KR19990070137A - Manufacturing method of flame retardant polyester - Google Patents

Abstract

The present invention relates to the production of polyester, which is widely used as a molded article in clothing, beddings, interior materials such as automobiles, electrical and electronic fields, in particular, there is no generation of harmful gases to the human body during combustion and excellent in almost no deterioration of mechanical properties. It relates to a method for producing a flame retardant polyester having a flame retardant effect.

The present invention is a polycondensation reaction through an esterification reaction or an ester exchange reaction with an alkylene terephthalate as a main component to produce a polyester, the temperature of the specific phosphorus compound and acrylic acid or methacrylic acid during the reaction does not exceed 110 ℃ It is characterized in that the hydroxyphosphinyl propanoic acid derivatives obtained by the reaction at is added so that the content of the number of people in the final polyester is 0.05 to 10% by weight, the polyester produced by such a method is particularly flame retardant It is very useful when used in certain products that are excellent in flame retardancy.

Description

Manufacturing method of flame retardant polyester

The present invention relates to the production of a polyester having excellent flame retardancy, more specifically, in the production of polyester by adding a specific flame retardant compound and copolymerized together, there is no generation of harmful gases to the body during combustion and almost no deterioration of mechanical properties The present invention relates to a method for producing a flame retardant polyester having no excellent flame retardancy.

Polyesters containing polyethylene terephthalate as a main component have high crystallinity, high softening point, and have excellent mechanical and thermal properties, chemical resistance, and moldability, and are widely used as a molding material such as fibers or films. . However, since polyester is composed of only three elements of carbon, hydrogen, and oxygen, it is easy to burn, and in particular, textile clothing, curtains, bed covers, beddings such as duvets, automobiles, aircraft interior materials, and molded articles of electric and electronic products. Because of the high risk of fire when used in the fire retardant is required to inhibit the combustion effect in the event of a fire in order to prevent a large fire accident.

Until recently, various methods of imparting flame retardancy to polyester fibers or films which are easily combusted have been studied.A typical representative method of imparting flame retardancy is a post-processing method for treating halogen-based flame retardants during fabric salt processing and halogen or phosphorus compounds for polymerization There is a method to add. However, the method of post-treatment with a flame retardant has problems such as decommission of the flame retardant during washing and rubbing and generation of toxic gases such as dioxins in the event of fire, and the addition of halogen-containing compounds improves flame retardancy. However, not only the light resistance is severely lowered, but also the polyester is yellowed, and the compound containing it is inherently poor in thermal stability and has a disadvantage in that it is less reactive with polyester.

On the other hand, in the United States, Europe, etc., the use of halogen-based flame retardant fibers having a problem that dioxin occurs during combustion is being strengthened, the demand for flame retardant fibers that can prevent this is increasing.

Therefore, various methods for solving the above problems have been developed, and a method of adding a flame retardant such as halogen or phosphorus compounds when polymerizing a polymer by one method has been proposed. For example, JP 36-20771, JP 52-10351, JP 59-191716, JP 60-101144, and USP 4,033,936, USP 3,941,752, etc., after the polycondensation reaction proceeds to some extent, phenylphosphonic acid aliphatic glycol ester is used. Method to impart flame retardancy by polycondensation like reactive component of polyester, copolymerize to contain 15-60% of arylphosphonic acid monomer in advance, and then mix with existing polyester, add organic phosphorus compound during BHT reaction A method of preparing polyester by polycondensation and a method of imparting flame retardancy by adding an organic phosphorus compound such as magnesium and manganese to impart flame retardancy are known, but the process is complicated or substantially the residual rate of phosphorus compound Low polyesters exhibit satisfactory flame retardancy by applying these methods.

As a flame retardant used in flame retardant polyester, U.S. Patent Nos. 4,081,463, 4,169,782 and the like have been described for the preparation of hydroxyphosphinylpropinic acid derivatives. By reacting, the flame retardant jumps yellow, and when used as a fiber by copolymerizing it with polyester, there are disadvantages such as yellowness of the fiber.

The present invention has been made for the purpose of producing a polyester that exhibits excellent color and flame retardancy, a flame retardant poly with improved color by adding a flame retardant excellent in purity and color tone than the conventional phosphorus flame retardant and added in the polyester polycondensation reaction step It is for the purpose to manufacture ester.

The present invention is a polycondensation reaction through an esterification reaction or an ester exchange reaction with an alkylene terephthalate as a main component to prepare a polyester, during the reaction, the phosphorus dichloride compound of formula 1 and acrylic acid or methacrylic acid 110 It relates to the production of flame-retardant polyester, characterized in that the hydroxyphosphinylpropanoic acid derivative of the formula (2) obtained by reacting at a temperature not exceeding ℃ ℃ is added so that the content of the number of people in the final polyester is 0.05 to 10% by weight .

[Formula 1]

[Formula 2]

(Wherein R, R ₁ in formula 1,2 is methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl)

Hereinafter, the present invention will be described in detail.

The hydroxyphosphinylpropanoic acid derivative of the formula (II) used in the present invention is specifically 1.05 to 1.2 mol% of acrylic acid or meta more than the phosphorus dichloride compound after heating the phosphorus dichloride compound of formula 1 to 65 ~ 90 ℃ It is prepared by adding krylic acid at a temperature not exceeding 110 ° C. and reacting at least 100 minutes at a temperature of 100 ° C. or lower for a first reaction and then hydrolyzing it. In this case, when the reaction temperature exceeds 110 ° C when the phosphorus dichloride compound and acrylic acid are reacted, side reactions are generated by alteration of additives added to acrylic acid (methacrylic acid), resulting in yellowing or deterioration of general properties. Occurs.

As the first and second components used in the polyester polymerization, alkylene glycols having 2 to 6 carbon atoms and terephthalic acid or ester derivatives thereof may be used. As the third component, isophthalic acid, naphthalene, dicarboxylic acid, diphenyl dicarboxylic acid, etc. Aromatic dicarboxylic acids such as main acid, diphenyl ether dicarboxylic acid, p-hydroxy benzoic acid, hydroxy ethoxy benzoic acid and the like, and derivatives of which chlorine is substituted in the aryl group of these compounds or ester derivatives thereof, propanediol, chloropropanediol, Divalent alcohol, such as butanediol, cyclohexanediol, and cyclohexane dimethanediol, polyhydric alcohols, such as glycerin, polyol, such as polyethyleneglycol and polyglycol glycol, can be added at least one.

On the other hand, the compound of formula (2), which is a feature of the present invention, can be added at any stage of the polyester polymerization, but especially at the stage where a polyester precursor having a polymerization degree of 2 to 10 after the completion of the esterification reaction or the transesterification reaction is produced. It is good to add.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Synthesis Example 1

After adding 895 g of methyl phosphinic dichloride to the reactor, it was heated to 90 ° C. and 380 g of acrylic acid was added while maintaining the temperature not to exceed 100 ° C., and further reacted at 90 ° C. for 1 hour. The reacted primary reactant was hydrolyzed in 1 liter of water at a temperature of 80 ° C., and then cooled to 5 ° C. to obtain a slurry product, which was filtered, washed, and dried to yield 1,015 g of 2-carboxyphenylphosphinic acid (yield). 94.9%). The color tone of the synthesized 2-carboxymethylphosphinic acid was measured by using a color difference meter to measure sulfur-blue, and sulfur-blue was 0.3.

Synthesis Example 2

895 g of methylphosphinic dichloride was added to the reactor, heated to 90 ° C., and 380 g of acrylic acid was added while maintaining a temperature of 125 to 130 ° C., followed by further reaction at 100 ° C. for 1 hour. The reacted primary reactant was hydrolyzed in 1 liter of water at a temperature of 80 ° C., and then cooled to 5 ° C. to obtain a slurry product, which was filtered, washed, and dried to obtain 1,000 g of 2-carboxyphenylphosphinic acid (yield). 93.5%). The color tone of the synthesized 2-carboxymethylphosphinic acid was measured using a color difference meter to measure sulfur-blue, and the sulfur-blue was 8.7.

Example 1

10 kg of dimethyl terephthalate and 4.8 kg of ethylene glycol were added to the reactor, and 5 g of manganese acetate was used as a catalyst to react until the reaction temperature reached 235 ° C to prepare an oligomer (BHET). 5 g of antimony trioxide, 40 g of titanium dioxide, and 510 g of 2-carboxymethylphosphinic acid synthesized in Synthesis Example 1 were added as a polycondensation catalyst, stirred for about 20 minutes, and transferred to a polycondensation reactor to 1 mmHg over 45 minutes. Under high vacuum, condensation polymerization was carried out for 5 hours until the reaction temperature reached 280 ° C. The inherent viscosity of the polymer was 0.653. The synthesized polyester was chipped, spun and stretched at a spinning temperature of 250 to 280 ° C. to produce 1.4de of fiber.

Example 2

A flame-retardant polyester was prepared in the same manner as in Example 1 except that 765 g of 2-carboxymethylphosphinic acid of Synthesis Example 1 was added to prepare 1.4de of fiber.

Comparative Example 1

A flame retardant polyester was prepared in the same manner as in Example 1 except that 510 g of 2-carboxymethylphosphinic acid synthesized in Synthesis Example 2 was added instead of the compound synthesized in Synthesis Example 1, thereby preparing 1.4de of fiber.

Comparative Example 1

A flame-retardant polyester was prepared in the same manner as in Example 1 except that 2-carboxymethylphosphinic acid was not used, and 1.4de of fiber was prepared.

The physical properties and flame retardancy test results of the polymer synthesized in Examples and Comparative Examples are shown in Table 1 below. The intrinsic viscosity was measured at 25 ° C. using a chlorophenol solution, and the hue was measured using a color difference meter (L) and sulfur-blue (b). Flame retardance evaluated flame retardancy by measuring the number of contact by the 45 degree coil method by JISL1091D.

TABLE 1

Item Example 1 Example 2 Comparative Example 1 Comparative Example 1 I.V. (dl / g) 0.653 0.651 0.651 0.652 Tint (L / b) 73.1 / 2.1 73.4 / 2.0 72.3 / 8.5 73.1 / 4.1 Flame retardant 4 5 4 One

As can be seen from the above examples and comparative examples, the polyester produced according to the present invention has excellent physical properties such as intrinsic viscosity and color tone, as well as excellent flame retardancy, so that interior materials such as clothing, beddings, automobiles, electric / electronics It is very useful when used as a molded article in the field.

Claims (3)

Polyester condensation reaction is carried out by esterification reaction or ester exchange reaction using alkylene terephthalate as a main component, and during the preparation of polyester, phosphoric dichloride compound of formula 1 and acrylic acid or methacrylic acid do not exceed 110 ° C. A method for producing a flame-retardant polyester, characterized in that the hydroxyphosphinylpropanoic acid derivative represented by the following Chemical Formula 2 obtained by reacting at a temperature is added so as to have a content of 0.05 to 10% by weight of the phosphorus in the final polyester. [Formula 1] [Formula 2] (R, R ₁ is hydrogen, methyl, phenyl, halophenyl, alkyl, haloalkyl or haloaryl) The method of claim 1, wherein the compound of Formula 2 is a temperature of not more than 110 ° C of 1.05 1.2 mole% excess acrylic acid or methacrylic acid after heating the phosphorus dichloride compound of Formula 1 to 65 ~ 90 ℃ The flame-retardant polyester production method characterized in that it is prepared through a process of reacting at least 100 minutes or less at a temperature of 100 ℃ or less and the first reaction and then hydrolyzed it. The method of claim 1, wherein the hydroxyphosphinylpropanoic acid derivative of the formula (2) is produced by flame retardant polyester, characterized in that in the step of producing a polyester precursor of the polymerization degree 2 to 10 by esterification reaction or transesterification reaction Way.