JP3109228B2 - Method for producing phosphinylcarboxylic acid or derivative thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phosphinyl carboxylic acid or a derivative thereof which is used for copolymerization of a polyester and imparts flame retardancy to the polyester.

[0002]

2. Description of the Related Art As esters of phosphinylcarboxylic acids, 3- (alkoxyallylphosphinyl) -propionic esters are already known. For example, ANPudovi
k and the like obtained 3- (alkoxyphenylphosphinyl) -propionate in a yield of 40 to 82% by the method shown below [ANPudovik, et. al., Izvest. Akad.
k, SSSR, Otdel Khim.Nauk, 1952 902, or AN
Pudovik, Doklady Akad. Nauk SSSR, 85 349 (1952)].

[0003]

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[0004] V.I. A. Kukhtin et al. Used the method shown below to prepare 3- (alkoxyphenylphosphinyl)
-Propionates are obtained in 32-52% yields [VAKukhtin, et. Al., Zhur., Obshcher Khim., 28 939].
(1958)].

[0005]

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[0006] However, these known methods only aim at synthesizing the propionate ester, and thus all of the methods have low yields. The literature does not disclose production conditions or the like relating to the improvement in yield. In addition, V. A. According to the method of Kukhtim et al., In addition to the low yield described above, the starting material dialkyl phosphonite is expensive, and it cannot be said that it is unsuitable as a method for producing phosphinylcarboxylic acid or a derivative thereof.

On the other hand, A. N. The method described by Pudovik et al. A. The yield is considerably higher than that of the method of Kukhtin et al. However, the yield is not industrially satisfactory. Further, in this method, it is essential to use sodium alcoholate as a catalyst, and there is no description about the reaction under non-catalytic conditions, which is a feature of the present invention. Further, only a phenyl group is disclosed as an aryl group of the propionate, but nothing is disclosed about those having a substituent.

[0008] The present invention solves the problems of yield and price in the above-mentioned known method for producing phosphinylcarboxylic acid or a derivative thereof, and produces phosphinylcarboxylic acid or a derivative thereof inexpensively with excellent yield. The aim is to provide a method.

Against this background, the present inventors have achieved the above object by using a specific alkylaryl phosphinate and reacting the mixture with an unsaturated carboxylic acid or a derivative thereof under specific conditions. It has been found that this has been achieved and the present invention has been completed.

That is, the process for producing a phosphinyl carboxylic acid or a derivative thereof according to the present invention comprises reacting a mixture of an alkylaryl phosphinate represented by the following general formula (I) with an unsaturated carboxylic acid or a derivative thereof. In producing the phosphinylcarboxylic acid represented by the formula (II) or a derivative thereof, the above mixture is subjected to 60 to 60 in the absence of a catalyst.
The reaction is performed at 200 ° C.

[0011]

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[0012]

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Hereinafter, the present invention will be described in more detail. In the method for producing a phosphinyl carboxylic acid or a derivative thereof according to the present invention, the mixing ratio of the alkylaryl phosphinate represented by the general formula (I) to the unsaturated carboxylic acid or the derivative thereof is alkyl aryl phosphinate / unsaturated Carboxylic acid or a derivative thereof has an equivalent ratio of 0.8 to
1/1 to 0.8, preferably 0.9 to 1/1 to 0.9.

The present invention is characterized in that the mixture having the above mixing ratio is reacted under heating at 60 to 200 ° C., preferably 80 to 180 ° C. in the absence of a catalyst. When this alkylaryl phosphinate is reacted with an unsaturated carboxylic acid or a derivative thereof in the above temperature range, the reaction proceeds without causing a side reaction, and the target phosphinyl carboxylic acid or a derivative thereof is 90% or more. In a yield of Therefore, there is no need to use a catalyst, and phosphinylcarboxylic acid or a derivative thereof can be produced inexpensively and with high yield.

If the reaction temperature is lower than 60 ° C., the activity of the alkylaryl phosphinate on the unsaturated carboxylic acid or its derivative is small, and the reaction does not proceed, which is not preferable. On the other hand, if the reaction temperature exceeds 200 ° C., an undesired side reaction is induced, and the decomposition of the formed phosphinylcarboxylic acid or a derivative thereof is accelerated, and the yield is undesirably reduced. In the present invention, it is desirable that the heating be performed within the above-mentioned temperature range and that the heating be performed under a nitrogen atmosphere in order to minimize the above-mentioned disadvantages.

In the above reaction, a solvent represented by the general formula HO (CH
₂ ) It can also be achieved by using a glycol represented by _m OH (where m means an integer from 2 to 12).

In this case, a known catalyst in the production of poly (ethylene terephthalate) is added to the glycol solution after completion of the reaction, and a transesterification reaction is carried out under heating at 100 to 240 ° C., whereby the following general formula (III) is obtained. It can be the glycol ester represented.

[0018]

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The reaction product obtained by the present invention is isolated once, dissolved in the above-mentioned glycol, and subjected to a transesterification reaction using a catalyst known in the production of poly (ethylene terephthalate). , The aforementioned general formula (III
)).

The starting material alkylaryl phosphinate used in the present invention may be, for example, GM Kosolapoff or the like;
It is produced by the following reaction shown by N. Pudovik et al. (GM Kosolapoff et. Al., J. Am. Chem. Soc., 72 42
92 (1950), ANPudovik et.al., DoKlady Akad.Nauk S.
SSR85 349 (1952)).

[0021]

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This reaction proceeds at a yield of 60 to 90% by controlling the reaction temperature to 10 ° C. or lower. This reaction can also be performed in the presence of a tertiary amine such as triethylamine N, N-dimethylaniline, N, N-dimethylaniline, pyridine, or an alcoholate of an alkali metal for the purpose of capturing the generated hydrochloric acid gas. .

The following are examples of the alkylaryl phosphinate used in the present invention, but the present invention is not limited thereto. That is,
Methyl phenyl phosphinate, ethyl phenyl phosphinate, propyl phenyl phosphinate, butyl phenyl phosphinate, pentyl phenyl phosphinate, hexyl phenyl phosphinate, isopropyl phenyl phosphinate, isobutyl phenyl phosphinate, methyl-4-methyl phenyl phosphinate, ethyl -4-methylphenylphosphinate, methyl-
2,4-dimethylphenylphosphinate, ethyl-
2,4-dimethylphenylphosphinate, methyl-4
-Ethylphenylphosphinate, ethyl-4-ethylphenylphosphinate, methyl-4-fluorophenylphosphinate, ethyl-4-fluorophenylphosphinate, methyl-4-chlorophenylphosphinate, ethyl-4-chlorophenylphosphinate, methyl -4-bromophenylphosphinate, ethyl-4-
Bromophenylphosphinate methyl-2,4-difluorophenylphosphinate, ethyl-2,4-difluorophenylphosphinate, methyl-2,4-dichlorophenylphosphinate, ethyl-2,4-dichlorophenylphosphinate, methyl-2, 4-Dibromophenylphosphinate, ethyl-2,4-dibromophenylphosphine, and the like can be used.

The alkylaryl phosphinate used in the present invention is, for example, WTDye or B. Buchne.
The reaction can also be performed using the aryldichlorophosphine of the general formula (IV) as a raw material by the following reaction such as r.
Am. Chem. So., 70 2595 (1948) and B. Buchner et.al., J.
Am. Chem. So., 73 755 (1951)].

[0025]

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On the other hand, examples of the unsaturated carboxylic acid or its derivative to be reacted with the above alkylaryl phosphinate include acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate,
Ethyl methacrylate, crotonic acid, methyl crotonic acid, ethyl crotonic acid, isocrotonic acid, methyl isocrotonic acid, ethyl isocrotonic acid , itaconic acid, itako
Acid anhydride, dimethyl itaconate, diethyl itaconate
, Mesaconic acid, dimethyl mesaconate, dieza mesaconate
Chill, fumaric acid, dimethyl fumarate, diethyl fumarate
Maleic acid, maleic anhydride, dimethyl maleate
And diethyl maleate .

The phosphinylcarboxylic acid or its derivative obtained by the method of the present invention described in detail above is represented by the following general formula (V).

[0028]

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Specific examples of the phosphinylcarboxylic acid or a derivative thereof include the following. That is, methyl 3- (methoxyphenylphosphinyl) propionate, ethyl 3- (ethoxyphenylphosphinyl) propionate, methyl 2-methyl-3- (methoxyphenylphosphinyl) propionate, 2-methyl-3 −
Ethyl (ethoxyphenylphosphinyl) propionate, methyl 3-methyl-3- (methoxyphenylphosphinyl) propionate, ethyl 3-methyl-3- (ethoxyphenylphosphinyl) propionate, 3- (methoxy- Methyl 4-methylphenylphosphinyl) propionate, ethyl 3- (ethoxy-4-methylphenylphosphinyl) propionate, methyl 2-methyl-3- (methoxy-4-methylphenylphosphinyl) propionate, Ethyl 2-methyl-3- (ethoxy-4-methylphenylphosphinyl) propionate, 3-methyl-
Methyl 3- (methoxy-4-methylphenylphosphinyl) propionate, 3-methyl-3- (ethoxy-4-
Methylphenylphosphinyl) methyl propionate, 3
Methyl- (methoxy-2,4-dimethylphenylphosphinyl) propionate, 3- (ethoxy-2,4-dimethylphenylphosphinyl), ethyl propionate,
Methyl 2-methyl-3- (methoxy-2,4-dimethylphenylphosphinyl) propionate, 2-methyl-3
Ethyl-(ethoxy-2,4-dimethylphenylphosphinyl) propionate, methyl 3-methyl-3- (methoxy-2,4-dimethylphenylphosphinyl) propionate, 3-methyl-3- (ethoxy- Ethyl 2,4-dimethylphenylphosphinyl) propionate, 3-
Methyl (methoxy-4-fluorophenylphosphinyl) propionate, ethyl 3- (ethoxy-4-fluorophenylphosphinyl) propionate, 2-methyl-3
Methyl-(methoxy-4-fluorophenylphosphinyl) propionate, 2-methyl-3- (ethoxy-4-
Fluorophenylphosphinyl) methyl propionate,
Methyl 3-methyl-3- (methoxy-4-fluorophenylphosphinyl) propionate, 3-methyl-3-
Ethyl (ethoxy-4-fluorophenylphosphinyl) propionate, methyl 3- (methoxy-4-chlorophenylphosphinyl) propionate, 3- (ethoxy-
Ethyl 4-chlorophenylphosphinyl) propionate, methyl 2-methyl-3- (methoxy-4-chlorophenylphosphinyl) propionate, 2-methyl-3-
(Ethoxy-2,4-dimethylphenylphosphinyl)
Ethyl propionate, 3-methyl-3- (methoxy-4
-Chlorophenylphosphinyl) methyl propionate,
Ethyl 3-methyl-3- (ethoxy-4-chlorophenylphosphinyl) propionate, 3- (methoxy-4-ethyl)
Bromophenylphosphinyl) methyl propionate, 3
Ethyl- (ethoxy-4-bromophenylphosphinyl) propionate, methyl 2-methyl-3- (methoxy-4-bromophenylphosphinyl) propionate, 2-
Ethyl methyl-3- (ethoxy-4-bromophenylphosphinyl) propionate, methyl 3-methyl-3- (methoxy-4-bromophenylphosphinyl) propionate, 3-methyl-3- (ethoxy-4) -Bromophenylphosphinyl) ethyl propionate, methyl 3- (methoxy-2,4-difluorophenylphosphinyl) propionate, ethyl 3- (ethoxy-2,4-difluorophenylphosphinyl) propionate, 2 -Methyl-
Methyl 3- (methoxy-2,4-difluorophenylphosphinyl) propionate, ethyl 2-methyl-3- (ethoxy-2,4-difluorophenylphosphinyl) propionate, 3-methyl-3- (methoxy) −2,4-
Methyl difluorophenylphosphinyl) propionate, ethyl 3-methyl-3- (ethoxy-2,4-difluorophenylphosphinyl) propionate, methyl 3- (methoxy-2,4-dichlorophenylphosphinyl) propionate Methyl, 3- (ethoxy-2,4-dichlorophenylphosphinyl) propionate, methyl 2-methyl-3- (methoxy-2,4dichlorophenylphosphinyl) propionate, 2-methyl-3- (ethoxy-2) Ethyl 3-, 4-dichlorophenylphosphinyl) propionate, Methyl 3-methyl-3- (methoxy-2,4 dichlorophenylphosphinyl) propionate, 3-Methyl-3- (ethoxy-2,4diphenylphosphinyl) Ethyl propionate, 3- (methoxy-2,4-cybromophenylphosphine ) Methyl propionate, 3-
Ethyl (ethoxy-2,4 dibromophenylphosphinyl) propionate, 2-methyl-3- (methoxy-2,
Methyl 4-dibromophenylphosphinyl) propionate, ethyl 2-methyl-3- (ethoxy-2,4-dibromophenylphosphinyl) propionate, 3-methyl-3- (methoxy-2,4-dibromophenyl) Methyl 3-phosphonyl) propionate, ethyl 3-methyl-3- (ethoxy-2,4 dibromophenylphosphinyl) propionate, propyl 3- (propoxyphenylphosphinyl) propionate, 3- (butoxyphenylphosphinyl) B) butyl propionate, propyl 2-methyl-3- (propoxyphenylphosphinyl) propionate, 2
Butyl 3-methyl-3- (butoxyphenylphosphinyl) propionate, propyl 3-methyl-3- (propoxyphenylphosphinyl) propionate, 3-methyl-
3- (butoxyphenylphosphinyl) propionate butyl, (methoxyphenylphosphinyl) dimethyl succinate, (ethoxyphenylphosphinyl) diethylsuccinate, (propoxyphenylphosphinyl) dipropyl succinate, (ethoxyphenylphospho) (Finyl) succinic anhydride, (methoxyphenylphosphinylmethylene) dimethyl succinate, (ethoxyphenylphosphinylmethylene) diethyl succinate, (propoxyphenylphosphinylmethylene) dipropyl succinate, (ethoxyphenylphosphinyl) ) Succinic anhydride and the like,
This does not limit the present invention.

The phosphinylcarboxylic acid or a derivative thereof produced in the present invention is used as a comonomer when producing a linear polyester polymer such as poly (ethylene terephthalate). Gives good difficulty and dyeability. Fibers and woven fabrics produced from such polyester copolymers have far greater durability in difficulty performance than those imparted with difficulty by post-processing or blending of a difficulty agent.

Further, the phosphinylcarboxylic acid or its derivative produced in the present invention is obtained by copolymerizing or blending a metal salt of 3- (alkoxyarylphosphinyl) propionic acid represented by the following general formula (V). By doing so, the crystallinity of the polyester polymer can be improved.

[0032]

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[0033]

The present invention will be described in more detail with reference to the following examples. Example 1 [Production of methyl 3- (methoxyphenylphosphinyl) propionate] 50 g of methylphenylphosphinate and methyl acrylate were placed in a 200-ml reaction flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, and a cooling tube. 29g
Was immersed in an oil bath at 80 ° C., a sudden heat generation occurred, and the internal temperature rose to nearly 150 ° C. The reaction is continued for 2 hours at a reaction temperature of 140 to 150 ° C. by controlling the temperature of the oil bath. After completion of the reaction, the residue was subjected to distillation under reduced pressure to obtain a target compound in a yield of 93%. The boiling point of this compound is 150 to 153 ° C./0.5 mmHg, and the elemental analysis value from NMR spectrum is C: 54.51 (54.5).
5), H: 6.19 (6.24) P: 12.81 (1
2.79). However, the values in parentheses are theoretical values.

Example 2 [Production of ethyl 3- (ethoxyphenylphosphinyl) propionate] A mixture of 50 g of ethylphenylphosphinate and 31 g of ethyl acrylate was prepared in the same manner as in Example 1,
The reaction was carried out by heating to 50 to 170 ° C. After completion of the reaction, distillation under reduced pressure gave the target compound in a yield of 95%. The boiling point of this compound is 154 to 157 ° C / 0.5 mmH
g, the elemental analysis value from the NMR spectrum is C: 57.
70 (57.78), H: 7.10 (7.09), P:
It was 11.47 (11.46). However, the values in parentheses are theoretical values.

EXAMPLE 3 [Production of diethyl (ethoxyphenylphosphinyl) succinate] A mixture of 50 g of ethylphenylphosphinate and 52 g of diethyl fumarate was prepared in the same manner as in Example 1 for 150 g.
The reaction was carried out by heating to ~ 170 ° C. After completion of the reaction, distillation under reduced pressure was performed to obtain a target compound in a yield of 92%. The boiling point of this compound is 191 ° -193 ° C./0.2 mmHg, and the elemental analysis values are C: 56.23% (56.14%), H: 6.
74% (6.77%), P: 9.08% (9.05%)
Met. However, the numbers in parentheses are theoretical values.

Example 4 [Production of diethyl (ethoxyphenylphosphinyl) succinate] A mixture of 50 g of ethylphenylphosphinate and 56 g of diethyl itaconate was reacted according to Example 1. After completion of the reaction, distillation under reduced pressure gave the target compound in a yield of 91%. The boiling point of this compound is 214-21.
6 ° C./0.1 mmHg, elemental analysis value: C: 57.26%
(57.30%) H: 7.13% (7.07%), P:
8.71% (8.69%). However, the numbers in parentheses are theoretical values.

Comparative Example 1 [Production of ethyl 3- (ethoxyphenylphosphinyl) propionate] The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was controlled at 45 ° C. A mixture of 50 g of ethylphenylphosphinate and 31 g of ethyl acrylate was heated to 45 ° C. and reacted for 3 hours. After completion of the reaction, the mixture was distilled under reduced pressure, and unreacted starting materials were recovered.

Comparative Example 2 [Production of ethyl 3- (ethoxyphenylphosphinyl) propionate] According to Example 3, the reaction was carried out without ethanol from the beginning. To a mixture of 50 g of ethylphenylphosphinate and 31 g of ethyl acrylate, 2
Add the prescribed sodium ethylate ethanol solution,
The reaction was performed at 80 to 90 ° C. for 30 minutes. After completion of the reaction, distillation was performed under reduced pressure to obtain a target compound in a yield of 78%. The yield was as low as 20% as compared with the method described in Example 3 of the present invention.

Comparative Example 3 [Production of ethyl 3- (ethoxyphenylphosphinyl) propionate] According to Example 3, a reaction was carried out using a 0.2 N sodium ethylate ethanol solution as a catalyst. To a mixture of 50 g of ethylphenylphosphinate, 31 g of ethyl acrylate and 5 g of ethanol was added dropwise an ethanol solution of 0.2N sodium ethylate. When 18 ml of the catalyst solution was added dropwise, the reaction temperature reached 43 ° C., and the temperature did not rise even if it was further added, and the temperature began to decrease. The reaction was performed for 2 hours while controlling the reaction temperature at 40 ° C. After completion of the reaction, distillation was performed under reduced pressure to obtain the target compound in a yield of 63%.
% Was too low.

[0040]

According to the method of the present invention, phosphinylcarboxylic acid or a derivative thereof can be produced at an excellent yield and at low cost without causing side reactions. Further, when this is used for the copolymerization reaction of polyester, it is useful because it can easily and inexpensively make the polyester flame-retardant.

(56) References JP-A-2-225488 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 9/32 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A phosphinyl carboxylic acid or a derivative thereof represented by the following general formula (II) by reacting a mixture of an alkylaryl phosphinate represented by the following general formula (I) and an unsaturated carboxylic acid or a derivative thereof: A process for producing phosphinylcarboxylic acid or a derivative thereof, wherein the mixture is reacted at 60 to 200 ° C. in the absence of a catalyst when producing the compound. Embedded image Embedded image