KR20010008908A - Non-hydrolyzable polyetherester polymer and manufacturing thereof - Google Patents

Abstract

PURPOSE: A process of preparing the titled compound by blocking a hydroxyl group or carboxyl group of a polyester copolymer to inhibit the hydrolysis of polyetherester copolymer by the end group is provided, which produces polyetherester having excellent hydrolysis resistance and without lowering polymerization degree. CONSTITUTION: In polycondensing a polyetherester polymer comprising polybutyleneterephthalate polyester as a hard segment and polytetramethyleneetherglycol polyether as a soft segment, 0.05 to 2.5% by weight of a carbodiimide compound having a melting point of 60 to 90deg.C based on the weight of the polymer is added during polymerization. The polymer has a holding rate of limiting viscosity of more than 99% and a decrease rate of a carboxyl end group of less than 92%.

Description

Hydrolyzable polyetherester polymer and its manufacturing method {Non-hydrolyzable polyetherester polymer and manufacturing thereof}

The present invention relates to a polyether copolymer having excellent hydrolysis resistance and a method for producing the same, and more particularly, to a polybutylene terephthalate (hereinafter PBT) polyester as a hard segment and a polyoxyalkylene glycol polyether. The terminal hydroxyl group and / or carboxyl group of the block-copolymerized polyether ester copolymer having a soft segment are imidized to improve the hydrolysis resistance and a method for producing the same.

It is already known that polyether ester copolymers having aromatic polyesters as hard segments and polyoxyalkylene glycol-based polyethers as soft segments exhibit excellent elastic recovery.

Since such polyether ester copolymer is mostly used for outdoor use in its use, hydrolysis resistance is required.

However, the polyether ester copolymer has a disadvantage in that the hydrolysis resistance is weak due to the hydroxyl group and / or the carboxyl group.

The present invention is to block the hydroxy group and or carboxyl group of the polyether ester copolymer so that the hydrolysis of the polyether ester copolymer due to the terminal group is suppressed to excellent hydrolysis resistance and does not lower the degree of polymerization of the polyether ester air The purpose is to provide a coalescence and a method for producing the same.

The present invention is a compound having a carbodiimide group in order to reduce the carboxyl group when polycondensation of a polyether ester copolymer having a PBT-based polyester as a hard segment and a polytetramethylene ether glycol (PTMG) -based polyether as a soft segment. The present invention relates to a polyether ester copolymer prepared by condensation polymerization at the end of polycondensation and a method for producing the same.

The present invention is described in more detail as follows.

In the present invention, there are a number of compounds used to lower the carboxy terminal group, but the present inventors used Staaxol (Rhein-Chemie, Germany).

There are the following types of starbacsol depending on the purpose and the form of the compound.

Starbacsol 1, Starbacsol P, Starbacsol Masterbatch, Starbacsol 0115 and so on.

In the present invention, Starbacsol P, which is sold for extrusion, was used.

Starbacsol P is a polymer type carbodiimide, and its melting point is 60 to 90 ° C., which is lower than the polymerization temperature of polyether ester, so that there is no problem in uniformity in the reaction system. Since Starbacsol P is in powder form, it does not cause a problem even if it is added in powder form during polymerization or in a molten state.

The amount to be added is preferably 0.05 to 2.5% by weight relative to the polymer to be polymerized. If it is less than 0.05% by weight, it is difficult to obtain a desired hydrolysis resistant polymer, and if it is more than 2.5% by weight, there is a problem in that the manufacturing cost of the elastomer becomes too high.

Specific examples of the carbodiimide compound used in the present invention include N, N'-dioctadecylcarbodiimide, N-octadecyl-N'-tricarbodiimide, N, N'-di-0-isopropylphenyl Carbodiimide, 2, 4, 6-triisobutylphenylcarbodiimide, and the like.

The polyester portion constituting the hard segment of the polyether ester copolymer, which is the basis of the elastic yarn, is composed mainly of PBT made of terephthalic acid (hereinafter TPA) component and 1,4-butanediol (hereinafter BD) component. However, a part of the acid component, generally 20 mol% or less, is substituted with a dicarboxylic acid component or an oxydicarboxylic acid component other than the TPA component, and a part of the glycol component, generally 20 mol% or less, is other than the BD component. Substituted with the deoxy component is preferred.

Moreover, although the polyether part which comprises a soft segment has PTMG as a main component, the polyether in which 20 mol% or less of the repeating unit is substituted by the dioxy component other than BD component is preferable.

However, if the average molecular weight of the polyether moiety is less than 500, sufficient elastic properties are difficult to be obtained. If the average molecular weight of the polyether moiety is greater than 5,000, compatibility with the hard segment is deteriorated, and crystallization of the polyether moiety itself occurs, so that the molecular weight range is 500 to 5,000. More preferably, it is effective that it is 1,000-3,000.

In addition, the blending ratio of the polyether portion to the polyester portion is preferably in the range of 0.25 to 4.0 times. If the blending ratio is less than 0.25, the elastic recovery characteristics are lowered. A difficult problem arises.

The intrinsic viscosity of such a polyether copolymer is preferably between 1.0 and 2.5 dl / g, more preferably between 1.3 and 2.3 dl / g.

If the intrinsic viscosity is lower than 1.0dl / g, it is difficult to form in the processing process, and if the intrinsic viscosity is higher than 2.5dl / g, it is difficult to manufacture during condensation polymerization, thereby increasing the manufacturing cost.

The method commonly used in the art to which the present invention pertains is employed to prepare the polyether ester copolymer.

In general, a method of heating and reacting TPA or dimethyl terephthalate (hereinafter, DMT), BD, and PTMG is used, but a method of synthesizing bishydroxybutyl terephthalate in advance and heating it and PTMG is also effective.

In the case of the said method, arbitrary catalysts can be used as needed, Moreover, various stabilizers, a ultraviolet absorber, a thickener, a coloring agent, and other various improvement agents can also be used arbitrarily as needed.

Hydrolysis resistance in the present invention was evaluated by the retention rate of the extreme viscosity after treatment for 1 minute in a vacuum dryer after 30 minutes under pressure in boiling water of 100 ℃ and the carboxy terminal end reduction rate was dissolved in benzyl alcohol and then carboxylated by reverse titration The change in concentration of the end group was evaluated.

Example 1

DMT 390 parts, BD 235 parts, PTMG 600 parts with a number average molecular weight of 2000, 1.2 parts of Titanium tetrabutoxide (manufactured by DuPont) were placed in a reactor, and the temperature inside the reactor was raised to 210 ° C. Proceed with the exchange reaction. After the theoretical amount of methanol was distilled off, the reactor internal temperature was raised to 200 to 250 ° C., followed by reaction for 30 minutes under low vacuum and 300 minutes under high vacuum.

As a stabilizer, 2.5 parts of Iganox 1010 (manufactured by Ciba-Geigy Co., Ltd.) and 0.5 parts of tinuvin 622LD (manufactured by Ciba-Gaigi Co., Ltd.) were charged before the ester exchange reaction.

When the load on the stirrer rose by a desired value, the vacuum inside the reactor was destroyed with nitrogen, and 2.5 parts of Starbacsol P were added and stirred for 10 minutes to discharge. The polymer produced had an intrinsic viscosity of 1.90 and a melting point of 195 ° C. (high viscosity was measured at 25 ° C. in a solution of phenol / 1,1, 1,2-tetrachlorophenol = 6/4). The polymer was discharged into chips and treated under pressure in boiling water at 100 ° C. for 30 minutes, and then dried in a vacuum dryer for 1 day, and then the ultimate viscosity and carboxyl end groups were measured and shown in Table 1 (parts by weight).

Example 2

Table 1 shows the values obtained by carrying out the same method as in Example 1, except that 5 parts by weight of Starbacsol P was added.

Comparative Example 1

Except that Starbacsol P was not added, the same procedure as in Example 1 was carried out and the results are shown in Table 1.

<Table 1>

The present invention can easily produce a polyether ester polymer having excellent hydrolysis resistance and no decrease in the degree of polymerization by a simple method.

Claims (3)

A block copolymer having a polybutylene terephthalate polyester as a hard segment and a polytetramethylene ether glycol polyether as a soft segment, in which 0.05 to 2.5% by weight of a carbodiimide compound is copolymerized with respect to the polymer weight. A polyether ester polymer having excellent hydrolysis property. In the polycondensation polymerization of a polyether ester polymer having a polybutylene terephthalate polyester as a hard segment and a polytetramethylene ether glycol polyether as a soft segment, the carbodiimide compound is 0.05 to the polymer weight during the polymerization. A method for producing a polyether ester polymer having excellent hydrolysis resistance, characterized in that the polymerization is carried out by adding to 2.5 wt%. The method for producing a polyether ester polymer having excellent hydrolysis resistance according to claim 2, wherein a carbodiimide compound having a melting point of 60 to 90 ° C is used.