KR100795169B1 - Thermoplastic elastomer resin - Google Patents

Abstract

The present invention is characterized in that it was prepared by introducing a chain extender and a hydrolysis agent in the presence of a hydroxycarboxylic acid compound (Hydroxy Carboxlic acid compound) to the thermoplastic elastomer produced by melt polymerization to increase the molecular weight and the degree of crosslinking, The present invention relates to a thermoplastic elastomer having excellent melt viscosity, melt tension and heat resistance, and the thermoplastic elastomer according to the present invention has excellent properties for use in automobile parts, particularly for constant velocity joint boots and bellows.

Thermoplastic Elastomer Resin, Constant Velocity Joint Boots

Description

Thermoplastic elastomer resin

The present invention relates to a novel thermoplastic elastomer resin and a method for producing the same, which are excellent in melt viscosity, melt tension and heat resistance and suitable for use in automobile parts, in particular for constant velocity joint boots and bellows. More specifically, the present invention is melt polymerized using an alternating copolymer oligomer of bisphenol and dibromoethane (hereinafter referred to as BPA-Alt-DBE oligomer), and a hydroxycarboxylic acid compound (Hydroxy Carboxlic acid compound), diisocyanate and car The present invention relates to a thermoplastic elastomer resin having excellent properties and to a method for producing the same, which is produced by reaction extrusion using a bodyimide.

Polyester-based thermoplastic elastomers (hereinafter, TPEs) are not only excellent in low-temperature impact characteristics but also excellent in oil resistance and chemical resistance, and thus are widely used in automotive and electric / electronic fields. In particular, CR (Chloroprene Rubber), which is widely used for automobile parts, is considered to have a problem in durability, and recently, it is being replaced by TPE. Compared with CR, TPE has light weight, fatigue resistance, chemical resistance, and ozone resistance, and its application range is expanding in North America and Europe. In particular, in the case of extrusion blowing TPE, since the molten resin is produced through a blowing process, the molten resin should have excellent melt viscosity and melt tension, and the thickness distribution of the molded part during extrusion blowing. Should remain constant.

In general, TPE cannot melt extrusion due to low melt viscosity and melt tension in the molten state, and can increase melt viscosity or melt tension during melt polymerization using a branching agent, but this is not sufficient. In order to solve this problem, after melt polymerization, an attempt was made to increase melt viscosity and melt tension by using a crosslinking agent in an extruder. For example, US Pat. No. 4,071,503 uses a diisocyanate or polycarbodiimide to react the hydroxyl group, which is an end group of the elastomer, with a carboxylic acid group, thereby improving melt viscosity and melt tension, thereby making extrusion blowing possible. Although the residence time in the extruder was excessively long, there was a problem in its productivity, and in USP 5,733,986, the number of end groups of TPE to completely react the hydroxyl group and the carboxylic acid group, which is the end group of TPE, was obtained. By inducing the reaction between the isocyanate group and the hydroxyl group and inducing the reaction of the carboxylic acid group and the polyepoxy compound to obtain the TPE for blowing, the problem of heat resistance and residence time is still solved. It didn't work. The diisocyanate group has a fast reactivity with the hydroxyl group, and the polyepoxy compound has a high reactivity with the carboxylic acid group, which can lead to a viscosity increase, but in order to control the difference in the reaction rate between these groups in the extruder, This is closely related to productivity. In particular, the diisocyanate is mainly reacted with the hydroxyl group of the chain. If the residence time in the extruder is insufficient, the reaction is not sufficient. As a result, the gas caused by the unreacted diisocyanate is caused during extrusion blowing. There is. In addition, unreacted diisocyanate may cause a continuous reaction during remelting during molding, which also affects the control of molding conditions. Therefore, the reaction of diisocyanate should be completed completely and the reactivity should be minimized to minimize the variation of physical properties of each lot.

In order to solve the problems as described above, the present inventors have carried out continuous research, and as a result, in preparing thermoplastic elastomers, thermoplastic elastomers containing aromatic dicarboxylic acid, lower diol, polyalkylene oxide, and BPA-Alt-DBE oligomer After the resin (TPE-A) is formed by melt polymerization, a chain extender and a hydrolysis agent are added together with the hydroxycarboxylic acid compound in order to increase the molecular weight and use it for blowing, so that the melt viscosity, melt tension and heat resistance are excellent. It was confirmed that the thermoplastic elastomer resin (TPE-B) was produced and completed the present invention.

That is, the hydroxycarboxylic acid compound added during the reaction extrusion in the present invention optimally maintains the number of hydroxyl groups to which the isocyanate group can react, thereby making the reactivity of the diisocyanate as a chain lengthening agent optimal. Since carbodiimide is used to increase the hydrolysis resistance, the chain extender and the hydrolysis agent are completely reacted with the elastomer in the twin screw extruder, thereby producing a thermoplastic elastomer having excellent heat resistance and no variation in product properties. Can be. In addition, by adding the hydroxycarboxylic acid compound in the production of the thermoplastic elastomer resin (TPE-B), hardness control can be easily and freely performed. The hardness of the thermoplastic elastomer resin (TPE-B) can be controlled by the content of the polyalkylene oxide introduced during the production of the thermoplastic elastomer resin (TPE-A). Therefore, in order to make the hardness different according to the use of the elastomer, the polymerization reaction was conventionally performed by controlling the content of the polyalkylene oxide, but in the present invention, the content of the polyalkylene oxide by using a hydroxycarboxylic acid compound during the reaction extrusion There is an advantage that can control the hardness through the reaction for a short time instead of adjusting.

Accordingly, an object of the present invention is to provide a thermoplastic elastomer resin (TPE-) containing 0.3-9.0% by weight of BPA-Alt-DBE oligomer together with aromatic dicarboxylic acid, lower diol, and polyalkylene oxide. A) is to provide.

It is another object of the present invention to contain a hydroxycarboxylic acid compound, diisocyanate and carbodiimide together with the TPE-A, which is excellent in melt viscosity, melt tension and heat resistance, and thus for automotive parts, especially for constant velocity joint boots and bellows. It is to provide a thermoplastic elastomer resin (TPE-B) suitable for use.

Still another object of the present invention is to provide a method for preparing the thermoplastic elastomer resin (TPE-B).

The thermoplastic elastomer resin (TPE-A) according to the present invention contains an aromatic dicarboxylic acid, a lower diol, a polyalkylene oxide, and a BPA-Alt-DBE oligomer, and the thermoplastic elastomer resin (TPE-B) is the thermoplastic elastomer resin. Together with (TPE-A), a hydroxycarboxylic acid compound, diisocyanate, and carbodiimide are contained.

The thermoplastic elastomer resin is a thermoplastic polymer in which hard hard segments and soft soft segments are block copolymerized, and in the thermoplastic elastomer resin (TPE) of the present invention, it is a hard hard segment component. Aromatic dicarboxylic acids and lower diols are used, and polyalkylene oxides are used as soft soft segments.

Aromatic dicarboxylic acids include terephthalic acid (TPA), isophthalic acid (IPA), 1,5-dinaphthalenedicarboxylic acid (1,5-Dinaphthalenedicarboxylic acid, 1,5-NDCA), 2,6-di Dimethyl Terephthalate (DMT), Dimethyl isophthalate (2,6-Dinaphthalenedicarboxylic Acid, 2,6-NDCA) Isophthalate, hereinafter referred to as DMI), or mixtures thereof, preferably DMT. In preparing the thermoplastic elastomer resin (TPE-A) according to the present invention, the aromatic dicarboxylic acid is used in an amount of 30 to 45% by weight, preferably 33 to 40% by weight. When the aromatic dicarboxylic acid is used in less than 30% by weight, or when used in excess of 45% by weight, the reaction balance is not appropriate and the reaction does not proceed.

Lower diols include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propane diol, 1,4-butane diol, 1,5-pentanediol, 1,6-hexane Diol, 1,4-cyclohexanedimethanol, and the like, and preferably 1,4-butanediol. Lower diol is used 15 to 30% by weight, preferably 20 to 25% by weight. When less than 15% by weight or more than 30% by weight, the reaction balance is not matched as in the case of aromatic dicarboxylic acid, and thus the reaction does not proceed.

As polyalkylene oxide, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol (PTMEG) and the like may be used. Among these, PTMEG is preferably used, and in particular, PTMEG having a number average molecular weight in the range of 1,000 to 3,000 is preferably used, and more preferably, a number average molecular weight of 2,000 is used. In general, the hardness of the polyester-based elastomer is expressed as Shore hardness-D (Shore-D), the hardness is determined by the content of the polyalkylene oxide. That is, the higher the content of the polyalkylene oxide, the lower the hardness (Shore hardness-D).

In the present invention, 20 to 50% by weight, preferably 30 to 45% by weight of polyalkylene oxide is used in preparing the thermoplastic elastomer resin (TPE-A). When the polyalkylene oxide is less than 20% by weight, the hardness of the TPE is high, so that the wear resistance by friction in the product state after molding is increased, and when the weight is more than 50% by weight, the heat resistance of the TPE itself is low.

BPA-Alt-DBE oligomer may be represented by the following formula (1).

Wherein n is a positive integer from 1 to 5.

The BPA-Alt-DBE oligomer of the above formula reacts with the aromatic dicarboxylic acid during the production of TPE-A, and the BPA-Alt-DBE oligomer substitutes a part of the hard segments of the aromatic dicarboxylic acid and the lower diol to play a role of excellent heat resistance. do.

In preparing the TPE-A according to the present invention, the BPA-Alt-DBE oligomer is used in an amount of 0.3-9.0% by weight, preferably 0.5-5.0% by weight, more preferably 1.5-4.0% by weight. When the BPA-Alt-DBE oligomer is less than 0.3% by weight, the increase in elastic recovery rate and processability is insignificant, and when it exceeds 9.0% by weight, it is difficult to control the hardness of the TPE.

In the thermoplastic elastomer resin (TPE-A) according to the present invention, additives such as branching agents may also be used. Branching agents can increase the melt viscosity and melt tension of the elastomer. As the branching agent, glycerol (Glycerol), pentaerythritol, neopentyl glycol (Neopentylglycol) and the like are used in an amount of 0.05 to 0.10% by weight, preferably glycerol is used. If the branching agent is less than 0.05% by weight, it is difficult to expect an increase in the melt viscosity, and when the amount of the branching agent exceeds 0.10% by weight, the melt viscosity of the TPE-A is excessively increased, making it difficult to control the intrinsic viscosity during melt polymerization.

The preparation of the thermoplastic elastomer resin (TPE-A) according to the present invention consists of two steps, an oligomerization reaction and a polycondensation reaction. The oligomerization reaction is carried out using 0.025 to 0.03 wt% of titanium butoxide (TBT) as a catalyst for 3 to 4 hours at 140 to 215 ° C, and the polycondensation reaction is performed for 4 to 5 hours at 210 to 250 ° C. Using 0.030 ~ 0.075% by weight is carried out in a step of depressurizing stepwise from 760torr to 0.3torr.

Tetrahydroxyfurane (THF) may be generated by the decomposition of PTMEG during the polycondensation reaction, and this THF is highly volatile and may cause appearance defects of molded products due to odor and gas generation during molding. . Therefore, in the present invention, to reduce the generation of THF as much as possible to depressurize for 1 hour from 760torr to 0.3torr, and gives the vacuum conditions of 0.3torr or less for the remaining 3-4 hours, the temperature of the reactor is 210 ℃ to 250 ℃ The temperature is raised for 2 hours, and the final temperature is maintained at 250 ° C. for 2 to 3 hours to complete the polycondensation.

The branched polyester-based elastomer (TPE-A) prepared through such a melt polymerization reaction is 30 to 45% by weight of aromatic dicarboxylic acid, 15 to 30% by weight of lower diol, 20 to 50% by weight of polyalkylene oxide, and Chemical Formula 1 It will contain 0.3 to 9.0% by weight of BPA-Alt-DBE oligomer represented by. TPE-A is obtained by predicting the molecular weight based on the torque applied to the stirrer of the polycondensation reactor. The molecular weight of the obtained thermoplastic elastomer resin (TPE-A) is represented by an intrinsic viscosity (hereinafter referred to as IV), and the intrinsic viscosity is 1.6 to 1.8 dl / when measured under a solvent of phenol (Phenol) / tetrachloroethane (TCE) = 50/50. has a value of g. If I.V. is less than 1.6 dl / g, a large amount of diisocyanate is required to obtain the extrusion properties when producing TPE-B, and the reaction extrusion time for obtaining the extrusion properties is longer. In addition, if it exceeds 1.8 dl / g, the number of hydroxy end to react with diisocyanate is small, leaving unreacted diisocyanate, which makes it difficult to produce a constant rate during molding.

TPE-A of the present invention has excellent elastic recovery and heat resistance as compared to TPE containing no BPA-Alt DBE oligomer. That is, TPE-A can be used for the inside of the automotive constant velocity joint boots that require high heat resistance by increasing the heat deformation temperature of the resin 20 ~ 30 ℃ compared to the TPE does not contain the BPA-Alt-DBE oligomer. Melt Index (Melt Index, MI) of TPE-A is preferably in the range of 13 ~ 17g / 10min, preferably 14 ~ 16g / 10min at 230 ℃, 2.16kg. Melt Index 13g / 10min. If less than a large amount of diisocyanate is required to obtain the extrusion properties when the TPE-B is produced, and the reaction extrusion time for obtaining the extrusion properties is longer. And also 16g / 10min. If exceeded, the number of hydroxy terminal to react with diisocyanate is small, leaving unreacted diisocyanate, which makes it difficult to produce a constant rate when forming a product.

In addition, since BPA-Alt-DBE oligomer lowers the melting temperature of TPE-A, it is excellent in workability because the molding temperature is lower during molding after extrusion compared to TPE polymerized only with aromatic dicarboxylic acid, lower diol and polyalkylene oxide. However, TPE-A by itself still has low melt viscosity or melt tension and does not have optimal properties for extrusion blowing for constant velocity joint boots or bellows.

The increase in molecular weight and cross linking degree of TPE-A leads to an increase in melt viscosity and an increase in melt tension, thereby making it possible to have excellent extrusion characteristics. Therefore, in the present invention, by adding a diisocyanate, a hydroxycarboxylic acid compound, and a hydrolysis agent carbodiimide, which is a chain extender during the reaction extrusion, as a means for increasing the molecular weight and the degree of crosslinking of the TPE-A prepared by the above method, By improving, the thermoplastic elastomer resin (hereinafter TPE-B) of the present invention was produced. That is, when the chain extender diisocyanate, the hydroxycarboxylic acid compound, and the hydrolysis agent carbodiimide are reacted together with TPE-A, the reaction rate of the diisocyanate and carbodiimide can be increased.

Examples of the hydroxycarboxylic acid compound include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polycyclohexane terephthalate (PCT), polybutylene terephthalate (PBT), and the like. Can be. Among PET, PEN, PBN and PCT, it is preferable to have intrinsic viscosity (IV) in the range of 0.5 to 1.0 dl / g, and in order to obtain extrusion characteristics when preparing TPE-B when the intrinsic viscosity is less than 0.5 dl / g. A large amount of diisocyanate is required and the reaction extrusion time for obtaining extrusion characteristics is longer. In addition, if it exceeds 1.0dl / g, the number of hydroxyl end to react with diisocyanate is small, leaving unreacted diisocyanate, making it difficult to produce a constant rate during product molding.

As PBT, those having an intrinsic viscosity of 0.7 to 1.3 dl / g, preferably 0.75 to 1.1 dl / g, more preferably 0.8 to 0.9 dl / g, and having the structure of Formula 2 are used. When the intrinsic viscosity of PBT is less than 0.7 dl / g, a large amount of diisocyanate is required in order to obtain extrusion characteristics when preparing TPE-B, and the reaction extrusion time for obtaining extrusion characteristics becomes longer. In addition, when it exceeds 1.3 dl / g, the number of hydroxyl end to react with diisocyanate is small, leaving unreacted diisocyanate, making it difficult to produce a constant rate during product molding.

N is a positive integer of 70-100, Preferably it is 80-90.

The hydroxycarboxylic acid compound content in TPE-B is used in the range of 3 to 28% by weight, preferably 3 to 25% by weight, more preferably 3 to 20% by weight. When the content of the hydroxycarboxylic acid compound is less than 3% by weight, it is difficult to expect complete reactivity of the diisocyanate and carbodiimide, and when it exceeds 28% by weight, the low temperature impact resistance of the elastomer is significantly lowered.

The diisocyanate as a chain extender is used in an amount of 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight, more preferably 1.0 to 2.5% by weight. As diisocyanate, toluene diisocyanate, 4, 4- diphenylmethane diisocyanate, its modified substance, a mixture thereof, etc. can be used. However, 4,4-diphenylmethane diisocyanate may have low reactivity due to reaction with moisture, and is not easy to store, so it is not easy to control property deviations per lot of the product during extrusion reaction. Preference is given to using modified substances of methane diisocyanate. The modified form of 4,4-diphenylmethane diisocyanate is a mixture of 4,4-diphenylmethane diisocyanate represented by the formula (3) and carbodiimide diisocyanate represented by the formula (4), more preferably 4,4- It contains 95 to 99 weight% of diphenylmethane diisocyanate, and 1 to 5 weight% of carbodiimide diisocyanate.

Modified product of 4,4-diphenylmethane diisocyanate is maintained at room temperature in the liquid phase, so it is easy to add during extrusion and excellent long-term storage properties can minimize the properties of each lot of the product. In addition, it is possible to expect a greater increase in melt viscosity and formability even at a lower dosage compared to 4,4-diphenylmethane diisocyanate in the form of monomer, and it also contains some carbodiimide to further reduce the amount of hydrolysis agent. Can be.

On the other hand, carbodiimide satisfies the durability required for automobile parts such as constant velocity joint boots and bellows as a hydrolysis agent. In the present invention, carbodiimide as the hydrolysis agent is used at 0.05 to 1.0% by weight, preferably 0.1 to 0.8% by weight, more preferably 0.2 to 0.5% by weight. When the amount of carbodiimide is less than 0.05% by weight, it is difficult to obtain hydrolysis characteristics, and when it exceeds 1.0% by weight, there is a problem in processing due to crosslinking.

In addition, the thermoplastic elastomer resin according to the present invention may include other additives such as heat stabilizers, antioxidants, lubricants, silicon-based master batch, carbon black master batch (Carbon Black Master Batch).

The thermoplastic elastomer resin (TPE-B) is produced by reaction extrusion, and the residence time in the extruder at the time of manufacture is preferably 50 to 80 seconds, in particular 50 to 60 seconds, the temperature is 170 to 240 ℃, the screw rpm is 100 It is preferable that it is -300 rpm.

The thermoplastic elastomer resin (TPE-B) of the present invention prepared in this way is TPE-A 66-96.85% by weight, hydroxycarboxylic acid compound 3-28% by weight, diisocyanate 0.1-5.0% by weight, and carbodiimide 0.05- It will contain 1.0% by weight. In addition, the thermoplastic elastomer resin (TPE-B) of the present invention exhibits physical properties of melt index ratio (MIR) 1.0 to 1.5, melt tension of 40 mN or more, melt viscosity of 40,000 poise or more, and heat distortion temperature (HDT, Heat Distortion Temperature) of 75 ° C. It has the characteristics of having the above heat resistance.

Hereinafter, the present invention will be described in more detail based on the following Examples and Comparative Examples. However, these Examples and Comparative Examples are only for illustrating the present invention, and the scope of the present invention in any sense is not limited thereto.

Example 1

34.6% by weight of DMT, 21.2% by weight of 1,4-butanediol, 40.2% by weight of PTMEG having a molecular weight of 2,000, 3.8% by weight of BPA-Alt-DBE oligomer (n = 1) and 0.065% by weight of glycerol were placed in an oligomerization reactor and TBT as a catalyst. 0.025% by weight was added. The reaction temperature is in the range of 140 to 215 ° C., and the temperature is raised from 140 ° C. to 215 ° C. for 120 minutes, and the reaction is carried out for 120 minutes while maintaining 215 ° C. to convert the amount of methanol, which is a reaction effluent, into a reaction rate. The reaction was terminated. Thereafter, 0.04% by weight of a catalyst TBT and 0.07% by weight of a heat stabilizer Irganox 1010 were added to carry out a polycondensation reaction. The polycondensation reaction was performed by increasing the temperature from 215 ° C to 250 ° C for 120 minutes and reacting for the remaining 120 minutes while maintaining 250 ° C. At this time, the pressure was reduced for 1 hour from 760torr to 0.3torr, and the remaining 3 hours were vacuum conditions of 0.3torr or less. To, but the final reduced pressure was adjusted to 0.3torr or less to prepare TPE-A. The physical properties of the TPE-A thus prepared were measured and shown in Table 2.

The TPE-A prepared as described above was subjected to reaction extrusion using an extruder having a twin screw. Mainly composed of 93% by weight of TPE-A and 3.0% by weight of PBT, 4,4-diphenylmethane diisocyanate modified compound (n = 1, 4,4-diphenylmethane diisocyanate) of formula (3) to obtain desirable extrusion characteristics 95% by weight, 5% by weight of carbodiimide diisocyanate), 1.0% by weight, and 0.2% by weight of carbodiimide were simultaneously introduced into the extruder, and 0.5% by weight of heat stabilizer, 0.5% by weight of antioxidant, 0.5% by weight of lubricant, and silicone-based master 0.6 wt% of the batch and 0.7 wt% of the Carbon Black Master Batch were added to make the whole 100 wt%, and reaction extrusion was performed. At this time, the conditions in the twin screw extruder were adjusted to a temperature of 170 ~ 240 ℃, screw rpm 100 ~ 300rpm, residence time 50 ~ 60 seconds, the composition and physical properties of the TPE-B obtained in this way are shown in Tables 1, 3, 4 below It was.

Example 2

Prepared in the same manner as in Example 1, except for using the BPA-Alt-DBE oligomer (n = 2) was prepared in the same manner as in Example 1 TPE-A, TPE-B was measured by physical properties. .

Example 3

Prepared in the same manner as in Example 1, except that the use of BPA-Alt-DBE oligomer (n = 3) was prepared in the same manner as in Example 1 TPE-A, TPE-B was measured by physical properties. .

Example 4

Prepared in the same manner as in Example 1, except that the BPA-Alt-DBE oligomer (n = 4) was used in the same manner as in Example 1 TPE-A, TPE-B was prepared to measure the physical properties. .

Example 5

Prepared in the same manner as in Example 1, except for using the BPA-Alt-DBE oligomer (n = 5) was prepared in the same manner as in Example 1 TPE-A, TPE-B was measured by physical properties. .

Example 6

The reaction was carried out in the same manner as in Example 1, except that 76 wt% of TPE-A prepared in the same manner as in Example 1, and 20 wt% of PBT were used, and the composition of TPE-B thus obtained was obtained. And physical properties are shown in Tables 1, 3, and 4 below.

Example 7

TPE-A was prepared in the same manner as in Example 1, but in the oligomerization reaction, 36.3 wt% of DMT, 23.4 wt% of 1,4-butanediol, 39.7 wt% of PTMEG having a molecular weight of 2,000, and BPA-Alt-DBE oligomer (n = 1 0.4% by weight and 0.065% by weight of glycerol were placed in an oligomerization reactor and 0.025% by weight of TBT was added as a catalyst. Thereafter, in the polycondensation reaction, 0.04% by weight of the catalyst TBT and 0.07% by weight of the heat stabilizer Irganox 1010 were added to perform the polycondensation reaction. TPE-B was manufactured by the same composition as the manufacturing method of TPE-B of Example 1 using TPE-A obtained in this way. The composition and physical properties of the obtained TPE-B are shown in Tables 1, 3, and 4 below.

Example 8

TPE-A was prepared in the same manner as in Example 1, except that in the oligomerization reaction, 33.1 wt% DMT, 19.3 wt% 1,4-butanediol, 40.6 wt% PTMEG having a molecular weight of 2,000, and BPA-Alt-DBE oligomer (n = 1 6.8% by weight) and 0.059% by weight of glycerol were placed in an oligomerization reactor and 0.028% by weight of TBT was added as a catalyst. Thereafter, in the polycondensation reaction, 0.043% by weight of the catalyst TBT and 0.07% by weight of the heat stabilizer Irganox 1010 were added to perform the polycondensation reaction. TPE-B was manufactured by the same composition as the manufacturing method of TPE-B of Example 1 using TPE-A obtained in this way. The composition and physical properties of the obtained TPE-B are shown in Tables 1, 3, and 4 below.

Example 9

TPE-A was prepared in the same manner as in Example 1, except that PBT was used as PEN in preparing TPE-B, and the same reaction as in Example 1 was carried out, and the composition of TPE-B thus obtained was And physical properties are shown in Tables 1, 3, and 4 below.

Example 10

It was prepared in the same manner as in Example 1, except that PBN was used instead of PBT when preparing TPE-B, and was reacted in the same manner as in Example 1, and the composition and physical properties of TPE-B thus obtained were as follows. Tables 1, 3, and 4 are shown.

Example 11

Prepared in the same manner as in Example 1, except that PCTG instead of PBT in the preparation of TPE-B The reaction was carried out in the same manner as in Example 1 except for the use. The composition and physical properties of the TPE-B thus obtained were shown in Tables 1, 3, and 4 below.

Example 12

Prepared in the same manner as in Example 1, except that 4,4-diphenylmethane diisocyanate was used as toluene diisocyanate in preparing TPE-B, and was reacted in the same manner as in Example 1. The composition and physical properties of TPE-B are shown in Tables 1, 3, and 4 below.

Comparative Example 1

96 wt% of TPE-A prepared in the same manner as in Example 1 was used, except that PBT was not used, and was reacted in the same manner as in Example 1, and the composition and physical properties of the TPE-B thus obtained were Are shown in Tables 1, 3, and 4 below.

Comparative Example 2

The reaction was performed in the same manner as in Example 1, except that 66 wt% of TPE-A prepared in the same manner as in Example 1 and 30 wt% of PBT were used. And physical properties are shown in Tables 1, 3, and 4 below.

Comparative Example 3

Without using diisocyanate and carbodiimide, other additives total 4.0% by weight (0.8% by weight thermal stabilizer, 1.2% by weight antioxidant, 0.5% by weight lubricant, 0.8% by weight silicone-based master batch and 0.7% by weight carbon black master batch The reaction was carried out in the same manner as in Example 1 except for the point used, and the composition and physical properties of TPE-B thus obtained are shown in Tables 1, 3, and 4 below.

Comparative Example 4

Without using diisocyanate, the total amount of other additives (3.8 wt% (0.8 wt% thermal stabilizer, 1.0 wt% antioxidant, 0.5 wt% lubricant, 0.8 wt% silicone-based master batch and 0.7 wt% carbon black master batch) was used. Except for the same reaction as in Example 1, the composition and physical properties of the TPE-B thus obtained are shown in Tables 1, 3, and 4.

Comparative Example 5

The reaction was carried out in the same manner as in Example 1 except that the residence time of the extruder was 40 seconds, and the composition and physical properties of the TPE-B thus obtained were shown in Tables 1, 3, and 4 below.

Comparative Example 6

96% by weight of the TPE obtained without adding the BPA-Alt-DBE oligomer was used and reacted in the same manner as in Example 1 except that no PBT was used. Physical properties are shown in Tables 1, 3, and 4 below.

Comparative Example 7

The reaction was carried out in the same manner as in Example 1, except that 93 wt% of the TPE obtained without adding the BPA-Alt-DBE oligomer was used, and the composition and physical properties of the TPE-B thus obtained were shown in Table 1, 3 and 4 are shown.

* TPE: TPE polymerized without adding BPA-Alt-DBE oligomer

** Other Additives: Thermal Stabilizer, Antioxidant, Lubricant, Silicone Masterbatch, and Carbon Black Masterbatch

PBT: n = 80 ~ 90, Samyang Corp. TRIBIT 1500

Diisocyanate: Lupranate MM103C from BASF

Carbodiimide: Stabaxol 1 from Bayer

Thermal Stabilizer: 412S from SHIPRO Kasei

Antioxidant: Songnox 1076 from Songwon Industrial

Lubricant: EP861 by HENKEL

Silicone masterbatch: MB-50-010 by DOW CORNING

Carbon Black Masterbatch: BKA2 from Hyunjin Chemical

1) Measuring temperature: 230 ℃, Load: 2.16kg

2) Recovery rate after annealing at 120 ° C for 20 hours

3)-: No Break

4) Melt viscosity at shear rate s ^-1

5) RT: room temperature

6) Strength at 400% tensile strength of specimens molded according to ASTM D638 Type 1

As can be seen from the contents of Tables 1, 3, and 4, Comparative Examples 1 and 6 do not contain PBT, and MIR is 1.0 or less as compared with Examples, resulting in processing problems, high processing temperature and high elasticity at high temperatures. The recovery rate is also low. Comparative Example 2 has a low impact strength at low temperatures and a higher processing temperature than Example 6. Example 6 and Comparative Example 2 show that the hardness can be adjusted during the reaction extrusion by increasing the PBT content. Comparative Examples 3 and 4 have no extrusion characteristics and show the same extrusion characteristics and mechanical strength as TPE-A. Comparative Example 5 shows a problem in processing similarly to Comparative Example 1.

The polyester thermoplastic elastomer resin prepared by melt polymerization using a BPA-Alt-DBE oligomer according to the present invention and reacted and extruded using a hydroxycarboxylic acid compound, diisocyanate, carbodiimide and other additives in an extruder has a melting point. As the degree and melt index is improved, the extrusion property is excellent, and the heat resistance, chemical resistance, and durability are excellent, so that it can be used in various parts such as automobile parts, especially constant velocity joint boots, and various bellows.

Claims (17)

Alternate copolymerization oligomer (BPA-Alt-DBE) of 30 to 45% by weight of aromatic dicarboxylic acid, 15 to 30% by weight of lower diol, 20 to 50% by weight of polyalkylene oxide, and bisphenol and dibromoethane represented by the following general formula (1) Oligomer) thermoplastic elastomer resin (TPE-A), characterized by containing 0.3 to 9.0% by weight: [Formula 1]

Wherein n is a positive integer from 1 to 5. The thermoplastic elastomer resin (TPE-A) according to claim 1, wherein the intrinsic viscosity (I.V) is 1.6 to 1.8 dl / g. The thermoplastic elastomer resin (TPE-A) according to claim 1, further comprising 0.05 to 0.10% by weight of glycerol. The method of claim 1, wherein the aromatic dicarboxylic acid is any one selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-dinaphthalene dicarboxylic acid, 2,6-dinaphthalene dicarboxylic acid, dimethyl terephthalate, and dimethyl isophthalate, or Thermoplastic elastomer resin (TPE-A), characterized in that a mixture thereof. The lower diol of claim 1, wherein the lower diol is ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 Thermoplastic elastomer resin (TPE-A), characterized in that any one selected from the group consisting of, 4-cyclohexanediethanol, or a mixture thereof. The thermoplastic elastomer resin (TPE-A) according to claim 1, wherein the polyalkylene oxide is any one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, or a mixture thereof. ). 66-96.85 weight% of TPE-A in any one of Claims 1-6, 3-28 weight% of hydroxycarboxylic acid compounds, 0.1-5.0 weight% of diisocyanate, and 0.05-1.0 weight% of carbodiimide Thermoplastic elastomer resin (TPE-B). The hydroxycarboxylic acid compound of claim 7, wherein the hydroxycarboxylic acid compound is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polycyclohexane terephthalate (PCT), and polybutylene terephthalate ( Thermoplastic elastomer resin (TPE-B), characterized in that any one selected from the group consisting of PBT), or mixtures thereof. The thermoplastic elastomer resin (TPE-B) according to claim 8, wherein the hydroxycarboxylic acid compound is polybutylene terephthalate (PBT) represented by the following formula (2). [Formula 2]

       In Formula 2 n is a positive integer of 70 to 100. The diisocyanate is a modified product of 4,4-diphenylmethane diisocyanate according to claim 7, wherein the diisocyanate is a mixture of 4,4-diphenylmethane diisocyanate represented by the following formula (3) and carbodiimide diisocyanate represented by the formula (4): Thermoplastic elastomer resin (TPE-B) characterized in that. [Formula 3]

[Formula 4]

The modified product of 4,4-diphenylmethane diisocyanate contains 95 to 99% by weight of 4,4-diphenylmethane diisocyanate and 1 to 5% by weight of carbodiimide diisocyanate. Thermoplastic elastomer resin (TPE-B). 8. The thermoplastic elastomer resin (TPE-B) according to claim 7, wherein the melt index ratio (MIR) is 1.0 to 1.5. The thermoplastic elastomer resin (TPE-B) according to claim 9, wherein the intrinsic viscosity of the PBT is 0.7 to 1.3 dl / g. (a) 30 to 45% by weight of aromatic dicarboxylic acid, 15 to 30% by weight of lower diol, 20 to 50% by weight of polyalkylene oxide and alternating copolymerization oligomer of bisphenol and dibromoethane as defined in claim 1 (BPA-Alt -DBE oligomer) melt-polymerized 0.3 to 9.0% by weight to prepare TPE-A; And (b) reaction extrusion of 66 to 96.85% by weight of TPE-A prepared in (a), 3 to 28% by weight of hydroxycarboxylic acid compound, 0.1 to 5.0% by weight of diisocyanate, and 0.05 to 1.0% by weight of carbodiimide. Method for producing a thermoplastic elastomer resin (TPE-B) characterized in that it comprises a step of producing a TPE-B. 15. The method of claim 14, wherein the diisocyanate is a modification of 4,4-diphenylmethane diisocyanate as defined in claim 10. The method according to claim 14, characterized in that the step (a) further comprises 0.05 to 0.10% by weight of glycerol. 15. The process according to claim 14, wherein the residence time in the extruder in step (b) is between 50 and 80 seconds.