KR20170090707A - Manufacturing process of high viscosity isosorbide polyethyleneterephthalate polymer - Google Patents

Abstract

A method of producing a high viscosity isosorbide polyethylene terephthalate polymer according to the present invention comprises the steps of: mixing ethylene glycol (EG), terephthalic acid (TPA) and isosorbide of the following chemical formula 1 to prepare slurry; performing an esterification reaction process of the slurry; a step of melt-polymerizing the slurry passing through the esterification reaction process; and solid-state polymerizing the melt-polymerized slurry, wherein the isosorbide is injected in an amount of 4.0 to 10 mol%, and more preferably 4 to 6 mol% based on terephthalic acid. The method of the present invention can produce the high viscosity isosorbide polyethylene terephthalate polymer which can be used in industrial fibers by adding isosorbide when producing the polyethylene terephthalate polymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a high viscosity isosorbide polyethyleneterephthalate polymer,

The present invention relates to a process for preparing a copolymerized polyethylene terephthalate polymer, and more particularly, to a process for producing a copolymerized polyethylene terephthalate polymer, which comprises the steps of: (1) adding ethylene glycol (EG, Ethyleneglycol) and terephthalic acid Isosorbide) to produce a high viscosity isosorbide polyethylene terephthalate polymer which can be used in industrial fibers.

Generally, polyester resins, especially polyethylene terephthalate resins, are linear polymers synthesized from dicarboxylic acids or ester-forming derivatives thereof and diols or ester-forming derivatives thereof, which are low in cost and excellent in mechanical properties and chemical properties But also has excellent gas barrier properties and is widely used for the production of various containers, films and fibers. On the other hand, the polyester is produced by condensation polymerization method. In the equilibrium reaction according to external conditions, a commercially available viscosity is obtained through high temperature and high vacuum conditions, and a certain amount of oligomer remains in the final polymer.

In order to improve the moldability of the polyester resin and to eliminate the crystallinity, polyester resins copolymerized with two or more glycol or dicarboxylic acid components have been widely used commercially. In the case of a homopolyester composed of only terephthalic acid and ethylene glycol, it is possible to improve physical properties and heat resistance through stretching crystallization and heat fixation, but there are limitations in application and improvement in heat resistance, In the case of polyester, there is a drawback that it is difficult to improve the heat resistance by the stretching or crystallization process. As another method for improving the heat resistance of polyester, a method of using isosorbide, which is an environmentally-friendly diol compound derived from starch, as one of monomers is known, and is widely used for high heat resistant materials. It is widely used in beverage bottles, but it has not been used in industrial fibers that require high heat resistance.

Korea Patent Publication No. 2011-0028696 Korean Patent No. 1,058,974

It is an object of the present invention to provide a method for producing a highly viscous isosoboid polyethylene terephthalate polymer which can be used in industrial fibers by additionally introducing isosorbide in the production of a polyethylene terephthalate polymer.

According to one aspect of the present invention, there is provided a method for producing a slurry by mixing ethylene glycol (EG), terephthalic acid (TPA), and isosorbide represented by the following formula (1) step; An esterification reaction step of the slurry; A melt polymerization step; And a solid phase polymerization step; Wherein the isosorbide is added in an amount of 4.0 to 10 mol%, more preferably 4 to 6 mol%, based on the terephthalic acid. The present invention also provides a process for producing a highly viscous isosorbide polyethylene terephthalate polymer.

At this time, if the isosorbide content is less than 4.0 mol% or exceeds 10 mol%, interfusion bonding will occur. In addition, the basic properties of the isobaric reaction and the PET polymerization are determined according to an appropriate ratio of the isosorbide and ethylene glycol.

In the present invention, the molar ratio of ethylene glycol and isosorbide to TPA was 1.01 to 1.3 or less, and the isosorbide was reacted with 80% or more, and the DEG of the side reaction was attained to the level of 0.8%. If the molar ratio of ethylene glycol to isosorbide exceeds TPA of 1.3, the reaction can not be properly performed due to the volatility of isosorbide. If the molar ratio is less than 1.01, appropriate ester is not reacted and polymerization can not be performed. The polymer thus polymerized has a high viscosity through solid phase polymerization. In the solid phase polymerization, appropriate surface crystallization is not required, so that there is no fusion between the chips, and the solid phase time can be shortened and the production loss can be reduced. In the surface crystallization, the chip is subjected to surface crystallization by heating sufficiently in a vacuum or nitrogen flow state in the absence of water.

The polymerized and polymerized solid phase polymer is a high viscosity isosorbide pet which can be used for industrial and high rigidity high temperature applications.

[Chemical Formula 1]

In this case, it is preferable that the molten polymerized product prepared through the melt polymerization step has an intrinsic viscosity of 0.6 dl / g to 0.8 dl / g, a diethylene glycol content of 0.85 wt% or less, And having a viscosity of 0.9 dl / g to 1.3 dl / g. The present invention also provides a process for producing a highly viscous isosorbide polyethylene terephthalate polymer. If the intrinsic viscosity of the molten polymer is less than 0.6 dl / g, there is a problem that it is difficult to set the temperature for surface crystallization in the solid phase polymerization. If the intrinsic viscosity of the molten polymer exceeds 0.8 dl / g, the economical efficiency is lowered.

If the content of diethylene glycol is more than 0.85 wt%, the physical properties of the final product may deteriorate and fusion between chips may occur during solid-state polymerization. When the intrinsic viscosity of the solid polymer is less than 0.9 dl / g, sufficient physical properties can not be obtained. When the intrinsic viscosity is more than 1.3 dl / g,

The present invention relates to the production of polyethylene terephthalate polymerizates by adding isosorbide to prepare high viscosity isotemporal polyethylene terephthalate polymers which can be used in industrial fibers.

The method for preparing a highly viscous isosorbide polyethylene terephthalate polymer according to the present invention comprises the steps of: preparing a slurry by mixing ethylene glycol (EG, Ethyleneglycol), terephthalic acid (TPA, terephthalic acid) and isosobide; An esterification reaction step; A melt polymerization step; And a solid phase polymerization step.

At this time, the melt polymerized product obtained through the melt polymerization step has an intrinsic viscosity of 0.6 dl / g to 0.8 dl / g and a diethylene glycol content of 0.85 wt% or less, And a viscosity of 0.9 dl / g to 1.3 dl / g.

If the intrinsic viscosity of the molten polymer is too high, discoloration may occur.

The isosorbide which is further added in the present invention is a compound represented by the following general formula (1).

[Chemical Formula 1]

The isosorbide represented by the above formula (1) is an environmentally-friendly diol compound derived from starch.

The polyethylene terephthalate polymer according to the present invention is produced by copolymerizing an acid component and a diol component so that an acid moiety derived from an acid component and a diol moiety derived from a diol component It has a repeating structure.

The acid component used in the present invention is terephthalic acid, and the diol component is ethylene glycol and isosorbide.

Hereinafter, each step of the method for producing a high viscosity isosoboid poly (ethylene terephthalate) polymer according to the present invention will be described in detail.

In the method for preparing a high viscosity isosoboid polyethylene terephthalate polymer according to the present invention, the first step is a step of preparing a slurry by mixing terephthalic acid (TPA), ethylene glycol (EG), and isosorbide. At this time, the molar ratio of ethylene glycol / terephthalic acid is preferably 1.01 to 1.3, and the isosorbide is preferably 4 to 10 mol%, more preferably 4 to 6 mol%, based on terephthalic acid.

The antimony compound is added to the slurry prepared above at an amount of 150 to 250 ppm based on the antimony metal, and the esterification reaction and the melt polymerization are carried out. At this time, the antimony compound is preferably used as a polymerization catalyst in an amount of 150 to 250 ppm, preferably 150 to 220 ppm, based on the antimony metal. When the antimony compound is used in an amount exceeding 250 ppm based on the antimony metal, the filter of the spinning pack is clogged due to the precipitation of the antimony reducted metal, the pack use period is markedly shortened, and the stretchability is lowered and the workability is lowered. Further, when the antimony compound is used at less than 150 ppm based on the antimony metal, the polymerization rate can not be controlled only by the adjustment of the polymerization temperature and the degree of vacuum, and the polymerization rate becomes significantly slower, making commercial production difficult.

As the polymerization catalyst, a catalyst other than the antimony compound may be used in combination. Examples of other catalysts include a Ge-based compound, a Ti-based compound, and an Al-based compound. In addition, metal compounds such as titanium dioxide and silica other than the polymerization catalyst may be added for the purpose of improving spinning, drawing workability, or other purposes. In this case, however, the metal compound is preferably added within a range not adversely affecting the heat resistance and strong development of the yarn made from the polymerized product produced according to the present invention. For example, the metal compound may be added in an amount of 150 ppm or less.

The polymerization temperature during the melt polymerization is not particularly limited, but is preferably 275 to 288 ° C. It is also preferable to adjust the polymerization temperature and time to increase the esterification reaction rate by 90% or more. If the esterification reaction rate is not 90% or more, unreacted terephthalic acid is present in a large amount, and the polymer produced by the production method of the present invention is used to significantly lower the processability in the production of the yarn, which is disadvantageous to production of high strength yarn. Further, not only a proper polycondensation reaction can not be carried out, but even if the reaction is carried out, proper physical property of polymer can not be obtained.

In the latter half of the polymerization, polymerization can be efficiently carried out with a relatively small amount of a polymerization catalyst by keeping the polymerizate in a final polymerization reactor under a high vacuum of 2.5 torr or less for 1.5 hours or more, preferably 2 hours or more.

Next, according to the method of the present invention, the polymer obtained above is solid-phase polymerized. Unlike Regular PET, the solid phase polymerization is subjected to three stages of drying, crystallization and solid phase polymerization. The drying is carried out at a temperature of 100 ° C or lower for 6 hours to 12 hours, the crystallization varies depending on the isobide content, but the temperature is in the range of 150 ° C to 180 ° C for 3 to 5 hours and the solid phase polymerization temperature is 220 to 240 ° C, Atmosphere. ≪ / RTI > The solid polymer obtained by the solid phase polymerization has an intrinsic viscosity of 0.9 or more, preferably 0.9 to 1.3.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The properties of the polymers prepared in the examples and comparative examples of the present invention were evaluated in the following manner.

(1) Viscosity

0.1 g of a polyethylene terephthalate polymer was added to a reagent (90 DEG C) mixed with phenol and 1,1,2,2-tetrachloroetal in a weight ratio of 6: 4 according to ASTM D 4603 for 90 minutes so as to have a concentration of 0.4 g / The solution was transferred to a Ubbelohde viscometer and maintained in a 30 ° C thermostat for 10 minutes. The drop number of the solution was obtained using a viscometer and an aspirator.

The values of RV (relative viscosity) and I.V. (intrinsic viscosity) were calculated by equations (1) and (2).

&Quot; (1) "

R.V. = Samples falling in water / solvent drops in seconds

&Quot; (2) "

I.V. = 1/4 x [(R.V.-1) / C] + 3/4 (lnR.V./C)

(Where C represents the concentration (g / 100 ml) of the sample in the solution).

(2) Analysis of diethylene glycol (DEG) level

Aminolysis was performed using monoethanolamine and analyzed by GC. Specifically, 1 g of a polyethylene terephthalate polymer was taken, 3 ml of monoethanolamine was added thereto, and a cooler was attached, followed by completely decomposing by heating on a hot plate. After cooling, 20 ml of MeOH containing internal standard (1,6-hexanediol) and 10 g of terephthalic acid (TPA) were added and analyzed using GC. DEG standard curve was prepared using a MeOH solution containing the same internal standards and having DEG contents of 0, 0.05, 0.1 and 0.15%, respectively.

Example  One

The diol content of ethylene glycol and isobide was adjusted to a molar ratio of terephthalic acid of 1.15, and isosorbide was added thereto in an amount of 5 mol% based on terephthalic acid to prepare a slurry. The slurry was melted. Antimony trioxide 190 ppm (based on the weight of ethylene glycol and terephthalic acid) was added and polymerized at a temperature of 280-288 ° C. The polymer was allowed to stand in a final polymerization reactor at a vacuum of 1.3 torr for 2 hours. By such polymerization, a polyester melt polymer of 0.85 wt% of diethylene glycol (DEG) and 0.7 of intrinsic viscosity (I.V.) was obtained.

Subsequently, the polymer was solid-phase-polymerized at 225 ° C for 12 hours to prepare a solid-phase-polymerized polyethylene terephthalate chip having an intrinsic viscosity (I.V.) of 1.01.

Example  2

A solid phase polyethylene terephthalate chip was prepared in the same manner as in Example 1, except that the diol content of ethylene glycol and isobaride was changed to a molar ratio of terephthalic acid of 1.10, and 0.75 wt% of diethylene glycol (DEG) and an intrinsic viscosity ) Was 0.72, and a solid phase polymerized polyethylene terephthalate chip having an intrinsic viscosity (IV) of 1.04 was prepared.

Comparative Example  One

A solid phase polyethylene terephthalate chip was prepared in the same manner as in Example 1, except that the molar ratio of terephthalic acid to the diol content of ethylene glycol and isobarone was 1.40 and the solid phase temperature was 220 占 폚.

Comparative Example  2

A solid phase polyethylene terephthalate chip was produced in the same manner as in Example 1, except that the content of diol of ethylene glycol and isobide was 1.50, and the solid phase polymerization temperature was 215 캜 and the solid phase time was 16 hours Respectively.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 The intrinsic viscosity (I.V., dl / g) 0.7 0.72 0.75 0.7 DEG level (wt%) 0.85 0.75 1.2 1.4 Solid-state time (hr) 12 12 12 16 Solid temperature (℃) 225 225 220 215 Solid phase polymerization intrinsic viscosity (I.V., dl / g) 1.01 1.04 0.84 0.8 Fusion between chips or solidification of inner wall of reactor during solid phase polymerization radish radish U U

As shown in Table 1, it can be seen that in Examples 1 and 2, there was no fusing of the needle during the solid-state polymerization or fusion of the inner wall of the reactor.

Eliminating the fusion of the solid phase polymerization not only reduces the loss of the polymerizate, but also accelerates the solid phase velocity and has an energy saving effect, and the molecular weight distribution of the polymerizate can be more uniformly distributed while performing solid phase polymerization for a short time. Thus, the solid polymerized high viscosity polymer is superior to the solid state polymerized material for a long time.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Will be apparent to those skilled in the art. Accordingly, the scope of protection of the present invention should be defined in the appended claims and their equivalents.

Claims (3)

Preparing a slurry by mixing ethylene glycol (EG, Ethyleneglycol), terephthalic acid (TPA, terephthalic acid) and isosorbide of the following formula (1);
An esterification reaction step of the slurry;
A melt polymerization step; And
Solid phase polymerization stage; Lt; / RTI >
Wherein the isosorbide is added in an amount of 4.0 to 10 mol% based on terephthalic acid.
[Chemical Formula 1]

The method according to claim 1,
Wherein the melt viscosity of the melt polymerized product obtained through the melt polymerization step is 0.6 dl / g to 0.8 dl / g, and the diethylene glycol content is 0.85 wt% or less.
The method according to claim 1,
Wherein the intrinsic viscosity of the solid polymer produced through the solid phase polymerization step is from 0.9 dl / g to 1.3 dl / g. ≪ RTI ID = 0.0 > 11. < / RTI >