KR19980027483A - Polyetherester Block Copolymer Resin Composition and Manufacturing Method Thereof - Google Patents

Abstract

The present invention has excellent thermal stability and can be usefully used for coating and jacketing of various sports goods and various electric wires, gaskets subjected to high temperature heat for a long time, sealing materials, and the like, and a method for producing the polyether ester block copolymer. It is about.

The polyether ester block copolymer resin composition has a molecular weight of 25000 to 100000 in which the hard segment of the short-chain ester structure and the soft segment of the long-chain ester structure are formed at a ratio of 90:10 to 20: 80% by weight, and the polyether ester block copolymer In the polycondensation reaction during the copolymerization process, 1,4-butenediol component and dimethyl terephthalic acid were added at a molar ratio of 1: 2.1 to 1: 1.8, followed by esterification at a temperature of 180 to 230 ° C. for 1 to 4 hours. It is characterized by the fact that it is prepared by adding a compound.

Description

Polyetherester Block Copolymer Resin Composition and Manufacturing Method Thereof

The present invention relates to a polyether ester block copolymer resin composition, and more particularly, to a polyetherester block copolymer resin composition which is a high-performance thermoplastic elastic material that can be applied to various sports products, wire coating materials, and dustproof materials. It relates to a manufacturing method thereof.

In recent years, polyether ester block copolymer resins have been widely applied to sports articles, wire coating materials, and dustproof materials because of their excellent flexibility and moldability. Such a polyether ester block copolymer resin is generally manufactured by the same polymerization process as the manufacturing method of a polyester resin, and is used for product manufacture as a state mixed with a single component or other resin through a post process.

Looking at the properties of the polyether block copolymer resin is as follows.

The polyether ester block copolymer resin has a very low glass transition temperature as the content of the soft segment increases. This is because the glass transition temperature of the added polyether type raw material is very low. In addition, since the polyether-based raw material has excellent flexibility and rubber properties, the polyether ester block copolymer resin has excellent impact resistance properties by itself, specifically, a low temperature of -40 ° C at room temperature and -40 ° C in a conventional Izod notched impact strength evaluation. It has a very good level of impact resistance and low temperature flexibility that does not break even in

Such polyether ester block copolymer resins are well disclosed in US Pat. Nos. 3,023,192, 3,651,014, 3,763,109, and the like, and their constituents and structures are as follows.

[Equation 1]

In formula 1, R is terephthalic acid, its lower alkyl esterified product alone or a mixture thereof with aliphatic dicarboxylic acid in the form of isophthalic acid, old phthalic acid, naphthalenedicarboxylic acid or adipic acid, sebacic acid, dimer acid. , D is an aliphatic glycol component having 2 to 8 carbon atoms, mainly 1.4-butanediol or mixed with ethylene glycol, 1.2- or 1.3-propylene glycol, 1.5-pentanediol, 1.6-nucleic acid diol, 1.4-cyclonucleodimethanol It is.

[Equation 2]

In formula 2, R is the same as formula 1, G is a polyalkylene oxide glycol component having a molecular weight of 300-6000, and poly (tetramethylene oxide) glycol or polyethylene glycol or polypropylene glycol alone or in a mixture thereof. It is used as.

The polyether ester block copolymer consists of a block copolymer form of the hard segment represented by Formula 1 and the soft segment represented by Formula 2.

In addition, in order to improve stability, in addition to the basic components constituting the polyether ester block copolymer, a component capable of inducing chemical crosslinking may be added to the polymerization process. In this case, the crosslinking agent component may be one having three or more primary or secondary amine groups, hydroxyl groups or carboxyl groups so as to form a crosslinked structure in the polyetherester block copolymer resin manufacturing process. A polyetherester block copolymer having excellent melt viscosity may be first prepared by adding 0.05 to 3.0 mol% of a component having three or more functional groups capable of reacting with the component to the R components of Formulas 1 and 2. At this time, the components that can be used as a crosslinking agent include trimellitic acid or its anhydride, pyromellitic acid or its anhydride, nuxaglycerol, diethanolamine, triethanolamine, nusamethylenebis (aminoacetic acid), tricin, D- or DL- Serine, DL-threonine hemihydrate, DL-asphatic acid, DL-2-methylglutamic acid, 2-aminoadipic acid, tris (hydroxymethyl) aminomethane, pentaerythritol, glyceric acid, gluconic acid, glue Heptonic acid and the like.

When the above crosslinking agent component is used in an amount of 0.05 mol% or less with respect to the acid component R, it is not expected to improve the desired melt viscosity, and when it is used more than 3.0 mol%, as mentioned above, it is generated in the condensation polymerization process due to excessive increase in the melt viscosity. Since it is difficult to remove the low molecular weight material, bubbles may be generated during the increase and the degree of polymerization, or the discharge may be difficult, and in some cases, the discharge may be impossible.

However, the polyether ester block copolymer resin, which is prepared as described above, is highly sensitive to heat as a structural feature, and thus, a lot of improvements in thermal stability are required. As a method of improving thermal stability, passive methods using various heat stabilizers have been studied due to limitations of ether bonds. However, there have not been suggested methods for improving the structural stability of polyether ester block copolymers.

An object of the present invention is to provide a polyether ester block copolymer resin composition having improved thermal stability in terms of structure.

Another object of the present invention is to provide a preferable method for producing the polyether ester block copolymer resin composition.

The inventors of the present invention have studied the method to improve the thermal stability of the polyether ester block copolymer in terms of the structure, and as a result, D component used in the hard segment among the components constituting the polyether ester block copolymer It was found that the introduction of a certain amount of the unsaturated group into the polysulfate block copolymer significantly improved the thermal stability effect of the polyetherester block copolymer itself in the state excluding the effect of other additives.

In the polyetherester block copolymer resin composition for achieving the object of the present invention, the hard segment of the short-chain ester structure represented by the above hour 1 and the soft segment of the long-chain ester structure represented by the formula 2 are 90:10 to 20:80. It is characterized by having a ratio of weight percent, and its preferred molecular weight is 25000-100000.

Specifically, the hard segment of the short-chain ester structure is a terephthalic acid, a lower alkyl ester compound of terephthalic acid, a mixture of isophthalic acid, orthophthalic acid, 1,4-cyclonucleic acid dicarboxylic acid, adipic acid or a lower alkyl ester compound thereof at 60% by weight or more. 1 species selected from; 1,4-butanediol and 1,4-butenediol mixed at a ratio of 98/2 to 90/10 wt%, ethylene glycol, 1,3-propylene glycol, 1,6- at 80 wt% or more thereof One species selected from esters in the form of a mixture in which nucleic acid diol, 1.8-octamethylene glycol, 1,10-decamethylene glycol, and 1,4-cyclonucleic acid dimethanol are selectively mixed is mixed.

In addition, the soft segment of the long-chain ester structure is a mixture of terephthalic acid, lower alkyl ester compounds of terephthalic acid, at least 60% by weight of isophthalic acid, orthophthalic acid, 1,4-cyclonucleic acid dicarboxylic acid, adipic acid or lower alkyl ester compounds thereof. One selected from the blended mixtures; A polyalkylene oxide glycol alone or a mixture thereof, such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, ethylene oxide-terminated propylene oxide, and copoly (ethylene-propylene oxide) glycol, having a molecular weight of 500 to 6000 will be.

Moreover, in the manufacturing method of the polyether ester block copolymer resin composition, when manufacturing the polyether ester block copolymer resin composition comprised as mentioned above, the 1, 4- butenediol component and dimethyl terephthalic acid are 1: 2.1-1: 1.8. It is characterized by the fact that the compound prepared by adding in a molar ratio and esterifying reaction at a temperature of 180 to 230 ° C. for 1 to 4 hours is added during the polycondensation reaction in the polyether ester block copolymer production step.

The polyetherester block copolymer comprising an unsaturated group according to the present invention thus prepared has a feature that is significantly improved in thermal stability compared to known structures. In particular, the elongation reduction ratio during long-term use, which is most importantly required for the use of elastic materials, has been remarkably improved, and it is practically required in terms of use rather than the classical thermal stability determined in terms of reduction of melt viscosity or discoloration due to existing heat. The thermal stability of the elasticity, toughness, elongation maintenance side is improved and can be usefully used for coating and jacketing of various wires, gaskets that receive high temperature heat for a long time, sealing materials and the like.

The present invention will be described in more detail.

Equation 1 has a crystalline polyester structure referred to as a hard segment, Equation 2 is a soft segment exhibiting rubbery properties, the present invention is a ratio of the hard segment and soft segment 90:10 to 20:80 It consists of a percentage. As already indicated above, the molecular weight of the final polyether ester block copolymer is preferably 25,000 to 100,000.

The hard segment of the short-chain ester structure represented by Formula 1 consists of esterified component of the component represented by R and the component represented by D in a structural formula.

R component is a mixture of terephthalic acid or terephthalic acid, the lower alkyl ester compound alone, or a mixture of 60% by weight or more of isophthalic acid, orthophthalic acid, 1,4-cyclonucleic acid dicarboxylic acid, adipic acid or a lower alkyl ester compound thereof. Form. The component D is a mixture of 1,4-butanediol (D1) / 1,4-butenediol (D2) at a ratio of 98 / 2-90 / 10% by weight, but at least 80% by weight of ethylene glycol, 1, 3-propylene glycol, 1,6-nucleic acid diol, 1,8-octamethylene glycol, 1,10-decamethylene glycol, 1,4-cyclonucleic acid dimethanol, and the like are mixed forms.

The soft segment of the long-chain ester structure represented by Formula 2 consists of esterified component of the component represented by R and the component represented by G in the said structural formula.

R component is the same as R component of Formula 1. G component is polyalkylene oxide glycol alone or these, such as polytetramethylene glycol, polyethyleneglycol, polypropylene glycol, ethylene oxide terminal polypropylene glycol, and copoly (ethylene-propylene oxide) glycol which have an average molecular weight of 500-6000 In the form of a mixture.

The polyether ester block copolymer preferably has a weight ratio of hard segment / soft segment of 90:10 to 30:70. The reason is that when the ratio of hard segments is 90% by weight or more, it is difficult to exhibit the characteristics as an elastic material. When the ratio of hard segments is 30% by weight or less, the ratio of soft segments is increased, and the polymerization process is caused by the addition of excessive polyalkylene oxide glycol. It is because manufacture by this is difficult.

And the molecular weight of a polyether ester block copolymer is suitable about 25,000-100,000. If the molecular weight is 25,000 or less, not only the thermal stability is poor due to the low degree of polymerization, but the overall physical properties such as elastic recovery power is very low. none.

In the above formula, when the terephthalic acid or dimethyl terephthalate is not used in an amount of 60 wt% or more in the entire R component, the R component is very difficult to exhibit excellent heat resistance or strength.

In addition, the component D has thermal stability due to the introduction of an unsaturated group, which is the object of the present invention, when the weight ratio of 1,4-butenediol to the total amount of 1,4-butanediol / 1,4-butenediol is 2% or less. There is little improvement effect, in the case of more than 10% by weight, the adverse effect of reducing the heat resistance characteristics due to the introduction of excessive unsaturated groups occurs. In particular, when the total amount of 1,4-butanediol and 1,4-butenediol in the D component is 80% by weight or less in the total D component, the crystal properties of the final polyether ester block copolymer are reduced, which leads to a decrease in strength and thermal stability. appear.

The average molecular weight of the G component is suitably about 500 to 6000, because only the molecular weight in this range shows the characteristics as a block copolymer. If the molecular weight is less than 500, the block copolymer property is reduced, and the high melting point property of the hard segment is reduced, thereby reducing the overall thermal stability and strength property. If the molecular weight is 6,000 or more, the soft / hard repeats in one molecule of the polyether ester block copolymer. As the number of segments decreases, crystallinity and rubber properties are not harmonized similarly to diblocks and triblocks, and thus, there is a high possibility of adversely affecting physical properties in the final composition.

Moreover, it is suitable that the polyfunctional component thrown in at the time of manufacture of a polyether ester block copolymer is 0.05-3.0 mol% with respect to R component similarly to the case of manufacture of a normal polyetherester block copolymer.

The polyetherester block copolymer of the above composition can be manufactured according to a conventional polyester production method. However, in the present invention, the problem of how much to remain in the final resin relative to the amount of 1,4-butenediol added in the components used. In a typical polyester reaction, the reaction rate is determined by the rate at which excess glycol is used as a solvent during the reaction and is removed in the condensation polymerization process proceeding under vacuum. Therefore, since 1,4-butenediol is introduced into the molecule of the polyether ester block copolymer by the same mechanism as the excess 1,4-butanediol, it is very likely to be removed by vacuum out of the reaction relationship in the polycondensation step. Thus, the present inventors increase the molecular weight to some extent through pre-esterification reaction or transesterification reaction with an acid component, and the reaction is carried out at the intermediate stage of condensation polymerization in which the end of the reactant is mostly in the glycol state. The loss to the outside of the pipe shall be minimized. In the preliminary reaction, if there is a glycol excess atmosphere, a normal esterification reaction or an exchange reaction proceeds easily, but if an acid is excessive, a vacuum of about 200 to 400 mmHg is introduced into the esterification or exchange reaction to increase the ester conversion rate. It is advantageous to. In particular, the molar ratio of the acid component and 1,4-butenediol is very large at 1: 2.1 to 1: 1.8.

As described above, a method for producing a polyetherester block copolymer when 1,4-butenediol is used by preliminarily reacting with an excessive acid component or in the form of 1,4-butenediol alone is as follows.

Various raw materials are put into a polyester reaction vessel equipped with a stirrer, and the esterification reaction or the transesterification reaction is performed while raising the temperature of the reaction tube to 180 to 230 ° C. for 1 to 3 hours at room temperature and normal pressure. In the case of an esterification reaction, you may pressurize about 1-3 kg / cm <2>. These esterification reactions or transesterification reactions produce alcohol or water as by-products, which are vaporized or leaked by the heat of the reaction tube. Normally, by-products corresponding to two mole times of the acid component introduced are theoretically produced. However, if 95% of the by-products flow out of the theoretical amount, the outflow rate is drastically reduced. Therefore, this point is regarded as the end of the esterification reaction or the exchange reaction, and the reaction is stopped. Then, the temperature of the reaction tube near 200 ° C. is increased to 240 to 260 ° C. for 0.5 to 2.0 hours, and at the same time, the pressure in the reaction tube is adjusted to a reduced pressure of 1 mm Hg or less at a normal pressure of 760 mm Hg during the period of temperature increase. After the pressure in the reaction tube reaches 1 mmHg, the condensation reaction is carried out for 0.5 to 3 hours, then the stirring is stopped and the reaction is stopped by restoring the pressure to atmospheric pressure as nitrogen. After the reaction is stopped, the pellets at the bottom of the reaction tube are dismantled and discharged by applying a pressure of 1 to 4 kg / cm 2 as nitrogen to the reaction tube to obtain a pellet-like polyether ester block copolymer resin.

In this case, 1,4-butenediol may be added before the esterification reaction or exchange reaction, or before condensation polymerization or in the middle of condensation polymerization.However, in the case of 1.4-butenediol alone, similar effects are obtained at any point. In the preliminary reaction, it was found that 1,4-butenediol having a carboxyl terminal was most suitable in a state in which the pressure of the reaction tube was about 200 to 300 mmHg. The reason for this is that at the above degree of vacuum, most of the over-injected glycol component 1,4-butanediol is removed, and the molecular weight of the polyether ester block copolymer is increased to some extent so that the pre-reactant at the carboxyl terminal is added to the esterification reaction. This is because it is easily introduced into the structure of the main molecule by the exchange reaction.

In the present invention, additives such as catalysts, heat resistant agents, antistatic agents, mold release agents, nucleating agents, pigments and weathering agents can be used.

As the catalyst, titanium-based catalysts such as tetrabutyl titanate, tetraisopropyltinate, etc., and other tin-based catalysts may be used alone or in combination. However, in the case of tin-based catalysts, mainly titanium is used. It is recommended to use a mixture of titanium alone and titanium.

As a heat resistant agent, a phosphorus heat resistant agent such as phosphoric acid, triphenyl phosphate, triphenyl phosphite, tris (butyl butylphenyl) phosphite, a steric hindrance type phenolic heat resistant agent, an amine heat resistant agent, a sulfur heat resistant agent, etc. It can be selected according to use, and other additives such as antistatic agent, mold release agent, nucleating agent, pigment, weathering agent can be added as desired.

Hereinafter, the present invention will be described in detail through examples.

Example 1

Each component of Table 1 was added to a polyester reaction vessel equipped with a stirrer, and transesterification was carried out while raising the temperature of the reaction tube to 200 ° C. for 2 hours at room temperature and normal pressure. Methanol flows out as a by-product during the transesterification reaction, while maintaining the temperature of the reaction tube at 200 ° C., the amount of methanol corresponding to 2 mole times the acid component is set as the theoretical effluent amount, and 95% of the theoretical effluent The reaction was stopped at the time of the exit of the transesterification reaction of the hard segment. And the reaction tube temperature of 200 degreeC was raised to 250 degreeC for 1 hour, and the pressure was depressurized so that it might become 1 mmHg at normal pressure for 1 hour when temperature rises. After the pressure of the reaction tube reached 1 mmHg, the condensation reaction was performed for 60 minutes, the stirring was stopped, and the reaction was stopped by restoring the pressure to atmospheric pressure as nitrogen. After the reaction was stopped, the pellets at the bottom of the reaction tube were dismantled, and a pellet-like polyether ester block copolymer resin was obtained while discharging by applying a pressure of 2 kg / cm 2 as nitrogen to the reaction tube.

(Examples 2 to 5 and Comparative Examples 1 to 3)

Except using the raw material of the composition shown in Table 1, the polyether ester block copolymer resin was manufactured on condition and method similar to Example 1.

(Examples 6-14, Comparative Examples 4-5)

A polyether ester block copolymer resin was prepared in the same conditions and methods as in Example 1, except that the input composition was changed as in Table 2 in Example 2.

Raw material composition Example Number DMT BD1 BD2 PTMG1000 TBT ADD TMP BD2 weight ratio Example 1 2000 1520 80 600 5 9 1.4 5 Example 2 1800 1330 70 1000 5 9 1.2 5 Example 3 1400 950 50 1500 5 9 1.0 5 Comparative Example 1 1000 570 30 2200 5 9 0.7 5 Example 4 1800 1358 42 1000 5 9 1.2 3 Example 5 1800 1288 112 1000 5 9 1.2 8 Comparative Example 2 1800 1393 7 1000 5 9 1.2 0.5 Comparative Example 3 1800 1190 210 1000 5 9 1.2 17

In Table 1, DMT is dimethyl terephthalate, BD1 is 1,4-butanediol, BD2 is 1,4-butenediol, PTMG1000 is polytetramethylene oxide glycol having an average molecular weight of 1000, TBT is tetrabutyl titanate (catalyst), ADD, TMP is trimetholol propane, BD2 weight ratio is the weight% of BD2 to the total amount of BD1 + BD2.

Example Content of Example 2 Changes Example 6 PTMG1000 1000g PTMG2000 1000g Example 7 PTMG1000 1000g PTMG1000 500gPTMG2000 500g Example 8 PTMG1000 1000g PTMG1000 900gPEG4000 100g Example 9 PTMG1000 1000g PTMG1000 900gEOPPG2000 100g Example 10 DMT 1800g DMT 1440gDMI 360g Comparative Example 4 DMT 1800g DMT 900g DMI 900g Example 11 DMT 1800g DMT 1700gCHDA 100g Example 12 DMT 1800g DMT 1700gAA 50g Example 13 BD1 1400g BD1 1200gEG 130g Comparative Example 5 BD1 1400g BD1 930gEG 400g Example 14 BD1 1400g BD1 1230gCHDM 100g Example 15 TMP 1.2g TMA 1.8g Example 16 TMP 1.2g DEA 1.0g

In Table 2, PTMG2000 is polytetramethylene oxide glycol having an average molecular weight of 2000, PEG4000 is polyethylene glycol having an average molecular weight of 4000, EOPPG2000 is polypropylene glycol at the end of ethylene oxide having an average molecular weight of 2000, DMI is dimethylisophthalate, and CHDA is 1,4-cyclonucleic acid dicarboxylic acid, AA for adipic acid, EG for ethylene glycol, CHDM for 1,4-cyclonucleodimethanol, TMA for trimellitic anhydride, DEA for diethanolamine.

Example Properties Tensile Strength (㎏ / ㎠) Elongation at Break (%) Melting Point (℃) Heat resistance (%) Example 1 385 485 212 67.0 Example 2 334 521 203 59.9 Example 3 257 841 183 47.8 Comparative Example 1 142 1127 149 Not measurable Example 4 342 536 204 57.1 Comparative Example 5 323 542 202 60.2 Comparative Example 2 338 512 204 32.6 Comparative Example 3 314 652 200 49.5 Example 6 210 859 212 53.3 Example 7 276 726 208 52.4 Example 8 298 582 209 55.4 Example 9 302 595 207 58.4 Example 10 287 584 192 49.5 Comparative Example 4 173 876 171 6.1 Example 11 320 538 196 63.1 Example 12 318 564 194 56.7 Example 13 347 520 200 65.4 Comparative Example 5 352 498 196 38.5 Example 14 349 528 202 66.4 Example 15 335 534 203 60.1 Example 16 341 528 203 61.2

Low-molecular substances such as moisture were removed by vacuum drying the reactants prepared in each of Examples and Comparative Examples for 6 hours at 100 ° C., and specimens of the No. 4 form of ASTM D-638 were prepared in an injection molding machine having a clamping force of 200 tons. Tensile strength was evaluated at a speed of 200 mm per minute using an Instron universal tester, and the tensile specimens were heat-treated in a hot air oven at 160 ° C. for 50 hours, and then measured for elongation. The results are shown in Table 3 above. Heat resistance was calculated and described by the following equation (3).

[Equation 3]

(Example 17)

In Example 2, the method of adding 1,4-butenediol (BD2) was changed. First, 70 g of butenediol and 309 g of DMT of 2 times mole of this butenediol were added to a polyester reaction vessel, and the temperature was at 200 ° C. An esterified product was prepared through the reaction for 2 hours. In Example 2, the entire amount of 1,4-butenediol and the remaining reactants except DMT 309g were added thereto, and the transesterification reaction was carried out in the same manner, and the condensation polymerization reaction was started while introducing a reduced pressure process. 30 minutes after the start of the condensation polymerization, the temperature of the reaction tube was 241 ° C when the pressure of the reaction tube was 260 mmHg. Here, the reaction product of 1,4-butenediol and DMT prepared above was added thereto, and then a polyether ester block copolymer resin was prepared using the same method as in Example 2.

(Example 18)

A polyetherester block copolymer resin was prepared in the same manner as in Example 17, except that the reaction of 1,4-butenediol and DMT was carried out in a vacuum of 300 mmHg.

(Example 19)

A polyether ester block copolymer resin was prepared in the same manner as in Example 17, except that the reactant of 1,4-butenediol and DMT were added to the initial polycondensation polymerization.

Comparative Example 6

A polyetherester block copolymer resin was prepared in the same manner as in Example 17, except that the reaction product of 1,4-butenediol and DMT was added at the beginning of the ester reaction, that is, at the time when all the raw materials were added.

Comparative Example 7

Polyetherester block air was prepared in the same manner as in Example 17, except that DMT was increased to 340 g to prepare a reactant of 1,4-butenediol and DMT so that the molar ratio of DMT / 1,4-butenediol was 2.2 / 1. Copolymer resin was prepared.

(Comparative Example 8)

Polyetherester block air was prepared in the same manner as in Example 17, except that DMT was reduced to 262 g so that the molar ratio of DMT / 1,4-butenediol was 1.7 / 1 when preparing reactants of 1,4-butenediol and DMT. Copolymer resin was prepared.

(Example 20)

A polyetherester block copolymer resin was prepared in the same manner as in Example 17, except that 59.9 g of isophthalic acid having the same molar number was added instead of 70 g of DMT.

(Example 21)

A polyether ester block copolymer resin was prepared in the same manner as in Example 17, except that 52.7 g of the same mole of adipic acid was added instead of 70 g of DMT.

The specimens were made in the same manner as described above with the reactants prepared in Examples 17 to 21 and Comparative Examples 6 to 8, and physical properties were tested. The results are shown in Table 4 below.

Example Properties Tensile Strength (㎏ / ㎠) Elongation at Break (%) Melting Point (℃) Heat resistance (%) Example 17 338 522 205 60.7 Example 18 345 520 205 62.7 Example 19 326 536 204 58.0 Comparative Example 6 338 530 204 58.1 Comparative Example 7 345 519 203 57.2 Comparative Example 8 336 523 203 56.8 Example 20 329 542 201 62.3 Example 21 325 545 202 61.7

As can be seen from Table 3 and Table 4, when the polyether ester block copolymer resin is manufactured using the same material, the specimen using the polyether ester block copolymer resin prepared according to the present invention is compared with the conventional method. It can be seen that the heat resistance is excellent. Specifically, in Table 3, the heat resistance of the specimen prepared by the conventional method is 6.1 to 49.5%, whereas the heat resistance of the specimen by the present invention is 47.8 to 67%, and in Table 4, the heat resistance of the specimen by the conventional method is 56.8 to 58.1%. The thing by this invention was 58.0-62.7%.

As described in detail above, the polyether ester block copolymer resin composition according to the present invention has a remarkably improved elongation reduction ratio during long-term use, which is most importantly required in applications in which elastic materials are used, as compared with the existing ones. It has excellent thermal stability in terms of elasticity, toughness, and elongation, which are required for use, and can be usefully used for coating or jacketing various wires, gaskets subjected to high temperature heat for a long time, and sealing materials.

Claims (6)

A polyetherester block copolymer having a molecular weight of 25000 to 100,000 with a hard segment of the short chain ester structure represented by the following formula 1 and a soft segment of the long chain ester structure represented by the formula 2 at a ratio of 90:10 to 20: 80% by weight. Resin composition. [Equation 1] Where R is terephthalic acid, its lower alkyl esterified product alone or a mixture thereof with aromatic dicarboxylic acid in the form of isophthalic acid, old phthalic acid, naphthalenedicarboxylic acid or aliphatic dicarboxylic acid in the form of adipic acid, sebacic acid, dimer acid , D is an aliphatic glycol component having 2 to 8 carbon atoms, mainly 1.4-butanediol or mixed with ethylene glycol, 1.2- or 1.3-propylene glycol, 1.5-pentanediol, 1.6-nucleic acid diol, 1.4-cyclonucleodimethanol It is done.) [Equation 2] (Equation 2, R is the same as formula 1, G is a polyalkylene oxide glycol component having a molecular weight of 300 to 6000, poly (tetramethylene oxide) glycol or polyethylene glycol or polypropylene glycol alone or in the form of a mixture thereof. It is used as.) The hard segment of the short-chain ester structure is a lower alkyl ester compound of terephthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-cyclonucleic acid dicarboxylic acid, adipic acid or lower alkyl thereof in 60% by weight or more. One selected from a mixture of ester compounds; 1,4-butanediol and 1,4-butenediol mixed at a ratio of 98/2 to 90/10 wt%, ethylene glycol, 1,3-propylene glycol, 1,6- at 80 wt% or more thereof Polyether ester block air, characterized in that one selected from the esterified form of the nucleic acid diol, 1.8-octamethylene glycol, 1,10- decamethylene glycol, 1,4-cyclonucleodimethanol is optionally mixed Copolymer Resin Composition. The soft segment of the long chain ester structure is a terephthalic acid, a lower alkyl ester compound of terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-cyclonucleic acid dicarboxylic acid, adipic acid or lower thereof in 60% by weight or more thereof. One selected from a mixture of alkyl ester compounds; A polyalkylene oxide glycol alone or a mixture thereof, such as polytetramethylene glycol, polyethyleneglycol, polypropylene glycol, ethylene oxide-terminated flopylene glycol, and copoly (ethylene-propylene oxide) glycol having a molecular weight of 500 to 6000 Polyether ester block copolymer resin composition, characterized in that. The polyether ester block copolymer according to claim 1, wherein the polyfunctional compound having three or more reactive functional groups composed of carboxyl, hydroxyl, primary or secondary amines or anhydrides thereof capable of reacting with the polyester forming component constitutes the polyetherester block copolymer. 0.05-3.0 mol% is injected | thrown-in with respect to the acid component to carry out, The polyether ester block copolymer resin composition characterized by the above-mentioned. In the method for producing a polyetherester block copolymer resin composition, 1,4-butenediol component and dimethyl terephthalic acid are added at a molar ratio of 1: 2.1 to 1: 1.8 during the polycondensation reaction during the polyetherester block copolymer production process. And a compound prepared by carrying out the ester reaction for 1 to 4 hours at a temperature of 180 to 230 ° C., wherein the compound prepared is a polyether ester block copolymer. The method according to claim 5, wherein terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-cyclonucleic acid dicarboxylic acid, adipic acid, or a lower alkyl ester compound thereof is used instead of dimethyl terephthalic acid which is added during reaction with 1,4 butenediol. Method for producing a polyether ester block copolymer, characterized in that.