JPH0453875B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to organic cyclic phosphorus compounds useful as stabilizers, flame retardants, and raw materials for flame-retardant and heat-resistant polymer compounds. BACKGROUND ART Conventionally, as flame retardants for organic polymer compounds, inorganic compounds, organic phosphorous compounds, organic phosphorous compounds, organic halogen compounds, etc. are known. In addition, in Special Publication No. 48-41009, formulas (a) to (c)

【formula】

【formula】

[Formula] {In formulas (b) and (c), R represents an alkyl group or an aryl group} It is disclosed that an organic cyclic phosphorus compound represented by the following is effective as a heat stabilizer for organic polymer compounds. There is. In addition, polyfunctional hydroxyl compounds used as manufacturing raw materials to make polyester resins and polyurethane resins heat resistant or flame retardant include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol,
Aliphatics such as polyethylene glycol, polypropylene glycol, cyclohexanedimethanol,
Alicyclic diols, hydroquinone, resorcinol, 1,5-dihydroxynaphthalene, 2,6-
Aromatic diols such as dihydroxynaphthalene, bisphenol A, and bisphenol F are listed. Problems to be Solved by the Invention However, there are various problems and improvements desired in such conventional techniques. For example, inorganic compounds used as flame retardants have problems with their compatibility with synthetic resins, the amount added and the degree of effectiveness, and the retention of the original physical and chemical properties of the base material. Improvements are desired in the degree of effectiveness, volatility, compatibility with substrates, solvent extractability, retention of the original physical and chemical properties of substrates, generation of harmful gases during combustion, etc. The same applies to organic phosphorous compounds and organic phosphorous compounds, and further improvements are desired in the hydrolyzability of the compounds themselves. Similar improvement needs exist for the compounds represented by formulas (a) to (c) above, and the hydrolysis products of the compounds represented by formula (a) exhibit acidity, and depending on the intended use. It may be a hindrance. Furthermore, polyester resins and polyurethane resins produced using the above-mentioned diols are still insufficient in flame retardancy and heat resistance, and improvement in melt moldability is desired for heat-resistant polyester resins. Means and Effects for Solving the Problems The present invention was achieved as a result of various studies to solve the above problems and desired improvements. That is, according to the invention, the general formula () {In the general formula (), m and n represent integers of 1 or more} An organic cyclic phosphorus compound (hereinafter referred to as HCA-
NQ-HE) is provided. Further in accordance with the invention, the formula () An organic cyclic phosphorus compound (hereinafter referred to as HCA-
A method for producing HCA-NQ-HE by reacting HCA-NQ) with ethylene carbonate, ethylene oxide or 2-haloethanol is provided. HCA-NQ-HE itself can be used as a stabilizer and flame retardant for polymeric compounds such as polyester resins, polyurethane resins, polybutyral resins, SBR, NBR, AS resins, and ABS resins, as well as epoxy group-added compounds and acrylic Group-added compounds are used as monomers for flame-retardant and heat-resistant resins, and polyester resins and polyurethane resins produced using HCA-NQ-HE as a diol component have excellent flame retardancy, heat resistance, and good melt moldability. It is promising as a synthetic resin. Embodiment of the invention A raw material for HCA-NQ-HE of the compound of the present invention
HCA-NQ is an organic cyclic phosphorus compound represented by the above formula (a) (hereinafter referred to as HCA) and 1,4
- Obtained by reaction with naphthoquinone. HCA and its manufacturing method are disclosed in Japanese Patent Publication No. 49-45397 and Japanese Patent Publication No. 17979-1987. By reaction between HCA and 1,4-naphthoquinone
HCA-NQ is produced according to the following reaction formula. In one embodiment, a mixture of ethyl cellosolve and HCA is kept warm at 50 to 80°C, and HCA
Once dissolved, 1,4-naphthoquinone (0.8 to 1.0 mol per 1 mol of HCA) is added little by little under stirring, either in the form of a fine powder or as an ethyl cellosolve solution. After the addition was completed, the reaction was further carried out at 120° to 130°C for 1.5 to 3 hours, then cooled to around room temperature, the precipitate was removed, and HCA
- Obtain NQ. HCA-NQ is used as a raw material for producing the compound of the present invention either as a wet mass or after being dried. HCA-NQ is a hydroxyethylating agent such as ethylene carbonate, ethylene oxide or
- HCA-NQ-HE is produced by reacting haloethanol in the presence of a suitable catalyst or acid scavenger.
Their reaction formulas are shown below. {In formula (3), X represents a halogen atom and A represents an acid scavenger} The reaction of formula (1) is as follows, and the reaction of formula (2) is usually carried out with HCA-NQ in an inert solvent. This is carried out by heating ethylene oxide in a molar ratio of 2 or more in a closed reactor in the presence of a catalyst (organic or inorganic base). The reaction of formula (3) is usually carried out by heating HCA-NQ and 2 moles or more of 2-haloethanol in an inert solvent in the presence of an acid scavenger (organic or inorganic base) in a closed reactor. It is done. Among the above three types of reactions, in the reaction of formula (2), it is difficult to control the number of added moles of ethylene oxide, and (3)
The reaction of the formula has a slow reaction rate and side reactions (especially
ring closure or self-polymerization reaction of CH ₂ CH ₂ OH). On the other hand, the reaction of formula (1) has a fast reaction rate and the number of moles added is easy to control, especially when m=n=1
HCA−NQ−HE, that is, the following formula (-a) It is suitable for the production of compounds represented by Next, an embodiment of the production method of the present invention in the case of using ethylene carbonate will be described. After stirring, HCA-NQ, ethylene carbonate, and an inert solvent are charged into a reactor equipped with a thermometer, reflux condenser, and charging port. The amount of ethylene carbonate to be used is selected depending on the number of ethyleneoxy groups contained in the target compound of formula (). For example expression ()
When m = n = 1, 2 mol or more (up to about 4 mol) of ethylene carbonate is used per 1 mol of HCA-NQ, and when m = n = 2, 4 mol or more (up to about 8 mol) is used. is the reaction temperature and time,
It is also controlled by the amount of catalyst, etc. The numbers m and n in formula () are selected depending on the purpose of use, but are usually up to about 20, and m=n=1 is widely and advantageously used. The inert solvent is used in an amount of 150 to 500 parts, usually about 150 to 250 parts, per 100 parts (by weight, same hereinafter) of HCA-NQ. Solvent is HCA-NQ and/or HCA-NQ
- It is not necessary to dissolve HE; the reaction proceeds satisfactorily even in a suspended state. Examples include ethylene glycol lower alkyl ether, propylene glycol lower alkyl ether, benzene, toluene, and xylene. Although a solvent is not necessarily required, it is convenient to use one from an operational standpoint. Stir the above mixture at reflux temperature or 110° to 130°C.
Heat to temperature and add catalyst. As a catalyst, a basic compound such as an alkali hydroxide or an alkali carbonate is used. The amount used is about 0.1 to 10% of HCA-NQ. The reaction is carried out at the same temperature for 3 to 15 hours, usually for 4 to 6 hours, but it is advantageous to control the reaction while checking the production status of the target product using a liquid chromatograph. After the reaction is completed, the reaction mixture is cooled, filtered, and washed to obtain the desired product. In this case, filtration is a little difficult, so the reaction mixture is allowed to stand and the supernatant is decanted.
A washing solution is added to the sediment, stirred, allowed to stand, separated, and then filtered or dried as is. The washing liquid is appropriately selected depending on the solvent used. The crude HCA-NQ-HE thus obtained is usually purified by recrystallization. Crude HCA−NQ−HE100
Add 80 to 150 parts of a suitable solvent, such as methanol, and heat to around 6℃ to dissolve. If necessary, add activated carbon, heat, and if necessary, concentrate for 5 to 10 minutes.
The precipitate is filtered, washed and dried to obtain a purified product. The purified mother liquor is further concentrated, (super)cooled, and filtered to obtain a secondary crystallized product and then a tertiary crystallized product. These can usually be recycled for recrystallization. Next, examples of the present invention will be described. Example A reactor was charged with 382 g of HCA-NQ (purity 98.0%, 1.0 mol), 265 g of ethylene carbonate (3.0 mol), and 750 g of xylene, and 1.0 g of anhydrous potassium carbonate powder was heated at 115° to 120°C with stirring for about 30 ml. Another 1.0 minutes later
g (total 2.0 g), and the reaction was continued at the same temperature for an additional 5 hours. 1000 ml of water was added to the reaction mixture, the pH was adjusted to below 2 with dilute sulfuric acid, the mixture was stirred at 40° to 60°C for about 1 hour, and then left to stand to separate the supernatant liquid. more water
After washing with 1000ml of water and drying under reduced pressure at 120° to 140°C, the crude HCA-NQ-HE409 becomes a pale gray-white powder.
g (crude yield 83.5% vs. HCA-NQ). The purified product obtained by recrystallizing this crude HCA-NQ-HE from the same amount of methanol was a pale gray-white powder with a melting point of 202.0-203.5°C and a purity of 99.0% as determined by liquid chromatography. The elemental analysis values of the material are as follows, and the compound represented by the above formula (a) where m and n in the general formula () are 1 (molecular formula
C ₂₆ H ₂₃ O ₆ P). Elemental analysis value C (%) H (%) P (%) Measured value 68.12 5.02 6.58 Theoretical value 67.53 4.97 6.70 (as C ₂₆ H ₂₃ O ₆ P) Also, the infrared absorption spectrum (potassium bromide tablet method) of this product was Shown in Figure 1.

[Brief explanation of drawings]

The attached drawing shows the purified HCA-NQ obtained in the example.
-HE {General formula () where m=n=1 (
This is an infrared absorption spectrum (potassium bromide tablet method) of compound (a)}, in which the horizontal axis shows the wave number (cm ^-1 ) and the vertical axis shows the transmittance (%).

Claims (1)

[Claims] 1 General formula () An organic cyclic phosphorus compound represented by the general formula (), where m and n represent integers of 1 or more. 2. The organic cyclic phosphorus compound according to claim 1, wherein m=n=1 in the general formula (). 3 formula () A compound represented by and ethylene carbonate,
General formula () by reacting with ethylene oxide or 2-haloethanol A method for producing an organic cyclic phosphorus compound represented by the general formula (), where m and n represent integers of 1 or more. 4. The method for producing an organic phosphorus compound according to claim 3, wherein the hydroxyethoxylating agent is ethylene carbonate, and m=n=1 in the general formula ().