JP2000290288A - Production of polyphosphoric acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply producing a polyphosphoric acid ester having high heat stability and low volatility, and having a high phosphor content so that the ester can give sufficient flame-resisting properties to a synthetic resin, even when added in a small amount. SOLUTION: This method for producing a polyphosphoric acid ester comprises reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane-3,9-dio xide with a diol expressed by the formula: HO-R-OH (R is a 2-8C alkylene or a 6-20C arylene) in an amount of 2.5 to 5 mol per mol of the above compound in an organic solvent, then further adding the 3,9-dichloro-2,4,8,10-tetraoxa-3,9- diphosphaspiro[5,5]undecane-3,9-dioxide to the reaction mixture in an amount of 1-4 times the amount that is added at the first time, and finally subjecting the reaction product to condensation polymerization reaction at a temp. of 90-150 deg.C to form the polyphosphoric acid ester of the formula [R is a 2-8C alkylene or a 6-20C arylene; (n) is 1.8 to 6].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a polyphosphate having a specific structure. More specifically, the present invention relates to a method for easily producing a polyphosphate having a spiro ring, which is useful as an additive type flame retardant or a reactive type flame retardant.

[0002]

2. Description of the Related Art Conventionally, it has been well known that a phosphate ester having a spiro ring is useful as a flame retardant for a synthetic resin, and many studies have been made. For example, U.S. Pat. No. 3,090,799 discloses 3,9-dichloro-
Reaction of 2,4,8,10-tetraoxa3,9-diphosphaspiro [5.5] undecane3,9-dioxide (hereinafter abbreviated as PPAE) and a hydroxy compound at a molar ratio of about 1: 2 A monomer and a composition of an organophosphorus compound having a spiro ring (wherein X represents an alkyl group or an aryl group) as shown in the following Chemical Formula 2 are described. It is characterized by having.

Embedded image

Further, US Pat. No. 4,178,281 discloses a polycarbonate resin composition containing a compound represented by the above formula (2). However, the compounds having a spiro ring disclosed in these prior arts have a low phosphorus concentration due to being monomers, and it has been difficult to say that sufficient flame retardancy can be imparted with a small amount of addition.

On the other hand, Japanese Patent Application Laid-Open No. Sho 60-133049 discloses an impact-resistant flame retardant obtained by blending a monomer or polymer of a phosphate ester having a spiro ring with a polyphenylene ether or a composition comprising polyphenylene ether and polystyrene. A polyphenylene ether-based resin composition has been proposed. However, this publication does not disclose a specific method for producing a polymer of a phosphate ester having a spiro ring or the flame retardant effect of a resin composition using a polymer of a phosphate ester having a spiro ring.

A method for producing a polymer of a phosphoric ester having a spiro ring is disclosed in US Pat. No. 3,159,602, but the reaction is a solid melting reaction in the absence of a solvent, so that the reaction is not carried out. There is a problem in scale-up, for example, it is heterogeneous, requires a lot of power to make the reaction proceed uniformly, and is difficult to collect because the product adheres to the wall of the reaction vessel. Further, the polymer of the phosphoric ester having a spiro ring obtained by the method has a problem that sufficient flame retardancy cannot be obtained because a large amount of the monomer component remains and a large amount of the raw material diol remains. .

[0006]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, polymerized an organic phosphate having a spiro skeleton, isolated it,
The method of increasing the phosphorus concentration makes it easy to produce high phosphorus concentration polyphosphates that have high thermal stability and low volatility, and that can impart sufficient flame retardancy to synthetic resins at low levels. Finding what they can do, based on this knowledge,
The present invention has been completed. As is apparent from the above description, an object of the present invention is to provide a polyphosphoric acid having a high phosphorus concentration, which has high thermal stability, low volatility, and can impart sufficient flame retardancy to a synthetic resin at a low addition amount. An object of the present invention is to provide a method for easily producing an ester.

[0007]

The present invention is constituted as follows. 1) In an organic solvent, 3,9-dichloro-2,
4,8,10-Tetraoxa3,9-diphosphaspiro [5.5] undecane3,9-dioxide is added to 1 mole of diol represented by HO—R—OH (where R is 2 to 8 carbon atoms). Represents an alkylene group or an arylene group having 6 to 20 carbon atoms) in a molar ratio of 2.5 to 5 times, and then reacts the 3,9-dichloro-2,4,8,
10-tetraoxa3,9-diphosphaspiro [5.
5] Undecane 3,9-dioxide was added in an amount 1 to 4 times the amount of the initially added mole, and the temperature was 90 to 150.
A method for producing a polyphosphate ester represented by the following chemical formula 3, wherein a polycondensation reaction is carried out at a temperature of 0 ° C.

Embedded image (Where, R represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 20 carbon atoms, and n is 1.
8 to 6).

The starting material of the present invention, PPAE, is a known substance, for example, Journal of Organic.
Chemistry (Journal of Organic Chemistry) vol.28,
The production method is described on pages 1608-1612. That is, it is a compound obtained by reacting about 2 moles of phosphorus oxychloride with respect to 1 mole of pentaerythritol.

The diol which is the other starting material of the present invention is a compound which can be represented by the general formula HO-R-OH, wherein R is a straight-chain or a straight-chain having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms. It is a branched alkylene group or an arylene group having 6 to 20 carbon atoms. Specifically, for example, carbon number 2-8
Examples of the diol having an alkylene group include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, , 5-pentanediol, 2,4-
Pentanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol,
1,6-hexanediol, 2,5-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methylpentane-2,4-diol, 3-methyl-1,5-pentanediol , 1,7-heptanediol, 2-2-diethyl-1,3-propanediol,
2,4-dimethyl-2,4-pentanediol, 1,8
-Octanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.

Examples of diols having an arylene group having 6 to 20 carbon atoms include dihydroxybenzenes such as catechol, hydroquinone, and resorcinol; alkyl-substituted dihydroxybenzenes having 1 to 6 carbon atoms such as methylhydroquinone; Bisphenols such as 2-methylresorcinol, for example, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (2,2-bis (4-hydroxyphenyl) sulfone), bisphenol F (2,2
-Bis (4-hydroxyphenyl) methane), bisphenol AD (2,2-bis (4-hydroxyphenyl))
Ethane), dihydroxynaphthylene and the like.
All of these diols can use a commercial item.

The method for producing a polyphosphate represented by the above formula (3) of the present invention comprises the steps of: One or more of the compounds are added in a molar amount of 2.5 to 5 times, preferably 2.8 to 3.5 times, and a Lewis acid catalyst such as anhydrous aluminum chloride, anhydrous magnesium chloride or anhydrous chloride is added. Ferric, anhydrous zinc chloride, anhydrous stannic chloride, titanium tetrachloride, zirconium tetrachloride, etc., in an amount of 0.1 to 5% by weight of the raw material weight;
Preferably, 0.2 to 2% by weight is added, and in a non-reactive organic solvent, for example, toluene, xylene, o-dichlorobenzene, p-dichlorobenzene, under a dry nitrogen atmosphere under stirring at 90 to 150 ° C. Preferably 95-1
The mixture is heated to a temperature of 20 ° C., and the reaction is carried out for a time sufficient for generating a theoretical amount of hydrochloric acid gas generated by the reaction.

Next, PPAE is added in an amount of 0.5 to 4 times, preferably 1.5 to 3 times, the molar amount of the initially charged PPAE, and 0.1% of the weight of the additionally charged PPAE.
５5% by weight, preferably 0.4-2% by weight of the above-mentioned Lewis acid catalyst is added, and the mixture is heated with stirring to the same temperature as above, and the time is sufficient for the theoretical generation of hydrochloric acid gas generated by the reaction. Perform a condensation reaction. After completion of the reaction, the obtained reaction product is placed in a cooled ketone-based, ester-based or alcohol-based solvent, for example, one or more solvents such as acetone, ethyl acetate, butyl acetate, methanol, ethanol, and propanol. By dropping while stirring, only the polymer component of the above formula (3) precipitates as a solid, which is recovered by filtration.

[0013] The product obtained by the production method of the present invention is characterized in that the content of unreacted raw materials is small and the content of polymer components is large. If a large amount of unreacted raw materials is contained, the product reacts with moisture in the atmosphere to generate corrosive hydrochloric acid gas, which not only deteriorates storage stability, but also generates hydrochloric acid gas when mixed with resin. It is a danger. Further, if the product contains a large amount of the monomer component, it has poor solvent resistance and heat resistance, and there is a problem that when it is mixed with a resin and molded, the mold is contaminated.

[0014]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which should not be construed as limiting the scope of the present invention. The evaluation in Examples and Comparative Examples was performed by the following method.

(1) Measurement of Average Degree of Polymerization, Content of Polymer Component, and Conversion The average degree of polymerization was determined by an absolute calibration curve method using gel permeation chromatography (GPC).
The polymer component content (the polymer component refers to a dimer or higher phosphate ester) was determined from the ratio of the peak area of the polymer component to the total peak area measured by the GPC method. The conversion is determined by the GP of the starting material remaining in the product.
The area obtained by subtracting the C peak area from the total peak area was divided by the total peak area to obtain a percentage. The measurement conditions of GPC are as follows. Column: Shim-pack GPC-801D, Sh
im-pack GPC-802D, Shim-pac
k Connect three GPC-803Ds in series. Solvent: DMF flow = 1 ml / min. Detector: RI Sample: diluted 1000 times with DMF Injection volume: 100 μl

(2) Measurement of Total Phosphorus Concentration The measurement was performed in accordance with the ammonium vanadomolybdate method.
That is, 2 g of the samples obtained in Examples and Comparative Examples were heated and decomposed with 40 ml of aqua regia for 30 minutes, and a certain amount thereof was placed in a volumetric flask, and a nitric acid aqueous solution in which ammonia metavanadate and ammonium molybdate as color developing solutions were dissolved. Was added and the absorbance at a wavelength of 420 nm was measured, and the total phosphorus concentration was calculated from a calibration curve obtained from an aqueous solution of monopotassium phosphate as a standard solution.

(3) Combustion test and bleed resistance Polycarbonate resin (trade name: Panlite L-125)
0, manufactured by Teijin Chemicals Limited) 75 parts by weight, acrylonitrile butadiene copolymer (ABS) resin (trade name: KRA)
(LASTIC GA-704, manufactured by Sumika A & L Co., Ltd.)
25 parts by weight, 0.5 parts by weight of polytetrafluoroethylene (trade name: Teflon 6J, manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.), and 15 parts by weight of the sample obtained in each of the working examples and comparative examples were mixed with a Henschel mixer ( Product name,
(Mitsubishi Miike Steel Works, Ltd.) for 3 minutes, and the mixture is twin-screw extruder (PCM-30, Ikegai Iron Works)
The mixture was melted and kneaded at a melting and kneading temperature of 240 ° C., and the extruded thread-like strand was cut into pellets. Then, the pellets were obtained using an injection molding machine (J28SC, manufactured by Nippon Steel Corporation) with a width of 12.7 mm and a length of 12 mm.
A 7 mm, 1.6 mm thick test piece for a combustion test and a 100 mm wide, 100 mm long, 2 mm thick test piece for a bleed resistance test were formed. Combustion test is based on U
A combustion test according to the L-94V standard was performed. The bleeding resistance test was performed by placing the test piece horizontally in a thermo-hygrostat (LHL-112M, manufactured by Tabai Espec Co., Ltd.) and exposing it to the surface after one week exposure at 40 ° C. and 90% humidity. Was visually evaluated in two stages (○: no bleed, x: bleed).

Reference Example PPAE used in the present invention was obtained by the following method. That is, 560 g of pentaerythritol and 3500 g of phosphorus oxychloride were charged into a 5 liter reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer, and heated to 78 ° C. at the same temperature. After stirring for 50 minutes, the temperature was further raised to 109 ° C., refluxed with stirring at the same temperature for 7 hours, cooled to room temperature, and filtered to obtain white crystals. The obtained white crystals were washed twice with 2 liters of chloroform and three times with 2 liters of dichloromethane, and then vacuum-dried at room temperature for 16 hours to obtain 791 g of PPAE.

Example 1 59.4 g of PPAE obtained in the above Reference Example was placed in a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer.
(0.2 mol), 136.8 g of bisphenol A
(0.6 mol), 0.6 g of anhydrous aluminum chloride and 250 g of toluene were added, and the temperature was raised to 95 to 105 ° C. while stirring, and the mixture was cooled when a theoretical amount of hydrochloric acid gas was generated in 2 hours. PPAE 89.1 was added to the obtained reaction solution.
g (0.3 mol) and anhydrous aluminum chloride 0.6
g, and the temperature was raised again while stirring to 95 to 105 ° C., and the reaction was terminated when a theoretical amount of hydrochloric acid gas was generated in 2.5 hours. The obtained viscous reaction solution was added dropwise to 500 g of cooled ethyl acetate while stirring, and the precipitated white solid was collected by filtration, and further 300 ml of acetone was added.
After washing twice with, vacuum drying was performed at room temperature for 16 hours to obtain 175 g of the target substance as a white solid. Table 1 shows the results of various evaluations of the obtained product.

Example 2 59.4 g (0.2 mol) of PPAE, 66.1 g (0.6 mol) of hydroquinone, 0.6 g of anhydrous aluminum chloride were placed in a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer. And 250 g of toluene,
The temperature was raised while stirring to 95 to 105 ° C., and the mixture was cooled when a theoretical amount of hydrochloric acid gas was generated in 2 hours. 89.1 g (0.3 mol) of PPAE and 0.6 g of anhydrous aluminum chloride were further added to the obtained reaction solution, and
The temperature was raised while stirring to １０５105 ° C., and the reaction was terminated when a theoretical amount of hydrochloric acid gas was generated in 2.5 hours. The resulting viscous reaction solution was added dropwise to 500 g of cooled ethyl acetate while stirring, and the precipitated white solid was collected by filtration, further washed twice with 300 ml of acetone, and vacuum dried at room temperature for 16 hours. 133 g of the target substance was obtained as a white solid. Table 1 shows the results of various evaluations of the obtained product.

Example 3 59.4 g (0.2 mol) of PPAE, 62.5 g (0.6 mol) of neopentyl glycol, 0 mol of anhydrous aluminum chloride were placed in a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer. Then, 2.6 g and 250 g of toluene were added, the temperature was raised while stirring to 95 to 105 ° C., and the mixture was cooled when a theoretical amount of hydrochloric acid gas was generated in 2 hours. 89.1 g (0.3 m) of PPAE was further added to the obtained reaction solution.
ol) and 0.6 g of anhydrous aluminum chloride,
The temperature was raised again while stirring to 95 to 105 ° C, and the reaction was terminated when a theoretical amount of hydrochloric acid gas was generated in 2.5 hours. The obtained viscous reaction solution was cooled with ethyl acetate 500.
g, the mixture was stirred while being dropped, and the precipitated white solid was collected by filtration, further washed twice with 300 ml of acetone, and vacuum-dried at room temperature for 16 hours to obtain the target substance 13 as a white solid.
3 g were obtained. Table 1 shows the results of various evaluations of the obtained product.

Comparative Example 1 148.5 g (0.5 mol) of PPAE was placed in a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer.
136.8 g (0.6 mol) of bisphenol A was added, the temperature was increased while stirring to 170 ° C., and the mixture was stirred for 30 minutes.
The mixture was heated to 185 ° C. and stirred for 3 hours. 200 ° C
The reaction was completed by stirring for 30 minutes. The obtained viscous reaction solution is taken out at a high temperature, cooled, and cooled to 245.
g of product were obtained. Table 1 shows the results of various evaluations of the obtained product.

Comparative Example 2 148.5 g (0.5 mol) of PPAE was added to a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer.
66.1 g (0.6 mol) of hydroquinone was charged,
The temperature was increased while stirring to 175 ° C, and after stirring for 30 minutes, 18
The mixture was heated to 5 ° C. and stirred for 3 hours. The resulting viscous reaction solution was taken out at a high temperature and cooled to obtain 143 g of a product. Table 1 shows the results of various evaluations of the obtained product.

Comparative Example 3 148.5 g (0.5 mol) of PPAE was placed in a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer.
62.5 g (0.6 mol) of neopentyl glycol was charged, the temperature was increased while stirring to 130 ° C., and the mixture was stirred for 30 minutes, and then heated to 150 ° C. and stirred for 3 hours. Further 17
The reaction was heated to 0 ° C. and stirred for 30 minutes to complete the reaction. The resulting viscous reaction solution is taken out at a high temperature and cooled to 1
53 g of product were obtained. Table 1 shows the results of various evaluations of the obtained product.

Comparative Example 4 297 g (1 mol) of PPAE, 216.2 g (2.3 mol) of phenol, and 3ethylamine 3 in a reaction vessel equipped with a heating device, a stirrer, a reflux tube, an inlet, and a thermometer.
00 ml and methylene chloride 2000 ml,
The temperature was raised while stirring to 0 ° C., and the reaction was completed when a theoretical amount of hydrochloric acid gas was generated in 2 hours. After collecting methylene chloride from the obtained reaction solution by distillation, the residue was stirred and mixed in a mixed solution of distilled water and methylene chloride, and allowed to stand to take out only the methylene chloride layer. The methylene chloride was recovered by evaporation to obtain 284 g of diphenylpentaerythritol phosphate. Table 1 shows the results of various evaluations of the obtained product.

Comparative Example 5 The flame retardancy was evaluated using triphenyl phosphate (manufactured by Chisso Corporation) as a flame retardant.

As is clear from the results of the Examples and Comparative Examples, in the production method of the present invention, the polycondensation reaction proceeds at a relatively low temperature, and the obtained compound contains a large amount of a polymer component. And high conversion. In addition, when incorporated into a synthetic resin, it exhibits high flame retardancy with a low amount of addition, and since it is low in volatility, it can be seen that there is no bleeding from the resin.

[0028]

[Table 1]

[0029]

According to the production method of the present invention, the polycondensation reaction proceeds at a relatively low temperature, and the obtained compound contains a large amount of a polymer component and has a high conversion. Moreover, when blended in a synthetic resin, it exhibits high flame retardancy with a small amount of addition and does not bleed from the resin because of its low volatility. Therefore, the polyphosphate obtained by the production method of the present invention is effective as one component of a flame retardant such as a thermoplastic resin and a thermosetting resin, and a molded product obtained by blending the polyphosphate is: Electronic and electrical equipment materials, automotive parts, building materials,
It can be suitably used for various applications such as materials for railway vehicles and materials for aircraft equipment.

Claims (1)

[Claims] 1. An organic solvent comprising 3,9-dichloro-2,
4,8,10-Tetraoxa3,9-diphosphaspiro [5.5] undecane3,9-dioxide is added to 1 mole of diol represented by HO—R—OH (where R is 2 to 8 carbon atoms). Represents an alkylene group or an arylene group having 6 to 20 carbon atoms) in a molar ratio of 2.5 to 5 times, and then the 3,9-dichloro-2,4,4
8,10-Tetraoxa3,9-diphosphaspiro [5.5] undecane3,9-dioxide was additionally added in an amount of 1 to 4 times the amount of the initially added amount, and the temperature was adjusted to 90 to 90%.
Wherein the polycondensation reaction is carried out at 150 ° C.
A method for producing a polyphosphate represented by the formula: Embedded image (Where R is an alkylene group having 2 to 8 carbon atoms, 6 to 2
0 represents an arylene group, and n represents a number from 1.8 to 6.)