KR19980068294A - Manufacturing method of flame retardant polyester - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of polyester fibers, which are commonly used as molding materials, such as fibers or films, and which have recently been used in interior materials, such as automobiles and aircrafts.

In the present invention, the hydroxyphenylphosphinylpropanoic acid derivative compound having a specific structure during the preparation of polyester is subjected to direct esterification reaction or ester exchange reaction, whereby a polyester precursor having a polymerization degree of 2 to 10 is produced and polycondensed. The present invention relates to a flame retardant polyester production method characterized by polycondensation at high polymerization in the presence of a catalyst, wherein the flame retardant polyester thus prepared exhibits excellent flame retardancy while maintaining physical properties of a conventional polyester resin.

Description

Manufacturing method of flame retardant polyester

The present invention relates to a method for producing a polyester having excellent flame retardancy by adding and copolymerizing a polyester polycondensation reaction using an aryl phosphonic acid derivative containing phosphorus, nitrogen and bromine atoms, which are flame retardant components.

Polyester based on polyethylene terephthalate has a high crystallinity, high softening point, and excellent strength, chemical resistance, and light resistance, and thus has occupied an industrially important position as a molding material such as fiber or film. There is a disadvantage that the combustion.

However, in recent years, there is an increasing demand for fibers having flame retardancy to prevent the risk of fire in beddings such as curtains, bed covers, duvets, textiles, clothing, automobiles, and aircraft interior materials, and applied to electrical and electronic products. There is an increasing demand for flame retardant films. Conventionally, post-processing methods for treating halogen-based flame retardants during fabric salt processing and adding halogen or phosphorus compounds as flame retardants during polymerization have been mainly used.

The post-treatment method with flame retardant has problems such as the flame retardant is removed during washing and rubbing, and the flame retardancy is reduced or toxic gas such as dioxins are generated in the case of fire, and the method of adding halogen-containing compound during polymerization improves flame retardancy. However, not only the light resistance is severely lowered, but the polyester has a disadvantage of discoloring to yellow, and the compound containing the same has a disadvantage of inherently poor thermal stability and less reactivity with polyester. Further, in the United States and Europe, the use of halogen-based flame retardant fibers having a problem of generating dioxin during combustion is being strengthened, and thus the demand for flame retardant fibers that can prevent them is increasing.

As a method for solving this problem, JP 36-20771, JP 52-10351, JP 59-191716, JP 60-101144, and USP 4,033,936 have been proposed. These methods include polycondensation of phenylphosphonic acid dialkyl esters or phenylphosphonic acid aliphatic glycol esters with the reactive components of polyester to impart flame retardancy, and copolymerize arylphosphonic acid monomers in advance to contain 15 to 60%. There is a method of blending into the ester, a method of adding the organophosphorus compound during the BHET reaction and polycondensation thereof to prepare a polyester and a method of imparting flame retardancy by adding an inorganic phosphor such as magnesium manganese and an organophosphorus compound to impart flame retardancy, However, there are few polyesters that show satisfactory flame retardancy by applying these methods because the process is complicated and the phosphorus residual rate is substantially low.

The present invention is to copolymerize the flame retardant containing phosphorus and bromine having a flame retardancy in the manufacture of polyester in order to improve this problem while maintaining the physical properties of the polyester fiber to prevent the loss of the flame retardant during washing is given permanent flame retardancy and magnetic It is an object of the present invention to provide a method for producing a flame retardant polyester having excellent digestibility.

The present invention relates to a method for producing a flame retardant polyester having excellent color tone, transparency, and excellent flame retardancy while having low physical properties during polyester production using the compound of the following general formula (I) as a flame retardant.

Wherein R is selected from hydrogen, methyl, phenyl, alkyl, haloalkyl, haloallyl, and the substituents of alkyl, haloalkyl and haloaryl groups include 1 to 5 alkyl groups, metal sulfonate groups and 1 carbon atoms Amine groups having 6 to 6, etc.)

In the present invention, the addition time of the hydroxy phenylphosphinylpropanoic acid derivative of the formula (I) is not particularly limited, but in the step of producing a polyester precursor having a polymerization degree of 2 to 10 by direct esterification or transesterification It is preferable to add the polycondensation with high polymerization in the presence of the polycondensation catalyst, and the amount of the phosphorus and bromine atoms in the final polyester is preferably 0.2 to 5.0% by weight.

In the present invention, the first and second components used in the polyester polymerization may be alkylene glycols having 2 to 6 carbon atoms and terephthalic acid or ester derivatives thereof, and the third component isophthalic acid, naphthalene dicarboxylic acid, diphenyl, etc. Aromatic dicarboxylic acids such as dicarboxylic 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-forming derivatives thereof, propane diol, chloro Compounds such as dihydric alcohols such as propanediol, butane diol, cyclohexanediol, cyclohexane dimethanediol, polyhydric alcohols such as glycerin, polyols such as polyethylene glycol, polyglycol glycol and the like can be used.

In the present invention, antimony trioxide is mainly used as a polymerization catalyst, and the catalyst may exhibit a synergistic effect of flame retardancy even when a small amount is added by acting together with a person atom, a bromine atom or a nitrogen atom in the flame retardant compound of general formula (I). .

The flame retardant compound of general formula (I) used in the present invention reacts phosphorus dichloride with acrylic acid, adds an acetic anhydride and removes the solvent to synthesize 3-hydroxyphosphinylpropanoic acid, and the divalent equivalent of R ₃ . It is obtained by heating reaction after adding 1 equivalent of alcohol.

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

Synthesis Example

After reacting phosphorus phenyl dichloride with acrylic acid, an excess of acetic anhydride was added and the solvent was removed to synthesize 3-hydroxyphenylphosphinylpropanoic acid. Thus, a compound containing phosphorus, nitrogen and bromine atoms was added by adding 1 equivalent of a dihydric alcohol compound reacted with an S-triazine group containing two bromine atoms at position 5 of diethylene glycolyl isophthalate. 5- (3 ', 5'-bromotriazinyl) -isophthaloylhydroxyethyl] hydroxyphenylphosphinylpropionate was synthesized.

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). 4.6 g of trimethyl phosphate as a heat stabilizer, 5 g of antimony trioxide, 40 g of titanium dioxide as a polycondensation catalyst, and 448 g of flame retardant compound synthesized in the synthesis example were added, stirred for about 20 minutes, and then transferred to a polycondensation reactor. Condensation polymerization was carried out for 5 hours after the reaction temperature was raised to 280 ° C under reduced pressure in a high vacuum state of 1 mmHg in minutes. The intrinsic viscosity of the produced polymer was 0.653. The synthesized polyester was chipped, spun and spun at a spinning temperature of 250 to 280 ° C. to prepare 1.4de of fiber, and the physical properties thereof were shown in Table 1 below.

Example 2

In Example 1, except that 597g of the compound of Synthesis Example was added, it was carried out in the same manner as in Example 1, and the physical properties thereof were shown in Table 1.

Example 3

In Example 1, except that 747g of the compound of Synthesis Example was added, the same process as in Example 1 was carried out, and the physical properties thereof were shown in Table 1 below.

Example 4

In Example 1, except that 896g of the compound of Synthesis Example was added, the same procedure as in Example 1 was carried out, and the physical properties thereof were shown in Table 1 below.

Comparative Example 1

In Example 1, except that 139g of 3-hydroxyphenylphosphinylpropanoic acid was added instead of the compound of Synthesis Example, it was carried out in the same manner as in Example 1, and the physical properties thereof were shown in Table 1 below.

In Table 1, the intrinsic viscosity was measured at 25 ° C. using a chlorophenol solution, and the hue was measured using a colorimeter (L) and sulfur-blue (b). DEG also quantifies diethylene glycol in the backbone and expresses diethylene glycol in mole% (denoted in deg%) relative to the total glycol. 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 Example 3 Example 4 Comparative Example 1 Flame Retardant Input 448 597 747 896 139 I.V. (dl / g) 0.653 0.657 0.651 0.660 0.640 Hue (L / b) 73.1 / 4.1 73.9 / 4.7 73.4 / 4.0 74.7 / 5.2 72.3 / 3.5 DEG 1.13 1.02 1.15 1.18 1.12 Flame retardant 3 4 4 5 4

As can be seen from the above examples and comparative examples, the flame retardant polyester produced by the present invention exhibits excellent flame retardancy with little effect on other properties by using the flame retardant compound of the general formula (I). It can be usefully used for fibers or films.

Claims (3)

A method for producing a flame retardant polyester, characterized in that the copolymerization is carried out by adding a hydroxyphenylphosphinylpropanoic acid derivative compound of the following general formula (I) to prepare a polyester mainly composed of alkylene terephthalate. (Wherein R is selected from hydrogen, methyl, phenyl, alkyl, haloalkyl, haloaryl, and as substituents of alkyl, haloalkyl, haloaryl groups, C1-5 alkyl, metal sulfonate, C1-6 Amine groups having dogs) The method for producing a flame retardant polyester according to claim 1, wherein the hydroxyphenylphosphinylpropanoic acid derivative compound is added at a stage in which a polyester precursor having a polymerization degree of 2 to 10 is produced by direct esterification or transesterification. . The method for producing a flame retardant polyester according to claim 1, wherein the hydroxyphenylphosphinylpropanoic acid derivative compound is used so that the content of phosphorus and bromine atoms in the final polymer is 0.05 to 10.0% by weight.