DE102007056179A1 - A process for producing a flameproof polyester polymer, polyester polymers prepared therefrom and fibers made using the polyester polymer - Google Patents

Abstract

There is provided a process for producing a flameproof polyester polymer by introducing a phosphorus flame retardant represented by Chemical Formula 1 into a first esterification reaction such that the amount of phosphorus relative to the polymer is 500 to 50,000 ppm and adding a manganese salt and a phosphorus compound, both of which are UV stabilizers, in a second esterification reaction such that the amount of manganese and phosphorus is 0.1 to 500 ppm, a polyester polymer prepared by this method, and a polyester fiber made using the polyester polymer. The polyester polymer and the polyester fiber each have permanent flame retardant properties and excellent UV stability.

Description

[Title of the invention]

method for producing a flameproof polyester polymer, made therefrom Polyester polymers and produced using the polyester polymer fibers

[Description of the drawing]

1 FIG. 10 is a schematic process view according to an embodiment of the present invention. FIG.

<Description of the elements in the drawing>

1

 suspension apparatus

2

 storage container for the suspension

3

 first Esterification Reactor (DE-1)

4

 first filter

5

 second Esterification Reactor (DE-2)

6

 second filter

7

 polycondensation

8th

 pelletizer

[Technical area]

The The present invention relates to a process for producing a Polyester polymer and produced using this method Polymers and fibers, in particular a process for the preparation of a flame-resistant polymer in that one produced by this method Polyester polymer and one using the polyester polymer produced polyester fiber one below by the chemical Formula 1 phosphorus-containing flame retardant in one first esterification reaction is added so that the Amount of phosphorus based on the polymer is 500 to 50,000 ppm, and that subsequently a manganese salt and a phosphorus compound, of which each substance is a UV stabilizer, in a second Esterification reaction can be added so that the amount both manganese and phosphorus are 0.1 to 500 ppm, and a polyester polymer prepared by this method, and a polyester fiber made using the polyester polymer.

[State of the art]

Usually is polyester, in particular polyethylene terephthalate (hereinafter referred to as PET), widely used for fibers, films, engineering plastics u. Like. Used as it has excellent mechanical Properties and good chemical resistance having. However, such a conventional polyester is disadvantageous because it is easily flammable. Lately, the editions have been for clothes, such as B. clothes for toddlers u. Like., And industrial textiles, such. B. car covers, Curtains, carpets and more. Like., By appropriate laws strictly regulated. Therefore, the demand for flame-resistant fibers increases Avoid fires.

Methods of imparting flame-resistant properties to a polyester are as follows. First, a method is known, after which the surface of the fiber is treated with a flame retardant. Although this method allows a cost-effective production, but is problematic in terms of durability. Second, a method is known whereby a flame retardant material is added to the fiber while it is being spun. In this method, according to one embodiment, a flame retardant material, ie, a flame retardant, is mixed with the fiber and the fiber is then spun, and according to another embodiment, a flameproof masterbatch with an excess is added Amount of flame retardant mixed and the masterbatch then spun. Of these two embodiments, the former is problematic in that spinnability is lowered and, moreover, physical properties of raw yarn are deteriorated, and the latter is troublesome in that it is difficult to make the flame-resistant masterbatch a polymer having desired physical properties in terms of, for example, viscosity , Color, etc., to produce. Third, a method is known in which a flame retardant material is added to the fiber and then the flame retardant material is copolymerized with the fiber at the time of spinning. This process has the advantage that the durability is good and it is similar to conventional processes for polyester production. In this third method, which is used for the production of flame-resistant polyester by copolymerization, mainly a halogen-containing flame retardant, in particular a flame retardant containing bromine (Br), and a flame retardant containing phosphorus (P) are used.

From the Japanese Patent Publication Sho62-6912 . Sho53-46398 and Sho51-28894 is a bromine-containing flame retardant known. Here, a large amount of flame retardant must be added to achieve effective flame retardant properties since the bromine compound is easily pyrolyzed at high temperatures. This causes problems because the color of the polymer deteriorates during combustion and the light resistance decreases and also toxic gases.

Furthermore, it is off US 3941752 . US 5399428 and US 5180793 as well as the Japanese Patent Laid-Open Publication No. Sho50-56488 and Sho52-47891 a phosphorus-containing flame retardant known. When the physical properties of a flame resistant polyester prepared by using this phosphorus flame retardant were studied by the inventors of the present invention, it was found that the physical properties of the flame resistant polyester thus produced were greatly deteriorated. Further, in most processes for producing PET using the phosphorus flame retardant, there is a problem that the process for producing PET by polymerization of dimethyl terephthalate (hereinafter referred to as DMT) as a raw material costs more than the process for producing PET by polymerizing Terephthalic acid (hereinafter referred to as TPA) as a starting material.

[Presentation of the invention]

[Technical problem]

Accordingly The present invention will be understood in consideration of the above Problems of the prior art proposed with the task of a process for producing a polyester polymer, the permanent Flame retardant properties and excellent UV resistance (Resistance to ultraviolet rays), provide.

It is also an object of the present invention, an after polyester polymer prepared by this method and one using to provide the polyester polymer produced polyester fiber.

[Technical solution[

worin R¹ Wasserstoff oder eine Hydroxyalkylgruppe mit 1 bis 10 Kohlenstoffenatomen, R² Wasserstoff, eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine Arylgruppe mit 6 bis 24 Kohlenstoffatomen und R³ Wasserstoff, eine Alkylgruppe oder eine Hydroxyalkylgruppe mit 1 bis 10 Kohlenstoffenatom oder eine zur Bildung eines Esters geeignete funktionelle Gruppe darstellen.In order to achieve the above objects, according to one aspect of the present invention, there is provided a process for producing a flameproof polyester polymer using terephthalic acid, which comprises preparing a suspension of terephthalic acid (TPA) and ethylene glycol (EG) as a reactant, that this suspension is introduced into a first esterification reactor to form an oligomer in a first esterification reaction such that the oligomer formed in the first esterification reaction is introduced into a second esterification reactor to produce a flame resistant oligomer such that a phosphorus containing compound represented below by Chemical Formula 1 Flame retardant is introduced so that the amount of phosphorus based on the polyester polymer is 500 to 50,000 ppm, that a manganese salt and a phosphorus compound, both of which are UV stabilizers, are added so that the amount of manganese sow Each of phosphorus is 0.1 to 500 ppm, for carrying out a second esterification reaction, and that an oligomer formed in the second esterification reaction is introduced into a polycondensation reactor and polycondensed there.

wherein R ^{1 is} hydrogen or a hydroxyalkyl group having 1 to 10 carbon atoms, R ^{2 is} hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms and R ^{3 is} hydrogen, an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms or a to Formation of an ester suitable functional group.

in the The present invention will now be described with reference to the appended drawings Drawing described in more detail.

1 FIG. 10 is a schematic process view according to an embodiment of the present invention. FIG. According to 1 For example, there is a step of producing a suspension from a step of preparing the suspension using terephthalic acid and ethylene glycol as reactants in a suspension apparatus 1 , In the stage of suspension production, a storage tank for the suspension may be provided.

A first esterification step consists in that the suspension is introduced into a first esterification reactor and there an oligomer is formed using the suspension. The first esterification reactor 3 always stores a base oligomer as a product. In a transfer line for the transport of the first esterification reactor 3 formed oligomer to a second esterification reactor 5 can be a first filter 4 be provided. The filter 4 can be designed as a basket filter.

A second esterification step consists in that the oligomer formed in the first esterification stage in a second esterification reactor 5 passed over and formed there a flame-resistant oligomer. In the second esterification step, a phosphorus-containing flame retardant, which is represented by Chemical Formula 1 below, is added so that the amount of phosphorus based on the amount of the polyester polymer is 500 to 50,000 ppm. Subsequently, a manganese salt and a phosphorus compound are added so that the amounts of manganese and phosphorus are 0.1 to 500 ppm, respectively.

A second filter 6 can in a transfer line for the transport of the second esterification reactor 5 formed oligomer to a polycondensation reactor 7 be provided. The filter 6 can be designed as a basket filter.

A Polykondensationsstufe is that in the second esterification stage transported oligomer transported and the transported oligomer is polycondensed under high vacuum.

Here is a pelleting machine 8th be provided for the production of pellets from the polymer produced.

method for the production of bishydroxyethyl terephthalate and its oligomers with low degree of polymerization by immediate reaction of Reactants terephthalic acid (TPA) and ethylene glycol (EG) and subsequent polycondensation under high vacuum are known per se in the art. However, a polyester polymer to produce permanent flame-resistant properties, according to the invention a Method for producing a flameproof polyester polymer provided which consists in that a phosphorus-containing flame retardant of the chemical formula 1 given above in the second esterification step is introduced into a polyester polymer, and that a manganese salt and a phosphorus compound, both of which are UV stabilizers are so introduced into a second esterification reaction be that the amount of manganese and phosphorus each 0.1 to 500 ppm.

The characteristic configuration of the present invention will be described in more detail below.

1. Selection of a flame retardant

When Result of the general considerations of physical Properties, such as safety for the environment, flame retardant properties, conducting the polymerization, Production costs, flame-retardant behavior of flame-resistant yarn u. Like., It was festgtellt that the phosphorus-containing flame retardant the above-mentioned chemical formula 1 as a flame retardant in Appropriate sense of the present invention.

There the phosphorus-containing flame retardant a large amount Phosphorus relative to its molecular weight, it may be a develop sufficient flame retardant effect and also ensure a favorable process stability. Furthermore, soot and toxic gases in small quantities produced because the phosphorus-containing flame retardant a small number on aromatic groups compared to the conventional ones Flame retardants containing a phosphaphenanthrene group, having.

2. Determination of the polymer to be introduced Amount of phosphorus-containing flame retardant.

The Inventors of the present invention have various tests for Determination of the quantity of phosphorus to be introduced into the polymer Flame retardant carried out. It was recognized that the in the polymer to be introduced amount of phosphorus-containing Flame retardant regardless of the structure of the phosphorus-containing Flame retardant of the above chemical formula 1 preferably 500 up to 50,000 ppm. In particular, it was found that the amount of phosphorus-containing flame retardant added based on the amount of the polymer under consideration the processability of the polymer and the production of raw yarn more preferably 1000 to 20,000 ppm. Lies the amount of phosphorus-containing flame retardant based on the Polymer below 500 ppm, so is not a desirable flame retardant Effect to be expected. In contrast, it is over 50,000 in quantities ppm, the produced polyester to a high degree of polymerization to polymerize, and it is difficult, the polymer thus prepared to process fibers because the crystallinity of the polymer is disadvantageously excessively reduced.

3. Procedure for introduction of the phosphorus-containing flame retardant in the reactor

The Process for the introduction of a phosphorus-containing flame retardant The above-mentioned chemical formula 1 in a reactor are each different according to state of aggregation of the phosphorus-containing flame retardant. Is the phosphorus-containing flame retardant of the above chemical Formula 1 is a solid, so it may be in the reactor in the form of a Solution in ethylene glycol (EG) or as a dispersion phase in ethylene glycol (EC). Is this phosphorus-containing Flame retardant of the above-mentioned chemical formula 1 a Liquid, it may be directly or in the form of a mixed Solution of EC and the phosphorus-containing flame retardant be introduced into the reactor. Will the phosphorus-containing Flame retardant as a solution in ethylene glycol (EG) or introduced into the reactor as a dispersion phase in ethylene glycol (EG), so the amount of EG is preferred according to the following mathematical Formula 1 calculated.

Mathematical Formula 1

• 0.2 x FR (g) · (FN FR · 62) / (MW FR )·(1 + α) ≤ EG (g) ≤ 3 · FR (G) * (FN FR · 62) / (MW FR )·(1 + α),
• wherein FR is the flame retardant, FN _{FR is} the number of carboxylic acid groups in 1 mole of the flame retardant, MW _FR (g / mol) is the molecular weight of the flame retardant and α is a constant number, where α is 1 when the flame retardant is solid, and 0 is when the flame retardant is liquid.

is the reaction rate of transferred to a second esterification reactor Oligomers 95% or more, so is the acid number of the oligomer low and can therefore be neglected. Is against the reaction rate of the oligomer is below 95%, then EG added according to the acid number of the oligomer and the amount of added EC should be the following mathematical formula 2 depending on the acid number of the oligomer meet.

Mathematical Formula 2

• AV oligomer · 31/1000 ≤ EG (g) ≤ AV oligomer · 62/1000,
• wherein AV _{oligomer represents} the acid number of the oligomer, wherein the acid number is given in units of (KOH equivalent) / (1 kg polymer).

If the amount (g) of EG added at the time of introduction of the flame retardant is less than FR (g) · (FN _FR · 62) / (MW _FR ) · (1 + α), the viscosity of the flame retardant is increases, and it is therefore difficult to introduce the flame retardant into the reactor and esterify it. On the other hand, if the amount (g) of EG added at the time of introduction of the flame retardant is more than FR (g) * (FN _FR * 62) / (2 * MW _FR ) * (1 + α), then Flame retardants are introduced with ease, However, the DEG is increasingly formed and the heat resistance is thus reduced.

4. Adjustment of the amount of diethylene glycol (hereinafter referred to as DEG)

In a process for producing a polyester polymer using There is a problem with TPA when the amount of DEG increases because, as a result, the heat resistance of the polymer is reduced. As the formation of DEG increases with acidity the reactant increases are methods of reduction the acidity of the same.

The inventors of the present invention have attempted to reduce acidity by introducing alkaline materials into a second esterification reactor 5 according to 1 or by introducing a phosphorus compound of the above-mentioned Chemical Formula 1 into the reactor. From this, it was recognized that the latter approach is advantageous in terms of quality stability. However, it is still within the scope of the present invention conceivable that alkaline material in a first esterification reactor 3 or in a second esterification reactor, or alkaline material is added to the phosphorus compound of Chemical Formula 1 given above.

If the phosphorus compound of the above chemical formula 1 in the second esterification reactor 5 according to 5 is introduced, the amount of DEG with respect to the polymer is preferably reduced to 3% by weight and then kept constant to prevent deterioration of the physical properties of the produced polyester polymer and to cause easy spinning, false twisting, dyeing, and the like. Like. Without problems to allow.

The phosphorus compound of the above chemical formula 1 is introduced into the storage tank 2 for the suspension or a first esterification reactor 3 The problem is that the acidity of the reactants increases and therefore the amount of DEG increases continuously.

5. Selection of a UV stabilizer

There flame retardant polyester fibers for indoor use, such as For example, curtains, used is a good one UV stability necessary. Therefore, the inventors of the present Invention researched the UV stability. Organic and inorganic Stabilizers are commonly used as UV stabilizers but the inventors of the present invention have found that that manganese phosphate is best in terms of function and cost UV stabilizer can be used.

Indeed It was found that manganese phosphate was insoluble in EC at the time of introduction to the reaction system coagulates with the result that impurities in large Quantities are formed in the polymer and thereby the spinning pressure for Time of spinning is rising. Accordingly, the inventors have different ones Process for forming manganese compounds in a polymerization system tested. As a result, it has been found that the above Problem due to the separate introduction of a manganese salt and a phosphorus compound can be solved.

Of Further, the amount of manganese should be used in the UV stabilizer Manganese salt based on the amount of the polymer 0.1 to 500 ppm, preferably 0.2 to 200 ppm. Is the amount of manganese in the manganese salt below 0.1 ppm, this leaves the desired UV stability difficult to reach. On the other hand, is the amount over 500 ppm, the dispersibility decreases so that the spinning pressure at the time of spinning increases.

Of Further, the amount of phosphorus in the phosphorus compound, the is introduced together with the manganese salt, based on the amount of the polymer is 0.1 to 500 ppm, preferably 0.2 to 200 ppm. The phosphorus compound can be added as long such as the reaction of the phosphorus compound with the manganese salt remains problematic. Is the amount of phosphorus compound more than 500 ppm, however, the activity decreases of the catalyst and conducting the polymerization difficult.

6. Additional introduction of monomers for the purpose of copolymerization

Monomers for copolymerization are commonly used to impart various functions to the polyester polymer. The monomers for the copolymerization can also be used to impart various functions to a flameproof polyester polymer according to the invention hen. Monomers for copolymerization which can be used according to the invention include dicarboxylic acid, its ester-forming derivatives and glycols.

When Dicarboxylic acid and its ester-forming derivatives can aromatic dicarboxylic acids, such as, for example, isophthalic acid, Biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and the like Like. And their esterbildene derivatives; alicyclic dicarboxylic acids, such as 1,4-cyclohexanedicarboxylic acid and the like etc .; and alkyl dicarboxylic acid with 2 to 6 carbon atoms and their ester-forming derivatives or their acyl chloride are used.

Around a severe impact on economic efficiency and the physical properties of the flame resistant polyester polymer To avoid, the molar ratio of terephthalic acid should be to the total dicarboxylic acid 70% or more. Lies the molar ratio is below 70%, so is the melting point or the glass transition temperature of the flameproof polyester polymer too low, so that the moldability of the same is more difficult. On On the other hand, production costs increase disproportionately when expensive monomers are used for the copolymerization.

The Glycols can alkanediols, such as 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like. etc .; alicyclic glycols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like etc .; aromatic glycols, such as Bisphenol A, bisphenol S u. etc .; and ethylene oxide or propylene oxide adducts with aromatic diols. So that the flame-resistant polyester polymer has the appropriate physical properties, should Molar ratio of ethylene glycol to the total polymer glycol 70%.

7. The molar ratio of glycol including EC to dicarboxylic acid including TPA for improving the reactivity in the reactor

The Molar ratio of glycol to dicarboxylic acid (glycol / dicarboxylic acid) should be in the range of 1.01 to 2.0. Is the molar ratio less than 1.01, problems occur that are noticeable that the esterification reaction between the glycol and the dicarboxylic acid not easily feasible will that the reaction speed decreases, as a large amount of unreacted Dicarboxylic acid is located in the reactor that increases the time span for the filter change during the polymerization shortens the optical properties, such as Transparency, veil u. Like. Worsen, because the unreacted Dicarboxylic acid acts as an impurity, and thereby a rapid increase in spinning pressure during polymerization can be observed. If the molar ratio is greater as 2.0 problems occur, which are noticeable in that because of a possible overflow of capacity a reflux apparatus the leadership of the process is difficult and the post-treatment of the polymer with difficulty because of the DEG, which is a reduction in heat resistance of the polymer and the products, in large quantities is produced.

8. Catalyst for the polycondensation

The Catalysts suitable for conventional polyester polymerizations can also be used as a catalyst for the polycondensation can be used. Antimony compounds, like For example, antimony trioxide, antimony triacetate u. Like., And titanium compounds, such as titanium tetrabutylate, titanium tetraisopropylate, and the like. the like., can be used as catalysts for the polycondensation be used.

The Amount of metal in the polycondensation catalyst based on the Amount of the polymer should be 10 to 1000 ppm. Is this Amount below 10 ppm, so is the activity of the catalyst too low, while in a crowd bigger when 1000 ppm of the catalyst leads to the formation of impurities, thereby increasing the manufacturing cost of the polyester polymer.

9. Additives

Various Additives may vary depending on the purpose of the application Polyester polymer can be added to this flame resistant Polyester polymer produce. In particular, inorganic Metal salts, such as cobalt acetate u. Like., And organic Pigments are used as colorants to match the color of the polyester polymer to improve. Furthermore, 100 to 30,000 ppm of titanium dioxide or Added 100 to 30,000 ppm of silica or barium sulfate when the polyester polymer is to be used as a fiber. The inorganic additive may be used in conventional amounts according to customary Procedures are added, as is the case with the application of polyesters for the production of fibers is known.

in the In the following, the present invention will be described in detail by way of examples described. However, the present invention is not on these examples are limited.

In front The description of the examples is intended to be a method of evaluation of the behavior of the examined fiber.

Intrinsic Viscosity Number (Intrinsic Viscosity) (IV):

The Intrinsic viscosity is measured using a Ubbelohde viscometer after dissolving a fiber in a solution of phenol in admixture with 1,1,2,2-tetrachloroethane in a weight ratio measured by 6: 4.

Melting point (T _m ):

Of the Melting point is measured with a Differential Scanning Calorimeter (DSC-7) from the company Perkin Elmer Corp. measured.

DEG:

The DEG is gas chromatographed after decomposition of the polymer with triethanolamine certainly.

Color of the polymer:

The L, a and b values are measured using an automatic color difference meter measured.

UV stability:

The UV stability is determined by means of the preservation ratio of the intrinsic viscosity by applying the prepared polymer to a glass plate and irradiating for 48 hours the UV rays of a QUV from Q-Panel Corp. and then its intrinsic viscosity is measured, where, under conservation ratio, the ratio (Input limiting viscosity minus output limiting viscosity after irradiation) / (input limiting viscosity) × 100 to understand.

Properties of the flame retardant:

The Properties of the flame retardant are determined by determining the Oxygen limit (limited oxygen index, LOI) after knitting a fiber.

example 1

A suspension was made from 1300 kg TPA and 560 kg EG. The resulting suspension was placed in a DE-1 reactor 3 in which 1.5 tons of bishydroxyethyl terephthalate and a low molecular weight oligomer thereof are stirred at a temperature of 260 ° C for 3 hours while keeping the temperature of the DE-1 reactor at 260 ° C. The introduced suspension was heated to reflux and stirred simultaneously for 30 minutes, whereby the esterification ratio of the suspension reached 97%. From the oligomer produced, 1.5 tons of oligomer remained in the DE-1 reactor 3 while the remaining oligomer in a DE-2 reactor 5 was conducted. 68 kg of a flame retardant of the abovementioned chemical formula 1, wherein R ^{1 is} hydrogen, R ^{2 is} a phenyl group and R ^{3 is} hydrogen, and 68 kg of EG were mixed and introduced into the DE-2 reactor at room temperature. Further, manganese acetate, which is a manganese salt for producing a UV stabilizer, was placed in the DE-2 reactor 5 so that the amount of manganese in the manganese acetate based on the amount of the polymer was 22 ppm. As the phosphorus compound, phosphoric acid was also added so that the amount of phosphorus in the phosphoric acid based on the amount of the polymer was 100 ppm, and titanium dioxide serving as a matting agent was added so that the amount of titanium dioxide would be 0 based on the amount of the polymer , 3 wt .-%, and these additives were stirred at a temperature of 260 ° C. Subsequently, the whole was in the DE-2 reactor 5 contained oligomer is passed into a polycondensation reactor. Then 200 g of a 2 wt .-% solution of antimony trioxide in EG were introduced into the polycondensation reactor. Subsequently, the product thus obtained was polycondensed by conventional polycondensation to form a flame-resistant polyester polymer. The process for producing the flame-resistant polyester polymer was repeated 5 times. The average values and the spread of the analysis results of the obtained flame-resistant polyester polymer are shown in Table 1.

Comparative Example 1

A suspension was prepared from 68 kg of a flame retardant of the formula 1 given above, wherein R ^{1 is} hydrogen, R ^{2 is} a phenyl group and R ^{3 is} hydrogen, 1300 kg of TPA and 560 kg of EG. The resulting suspension was placed in a DE-1 reactor 3 in which the oligomer having the same composition as the polymer was stirred at a temperature of 260 ° C for 3 hours while maintaining the temperature of the DE-1 reactor at 260 ° C. The introduced suspension was heated to reflux and stirred simultaneously for 30 minutes, whereby the esterification ratio of the suspension reached 96.7%. From the oligomer produced remained 1.5 tons of oligomer in the DE reactor 3 and the remainder of the oligomer was passed to a DE-2 reactor. Subsequently, manganese acetate, which is a manganese salt for producing a UV stabilizer, was placed in the DE-2 reactor 5 As the phosphorus compound, phosphoric acid was added so that the amount of phosphorus in the phosphoric acid based on the amount of the polymer was 30 ppm, and titanium dioxide used as the phosphorus acid Matting agent was also added so that the amount of titanium dioxide based on the amount of the polymer was 0.3 wt .-%. These additives were stirred at a temperature of 260 ° C. Subsequently, the entire in the DE-2 reactor 5 located oligomer introduced into a polycondensation reactor. Then 200 g of a 2 wt .-% solution of antimony trioxide in EG were introduced into the polycondensation reactor. Subsequently, the product thus obtained was polycondensed by conventional polycondensation to form a flame-resistant polyester polymer. The process for producing the flame-resistant polyester polymer was repeated 5 times. The average values and the spread of the analysis results of the obtained flame-resistant polyester polymer are shown in Table 1.

As from Table 1, the change in the amount was DEG was large and therefore also the change of the melting point large.

Example 2

One flame resistant polyester polymer was prepared by the same method as prepared in Example 1 with the difference that a phosphorus-containing Flame retardant and EC at a temperature of 190 ° C put together for 4 hours and then in the DE-2 reactor were introduced.

Example 3

One flame resistant polyester polymer was prepared by the same method as prepared in Example 1 with the difference that a phosphorus-containing Flame retardant and EC at a temperature of 190 ° C put together for 4 hours and then in the Polycondensation reactor were introduced.

Comparative Example 2

A flame resistant polyester polymer was prepared by the same method as in Example 1 except that 68 kg of a flame retardant of the above-mentioned Chemical Formula 1 wherein R ^{1 is} hydrogen, R ^{2 is} a phenyl group and R ^{3 is} hydrogen, independently into a second esterification reactor (DE-2 reactor) were introduced in a state wherein the flame retardant was not mixed with EG.

Example 4

A flame resistant polyester polymer was prepared by the same method as in Example 1 except that 82 kg of a flame retardant of the above-mentioned Chemical Formula 1 wherein R ^{1 is} hydrogen, R ^{2 is} a phenyl group and R ^{3 is} a hydroxyethyl group (-CH ₂ CH ₂ OH ) were introduced.

Comparative Example 3

One flame resistant polyester polymer was prepared by the same method as prepared in Example 1 with the difference that no manganese salt and no phosphorus compound were introduced.

Example 5

• *1. Zeit (min) ist die Polykondensationsreaktionszeit und bedeutet die Zeit ab der Einführung des Katalysators bis zum Abschluss der Polykondensationsreaktion.
• *2. IV ist die Grenzviskositätszahl mit der Einheit dl/g.
• *3. DEG: die Einheit ist Gew.-%.

The flameproof polyester polymer prepared according to Example 2 was dried for 24 hours by means of a vacuum dryer. Subsequently, the dried polyester polymer was extruded at a spinning temperature of 280 ° C by using an extruder having an inner diameter of 95 mm, and the extruded polyester polymer was made into a 75-denier fiber of 75 by a direct stretching method by a first one at 80 ° C heated Godet roll at a rotational speed of 1350 m / min and heated to 120 ° C second Godet roller at a rotational speed of 4100 m / min processed. The fiber produced was knitted and woven by a tube and then its oxygen limit (LOI) was determined. The LOI of the fiber was 32, which thus has excellent flame retardant properties. Table 1 class example 1 Comparative Example 1 Example 2 Example 3 Comparative Example 2 Example 4 Comparative Example 3 Time 190/9 190/16 185/10 200/12 185/14 190/8 190/10 IV 0.645 / 0.015 0.636 / 0.045 0.639 / 0.011 0.635 / 0.018 0.638 / 0.021 0.643 / 0.013 0.646 / 0.015 DEG 2.1 / 0.3 3.8 / 3.2 2.3 / 0.3 1.8 / 0.4 3.1 / 0.9 2.4 / 0.4 2.1 / 0.4 Tm (° C) 242 / 1.8 239 / 11.7 237 / 1.6 244 / 1.9 235 / 2.2 238 / 2.7 242 / 2.0 IV maintenance ratio (%) 97 / 0.3 97 / 0.4 96 / 0.4 96 / 0.3 96 / 0.4 97 / 0.3 88 / 0.2 (shown as average / span, spread = maximum - minimum)

• *1. Time (min) is the polycondensation reaction time and means the time from the introduction of the catalyst to the completion of the polycondensation reaction.
• * 2nd IV is the limiting viscosity number with the unit dl / g.
• * 3rd DEG: the unit is wt%.

As From Table 1, the amount of DEG in Examples became at 3% by weight or less, and the amount of DEG in the comparative example 3 was 3 wt% or less. There is no manganese salt and no Phosphorus compound were introduced, the conservation ratio the intrinsic viscosity number exceptional low.

[Advantageous Effects]

The flame resistant polyester polymer and the polyester fiber made therefrom have a good color and excellent flame retardant properties and have excellent UV stability when they are processed into final products in a spinning process.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - JP 62-6912 [0006]
• - JP 53-46398 [0006]
• - JP 51-28894 [0006]
• US 3941752 [0007]
• US 5399428 [0007]
• - US 5180793 [0007]
• - JP 50-56488 [0007]
• - JP 52-47891 [0007]

Claims (8)

A process for producing a flame resistant polyester polymer using terephthalic acid comprising the steps of: preparing a suspension of terephthalic acid (TPA) and ethylene glycol (EG) as a reactant, introducing this suspension into a first esterification reactor to form an oligomer in a first esterification reaction, Introduction of the Oligomer Formed in the First Esterification Reaction to a Second Esterification Reactor to Prepare a Flame Retardant Oligomer Introduction of a phosphorus flame retardant, represented below by Chemical Formula 1, such that the amount of phosphorus relative to the polyester polymer is 500 to 50,000 ppm, addition of a manganese salt, and a Phosphorus compound, both of which are UV stabilizers, such that the amount of manganese and phosphorus is 0.1 to 500 ppm, respectively, for carrying out a second esterification reaction, and initiating the reaction in the second esterification of oligomer formed in a polycondensation reactor and subsequent polycondensation of the same

wherein R ^{1 is} hydrogen or a hydroxyalkyl group having 1 to 10 carbon atoms, R ^{2 is} hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms and R ^{3 is} hydrogen, an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms or a to Formation of an ester suitable functional group. Process for the preparation of a flameproof polyester polymer according to claim 1, characterized in that the amount of diethylene glycol (DEG) based on the polyester polymer is kept at 3.0% by weight or less. Process for the preparation of a flameproof polyester polymer according to Claim 1, characterized in that, when the phosphorus-containing flame retardant is introduced into the reactor as a solution in ethylene glycol (EG) or as a dispersion phase in ethylene glycol (EG), the amount of EG is calculated according to the following mathematical formula 1: Mathematical Formula 1: 0.2 x FR (g) · (FN FR · 62) / (MW FR ) · (1 + α) ≦ EG (g) ≦ 3 · FR (g) · (FN FR · 62) / (MW FR · · (1 + α), wherein FR is a flame retardant, FN _{FR is} the number of carboxylic acid groups in 1 mole of the flame retardant, MW _FR (g / mol) is the molecular weight of the flame retardant, and α is a constant number, where α is 1 when the flame retardant is solid, and 0 is when the flame retardant is liquid. Process for the preparation of a flameproof polyester polymer according to claim 1, characterized in that as monomers for the copolymerization one or more Dicarboxylic acids and their ester-forming derivatives selected from the group consisting of aromatic dicarboxylic acids, such as isophthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid u. Like. And their ester-forming derivatives; alicyclic dicarboxylic acids, u. etc .; and an alkyl dicarboxylic acid having 2 to 6 carbon atoms, their ester-forming derivatives or their acyl chloride are used. Process for the preparation of a flameproof polyester polymer according to claim 1, characterized in that as monomers for the copolymerization one or more Glycols selected from the group consisting of alkane glycols, alicyclic glycols, aromatic glycols and propylene oxide additives be used. Process for the preparation of a flameproof polyester polymer according to claim 1, characterized in that the molar ratio of ethylene glycol to dicarboxylic acid including TPA ranges from 1.01 to 2.0. Flame-retardant polyester polymer obtained by the process according to any one of claims 1 to 6 was produced. Fiber made using the method A polyester polymer prepared according to any one of claims 1 to 6 was produced.