JPH06100577A - Novel reaction type flame retardant for polyester resin - Google Patents

Abstract

PURPOSE:To provide a novel flame retardant containing as a main component a cyclic phosphineoxide-dibasic carboxylic acid obtained by reacting a cyclic phosphinic acid compound with a dibasic unsaturated carboxylic acid, etc., and useful for fibers and films. CONSTITUTION:The objective flame retardant comprises as a main component a cyclic phosphineoxide-containing dibasic carboxylic acid obtained by addition- reacting a compound of formula I [R1-R8 8F{ H, Cl, Br. 1-4C hydrocarbon; X is N-H, N-R4 (R4 is 1-4C alkyl, benzyl), O, CH., etc.,] (e.g. a compound of formula II or III) with a dibasic unsaturated carboxylic acid or its lower alkyl ester in a solvent in the presence of a catalyst such as triethylamine preferably at 50-120 deg.C for 30min to 10hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel reactive flame retardant for polyester resins used for fibers or films.

[0002]

2. Description of the Related Art In recent years, the pursuit of safety has been emphasized, and in this sense, the necessity of making various molded articles such as fibers and films flame-retardant is increasing. Various studies have been conducted on molded articles derived from linear polyester resins, and some proposals have been made.

From the viewpoints of the sustainability of the effect and the productivity, the reaction type in which the polyester resin is added and copolymerized at the time of polymerization is considered to be particularly advantageous. Therefore, triphenyl phosphate, benzenephosphonic acid or the like is used. Phosphorus compounds have been used. However, such compounds deactivate the catalyst for the polyester polycondensation reaction, generate many ether bonds, lower the melting point of the polyester resin, volatilize these compounds themselves during the polycondensation reaction at high temperatures, etc. There were various problems.

In order to solve the above problems, a phosphinic acid ester having a specific structure is copolymerized in polyester (West Germany publication No. 2346787), and a phosphonic acid ester having a specific structure and a cyclic phosphinic acid ester are used in combination. (Japanese Patent Application Laid-Open No. 52-141860) and the like have been proposed and put to practical use, but the reaction rate during polyester polymerization is delayed, gelation occurs during the reaction, the product hue is deteriorated, Many problems remain, such as lowering the hydrolysis resistance derived from the P—O—C bond.

[0005]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a dibasic carboxylic acid containing a cyclic phosphine oxide, which does not have the above-mentioned drawbacks, as a reactive flame retardant for polyester resins. is there.

[0006]

In the present invention, a cyclic phosphinic acid compound represented by the following general formula (1) (hereinafter abbreviated as cyclic phosphinic acid compound) and a dibasic unsaturated carboxylic acid or a lower alkyl ester thereof are added. It is a novel reaction-type flame retardant for a polyester resin, which is mainly composed of a dibasic carboxylic acid containing a cyclic phosphine oxide obtained by the reaction.

[0007]

[Chemical 2]

(Wherein R ₁ , R ₂ and R ₃ are H, Cl,
Br or a hydrocarbon group having 1 to 4 carbon atoms is shown. X is N-
H, NR ₄ , O, CH ₂ , CO, SO ₂ , S, SO or C (CH ₃ ) ₂ is shown, and R ₄ is an alkyl group having 1 to ₄ carbon atoms or a benzyl group. same as below)

Examples of the cyclic phosphinic acid compound used in the reactive flame retardant for polyester resin of the present invention include the following chemical formulas, chemical formula 4, chemical formula 5, chemical formula 6, chemical formula 7, chemical formula 8, chemical formula 9, 10 and the like.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[0016]

[Chemical 9]

[0017]

[Chemical 10]

Examples of the dibasic unsaturated carboxylic acid or its lower alkyl ester include, for example, itaconic acid, crotonic acid, succinic acid, maleic acid, maleic anhydride, or their lower alkyls (methyl, ethyl, propyl, butyl, etc.). ) Ester etc. are mentioned.

The addition reaction of the above-mentioned cyclic phosphinic acid compound and the dibasic unsaturated carboxylic acid or its lower alkyl ester will be represented by the following reaction formula, if an example is shown based on the specific compound.

[0020]

[Chemical 11]

The reaction ratio between the cyclic phosphinic acid compound and the dibasic unsaturated carboxylic acid or its lower alkyl ester is usually 0.8 to 1.2 molar equivalents of the dibasic unsaturated carboxylic acid or its lower alkyl ester. A saturated carboxylic acid or a lower alkyl ester thereof is added, and a solvent and a catalyst are added if necessary, and the temperature is 30 to 150 ° C., preferably 5
It is carried out at 0 to 120 ° C. for 30 minutes to 10 hours.

Examples of the solvent include xylene, toluene, dimethylformaldehyde (DMF) and dimethylsulfoxide (DMSO), and examples of the catalyst include tertiary amines (eg triethylamine, pyridine etc.) and radical initiation catalysts. (For example, benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile, etc.) and the like. The amount of catalyst added is 0.01 to 1% by weight.

In the present invention, the cyclic phosphine oxide-containing dibasic carboxylic acid obtained as described above is added to the polyester resin as a reactive flame retardant. In addition, it is added during the production of the polyester resin so that the phosphorus atom content becomes 500 to 50,000 PPM, and particularly in order to obtain flame resistant fibers, it is desirable to add the phosphorus atom content to 1000 to 20,000 PPM. When the content is out of the above range, that is, when the content of phosphorus atom is small, sufficient flame retardancy cannot be obtained, and when it is large, the physical properties of the polyester resin are deteriorated undesirably.

The reactive flame retardant of the present invention may be added at any time during the esterification reaction, transesterification reaction, polycondensation reaction, etc. in the production of the flame-retardant polyester resin. In addition, the production conditions of the polyester resin are in accordance with conventionally known methods and conditions.

As an example, when terephthalic acid is used as the dibasic carboxylic acid component and ethylene glycol is used as the diol component, transesterification is performed at 150 ° C. under normal pressure.
If esterification is carried out at a temperature of 240 ° C., the reaction is carried out under normal pressure or under a pressure of up to 5 kg / cm ² at a temperature of 220 to 300 ° C.

The reaction catalyst used at this time is a conventionally known one, for example, a metal compound such as zinc, manganese, cobalt or titanium is used. The reaction product thus obtained is further subjected to polycondensation at a temperature of 250 to 300 ° C. under a high vacuum of 0.1 to 1 mmHg to obtain a predetermined polyester resin. The polycondensation reaction also utilizes conventionally known metal compounds such as antimony, germanium and titanium as catalysts.

[0027]

The reactive flame retardant containing a cyclic phosphine oxide-containing dibasic carboxylic acid as a main component, which is obtained according to the present invention, is a phosphine oxide having no P--O--C bond in the molecule, and therefore has a high heat resistance. It is excellent in water resistance and washing resistance because it does not cause deterioration in hue unlike conventional phosphorus compounds and does not cause the problem of volatilization during the reaction because of its reactivity.

[0028]

【Example】

Production Example 1. The cyclic phosphinic acid compound of Chemical formula 12 (melting point 21
(4 to 216 ° C.) 215.2 g (1 molar equivalent) was added, and 500 g of toluene and 1 wt% of triethylamine were added to the cyclic phosphinic acid compound. Next, 156.1 g (1.2 molar equivalents) of itaconic acid was added and reacted at reflux temperature for 5 hours to obtain 317.9 g of dibasic carboxylic acid containing cyclic phosphine oxide.

[0029]

[Chemical 12]

Production Example 2. 458.4 g (2 molar equivalents) of the cyclic phosphinic acid compound of Chemical formula 13 was added, and further 1000 g of toluene and 1% by weight of triethylamine were added to the cyclic phosphinic acid compound. Then itaconic acid 312.
2 g (2.4 molar equivalent) was added, and the mixture was reacted at reflux temperature for 5 hours to obtain 640.3 g of a cyclic phosphine oxide-containing dibasic carboxylic acid.

[0031]

[Chemical 13]

Production Example 3. 369.3 g (1.5 molar equivalent) of the cyclic phosphinic acid compound of Chemical formula 14 was added, and further, 500 g of xylene and 1% by weight of benzoyl peroxide were added to the cyclic phosphinic acid compound. Then maleic anhydride 1
76.5 g (1.8 molar equivalents) was added and the mixture was heated at 120 ° C for 10
The reaction was carried out for a period of time to obtain 490.7 g of a dibasic carboxylic acid containing a cyclic phosphine oxide.

[0033]

[Chemical 14]

Production Example 4. 214.2 g (1 molar equivalent) of the cyclic phosphinic acid compound of Chemical formula 15 was added, and further, 500 g of xylene and 1% by weight of benzoyl peroxide were added to the cyclic phosphinic acid compound. Next, maleic anhydride 11
7.7 g (1.2 molar equivalent) was added and reacted at 120 ° C. for 10 hours to obtain 285.2 g of dibasic carboxylic acid containing cyclic phosphine oxide.

[0035]

[Chemical 15]

Production Example 5. 228.2 g (1 molar equivalent) of the cyclic phosphinic acid compound of Chemical formula 16 was added, and further 500 g of xylene and 1% by weight of triethylamine were added to the cyclic phosphinic acid compound. Then itaconic acid 156.1
g (1.2 molar equivalent) was added, and the mixture was reacted at 120 ° C. for 5 hours to obtain 344.4 g of a cyclic phosphine oxide-containing dibasic carboxylic acid.

[0037]

[Chemical 16]

Production Example 6. 528.5 g (2 molar equivalents) of the cyclic phosphinic acid compound of Chemical formula 17 was added, and further, 1000 g of xylene and 0.5 wt% of triethylamine were added to the cyclic phosphinic acid compound. Then itaconic acid 31
2.2 g (2.4 molar equivalent) was added and reacted at 120 ° C. for 5 hours to obtain 765.5 g of a cyclic phosphine oxide-containing dibasic carboxylic acid.

[0039]

[Chemical 17]

Production Example 7. 232.2 g (1 molar equivalent) of the cyclic phosphinic acid compound of Chemical formula 18 was added, and further 500 g of toluene and 0.5% by weight of benzoyl peroxide were added to the cyclic phosphinic acid compound. Then maleic anhydride 1
17.7 g (1.2 molar equivalent) was added, and the mixture was reacted at reflux temperature for 5 hours to obtain 298.5 g of dibasic carboxylic acid containing cyclic phosphine oxide.

[0041]

[Chemical 18]

Production Example 8. 496.5 g (2 molar equivalents) of the cyclic phosphinic acid compound of Chemical formula 19 was added, and further 1000 g of toluene and 0.5% by weight of benzoyl peroxide were added to the cyclic phosphinic acid compound. Next, 235.3 g (2.4 molar equivalents) of maleic anhydride was added, and the mixture was refluxed at 5 ° C.
After reacting for a time, 610.3 g of a dibasic carboxylic acid containing a cyclic phosphine oxide was obtained.

[0043]

[Chemical 19]

Examples 1-10. 2500 g of dimethyl terephthalate, 1600 g of ethylene glycol, and 0.04% by weight of zinc acetate with respect to the dimethyl terephthalate were heated and reacted at a temperature of 150 to 230 ° C. for 120 minutes under normal pressure to cause a reaction. Then, the cyclic phosphine oxide-containing dibasic carboxylic acid shown in Production Examples 1 to 8 was added to the reaction system in a predetermined amount, and then the system temperature was changed to 275 ° C. for 100 minutes.
The temperature of the system is gradually reduced while gradually increasing the temperature to 0.1
mmHg, 54 at 275 ° C, 0.1 mmHg
Polymerization was continued for a minute to obtain a flame-retardant polyester resin. These properties and physical properties were measured, and the results are shown in Table 1.

[0045]

[Table 1]

[0046]

Since the reactive flame retardant of the present invention is a phosphine oxide having no P--O--C bond in the molecule, it sufficiently withstands a high reaction temperature during the production of a polyester resin and causes deterioration of hue. Moreover, since it is reactive, it does not cause the problem of volatilization during the reaction because it is reactive, and since it does not contain any hydrolyzable P--O--C bond at all, it has no wash resistance when used in polyester fiber. Is also excellent. Therefore, it can largely contribute to the expansion of the use of polyester resin fibers and films.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C08G 63/78 NMR 7107-4J C09K 21/12 8318-4H

Claims (1)

[Claims] 1. A main component is a cyclic phosphine oxide-containing dibasic carboxylic acid obtained by addition reaction of a cyclic phosphinic acid compound represented by the following general formula (1) with a dibasic unsaturated carboxylic acid or a lower alkyl ester thereof. A novel reactive flame retardant for polyester resins. [Chemical 1] (In the formula, R ₁ , R ₂ and R ₃ represent H, Cl, Br or a hydrocarbon group having 1 to 4 carbon atoms. X is NH, NR ₄ ,
O, CH ₂ , CO, SO ₂ , S, SO or C (CH ₃ )
₂ and R ₄ represents an alkyl group having 1 to ₄ carbon atoms or a benzyl group)