphoric acid esters. Further, R.M. Mc Connell and H.W. Cooper jr. [J. Org. Chem. 24 630-635 (1959)] further cyclic phosphoric esters syn thetisiert and characterized.
Überraschenderweise konnte nun eine Reihe neuer halogenfreier cyclischer Phosphorsäu reester synthetisiert und analytisch charakterisiert werden.Surprisingly, a number of new halogen-free cyclic Phosphorsäu be synthesized and analytically characterized.
Die vorliegende Erfindung betrifft daher neue halogenfreie cyclische Phosphorsäureester der allgemeinen Formel (I)The present invention therefore relates to novel halogen-free cyclic phosphoric acid esters of the general formula (I)
mit R = 2-Methylphenyl, 3-Methylphenyl, 4-Methylphenyl, 2,3-Dimethylphenyl, 2,4-Dimethylphenyl, 2,5-Dimethylphenyl oder 3,4-Dimethylphenyl. with R = 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl or 3,4-dimethylphenyl.
Die Erfindung betrifft ebenfalls ein Verfahren zur Herstellung der vorgenannten cyclischen Phosphorsäureester, bei dem man in einem 1. Reaktionsschritt 2,2-Dimethyl-1,3-propandiol mit Phosphoroxichlorid zum cyclischen Phosphorsäureesterchlorid (I) umsetzt:The invention also relates to a process for the preparation of the aforementioned cyclic Phosphoric acid ester, in which in a 1st reaction step 2,2-dimethyl-1,3-propanediol with phosphorus oxychloride to the cyclic phosphoric acid ester chloride (I) is reacted:
Das cyclische Phosphorsäureesterchlorid (I) wird dann in einem 2. Reaktionsschritt bei er höhter Temperatur mit einem Phenol R-OH, wobei R die eingangs beschriebene Bedeutung hat, zur Reaktion gebracht, wobei unter Abspaltung von Chlorwasserstoff der halogenfreie cyclische Phosphorsäureester (II) gebildet wird:The cyclic phosphoric acid ester chloride (I) is then in a 2nd reaction step in he elevated temperature with a phenol R-OH, where R is the meaning described above has, reacted with elimination of hydrogen chloride, the halogen-free cyclic phosphoric acid ester (II) is formed:
Die Umsetzungen können in geeigneten inerten Lösungsmitteln, wie Aromaten, Aliphaten, Cycloaliphaten oder Chloraliphaten, und in Gegenwart geeigneter tertiärer Amine, wie Triethylamin oder Pyridin, sowie in Gegenwart geeigneter Katalysatoren, wie Aluminium chlorid, durchgeführt werden.The reactions can be carried out in suitable inert solvents, such as aromatics, aliphatics, Cycloaliphaten or Chloraliphaten, and in the presence of suitable tertiary amines, such as Triethylamine or pyridine, as well as in the presence of suitable catalysts, such as aluminum chloride.
Die Umsetzungen können bei Normaldruck oder unter vermindertem Druck durchgeführt werden.The reactions can be carried out at atmospheric pressure or under reduced pressure become.
Die Erfindung betrifft weiterhin die Verwendung der erfindungsgemäßen halogenfreien cy clischen Phosphorsäureester als Flammschutzmittel.The invention further relates to the use of the halogen-free cy cical phosphoric acid esters as flame retardants.
In einem ersten Reaktionsschritt wurden 208 g 2,2-Dimethyl-1,3-propandiol mit 306 g Phosphoroxichlorid [analog Verfahrensweise A aus J. Org. Chem. 24, 632 (1959)] zum 2-Chloro-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinan umgesetzt. Das erhaltene Rohpro dukt wurde aus Toluol/Cyclohexan umkristallisiert.In a first reaction step, 208 g of 2,2-dimethyl-1,3-propanediol with 306 g Phosphorus oxychloride [analogous method A of J. Org. Chem. 24, 632 (1959)] to 2-chloro-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinan reacted. The crude product obtained The product was recrystallized from toluene / cyclohexane.
Für den nächsten Reaktionsschritt wurden dann 184,5 g (1 Mol) dieses Produkts in einem Rührreaktor in 1 l Toluol suspendiert, mit 108 g (1 Mol) 4-Methylphenol und 1,5 g Alumi niumchlorid (wasserfrei) versetzt und unter Rühren im Temperaturbereich von 20-110°C im Verlauf von 5 Stunden zur Reaktion gebracht.For the next reaction step then 184.5 g (1 mol) of this product in a Stirred reactor in 1 l of toluene, with 108 g (1 mol) of 4-methylphenol and 1.5 g of Alumi ammonium chloride (anhydrous) and stirred with stirring in the temperature range of 20-110 ° C. reacted in the course of 5 hours.
Nachdem die Hälfte des Toluols im Vakuum abdestilliert worden war, wurden 500 ml Cyclohexan zugesetzt. Dann wurde unter Rühren abgekühlt, wobei sich ein feinkristalliner Feststoff abschied, der nach Filtration aus Toluol/Cyclohexan umkristallisiert wurde. Es wurden 207 g eines farblosen, kristallinen Produkts mit dem Schmelzpunkt 95°C erhal ten, dessen Elementaranalyse folgende Werte ergab:After half of the toluene was distilled off in vacuo, 500 ml Added cyclohexane. It was then cooled with stirring, resulting in a finely crystalline Particle off, which was recrystallized after filtration from toluene / cyclohexane. There were 207 g of a colorless, crystalline product with the melting point 95 ° C erhal whose elemental analysis gave the following values:
Nach den obigen Analysenwerten sowie der ¹H-NMR-Analyse (Abb. 1) und der ³¹P-NMR-Analyse (Abb. 2) handelt es sich um das Produkt 5,5-Dimethyl-2-(4-me thyl)phenoxy-2-oxo-1,3,2-dioxaphosphorinan.After the above analysis values and the 1 H-NMR analysis (Fig. 1) and the 31 P-NMR analysis (Figure 2) is the product 5,5-dimethyl-2- (4-me thyl) phenoxy-2-oxo-1,3,2-dioxaphosphorinane.
Claims (6)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995146833 DE19546833A1 (en) | 1995-12-15 | 1995-12-15 | Halogen-free cyclic phosphate ester(s) useful as flame retardants |
| EP96118176A EP0779294A1 (en) | 1995-12-15 | 1996-11-13 | Halogen-free cyclic phosphoric acid esters and process for their preparation |
| JP33357896A JPH09183786A (en) | 1995-12-15 | 1996-12-13 | Halogen-free cyclic phosphoric acid ester and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995146833 DE19546833A1 (en) | 1995-12-15 | 1995-12-15 | Halogen-free cyclic phosphate ester(s) useful as flame retardants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19546833A1 true DE19546833A1 (en) | 1997-06-19 |
Family
ID=7780198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1995146833 Withdrawn DE19546833A1 (en) | 1995-12-15 | 1995-12-15 | Halogen-free cyclic phosphate ester(s) useful as flame retardants |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19546833A1 (en) |
-
1995
- 1995-12-15 DE DE1995146833 patent/DE19546833A1/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |