KR100830105B1 - Polyetherester block copolymer resin composition - Google Patents

Abstract

According to the present invention, there is provided a polyetherester block copolymer resin composition having a melt flow index of 10 to 25 g / 10 min, measured at a temperature of 200 ° C. and a load of 2160 g, and the composition having such characteristics is a polyether ester. It can be prepared by incorporating an appropriate amount of a specific siloxane compound and a phosphorus compound into the block copolymer resin, and has excellent melt flowability suitable for extrusion molding and excellent flexibility and elastic recovery ability, which are inherent to the polyether ester block copolymer resin. It has excellent heat resistance and is very suitable for automotive parts such as extruded wire sheathing, power transmission boot and cooling water circulation tube.

Description

Polyetherester Block Copolymer Resin Composition {POLYETHERESTER BLOCK COPOLYMER RESIN COMPOSITION}

 The present invention relates to a polyether ester copolymer resin composition, and more particularly, to a polyether ester block copolymer resin composition excellent in extrudability.

In general, polyether ester block copolymers are used as a substitute for conventional rubber materials because of their excellent flexibility and elastic recovery. Especially, they have excellent moldability and excellent heat resistance compared to vulcanized rubbers. It is a material that is widely used for automobile parts such as circulation tubes.

The thermoplastic polyether ester block copolymers have been applied to various applications such as high-stretch fibers and injection products, and these days, they are also applied to extrusion molding under more extreme conditions, and thus have high melt viscosity and high melt strength. The required melt flow index is required for extrusion.

Conventionally, the polyether ester block copolymer resin mainly uses terephthalic acid as an acid component and also uses isophthalic acid and other aliphatic saturated dicarboxylic acids in combination, and diols in hard segment units mainly include ethylene glycol and 1,4-butanediol. In use, other aliphatic diols were used in combination with this, and the diol components of the soft segment were mainly manufactured using polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Due to the poor thermal stability at high temperatures, it is restricted in use, and the mechanical strength and elastic recovery force are reduced due to the lack of absolute amount of crystal region that can concentrate stress and recover when external force is applied as well as stability of soft segment. Degraded.

In addition, the polyether ester block copolymer resin has excellent heat resistance and softness as it is, but has a disadvantage of low melt strength due to the polyether component added to improve the rubber properties of the copolymer. It does not have melt flowability that requires extrudability.

In order to solve the limitation of the molding process of such a polyether ester block copolymer resin, various methods have been proposed.

U.S. Patent No. 4,013,624 discloses a method of preparing a PEL resin having improved melt strength by copolymerizing a cross-linking agent of 3 to 6 hydroxy groups with a carboxyl group, but having a high melt viscosity in a polyether ester tube. The low molecular weight volatile reaction product generated during the polycondensation reaction is difficult to discharge out of the reaction system, so that the increase in the degree of polymerization is disadvantageous and bubbles are not generated, and the melt flowability required by the present invention is not provided.

US Patent No. 4,010,222 discloses a method for improving the melt strength of a polyetherester block copolymer by melt-adding 0.2 to 20% by weight of a metal salt compound of an ethylene / carboxylic acid copolymer after the preparation of the polyetherester block copolymer. However, the polyetherester block copolymer prepared by this method has a low compatibility between the polyetherester polymer and the ethylene / carboxylic acid copolymer, thereby lowering the synergistic effect of the melt strength, and Increasing the amount of addition decreases the rubber properties of the block copolymer, which leads to a problem of insufficient melt flowability during extrusion molding.

In addition, a method of adding a crosslinking agent having a hydroxy group and a carboxyl group as a crosslinking agent to a polyether ester block copolymer is disclosed in US Pat. No. 4,914,178.

Accordingly, an object of the present invention is to provide a polyether ester block copolymer resin composition having a melt flow property of a degree required for extrusion molding.

In the study of the present inventors to achieve the above object, the polyetherester block copolymer resin composition has a melt flow index of 10 to 25 g / 10 min under a measurement condition of a temperature of 200 ° C. and a load of 2160 g. It is also found that the composition of the above characteristics can be prepared by adding a certain amount of a specific siloxane compound and phosphorus compound during melt polymerization of the polyether ester block copolymer. Will be completed.

Therefore, according to the present invention, there is provided a polyetherester block copolymer resin composition for extrusion molding, characterized in that a melt flow index measured at a temperature of 200 ° C. and a load of 2160 g is 10 to 25 g / 10 min. .

In addition, according to the present invention, as one of the compositions satisfying the above characteristics, 0.01 to 0.05 parts by weight of the siloxane compound of Formula 1 and 0.03 to 0.1 parts by weight of the phosphorus compound of Formula 2 are contained based on 100 parts by weight of the polyether ester block copolymer resin. A polyetherester block copolymer resin composition is provided, characterized in that:

(Wherein R, R ₁ , R ₁ ', R ₂ and R ₂ ' are the same or different hydrogen or alkyl groups and n is an integer from 10 to 100.)

(Wherein R ₅ is hydrogen, methyl, ethyl, isopropyl, butyl or tertiary butyl, R ₆ is methylene or ethylene and M is sodium, potassium or lithium.)

In addition, according to the present invention, as one of the methods for the preparation of the composition, 0.01 to 0.05 of the siloxane compound of the formula (1) to 100 parts by weight of the polyether ester block copolymer resin at the time of melt polymerization of the polyether ester block copolymer Provided is a method for producing a polyetherester block copolymer resin composition, comprising adding parts by weight and 0.03 to 0.1 parts by weight of the phosphorus compound of formula (2).

Moreover, according to this invention, the electric wire coating containing said polyether ester block copolymer resin composition is provided.

 Hereinafter, the present invention will be described in more detail.

The composition of the present invention is characterized by a melt flow index (Melt Flow Index: MFI) of 10-25 g / 10 min, more preferably 15-20 g / 10 min, measured under conditions of a temperature of 200 ° C. and a load of 2160 g. If the MFI exceeds 25g / 10min, the flowability is too fast when the product is manufactured by extrusion molding (polymer flows too well), and it is impossible to maintain a predetermined shape after molding, in particular, to achieve a uniform thickness during extrusion molding. If the MFI is less than 10g / 10min, the extrusion pressure increases when manufacturing the extruded product, so that the polyether ester due to the wear of the extruder (or blow molding machine) and the increase of the processing temperature Degradation of the block copolymer leads to quality problems and productivity degradation.

One of the preferred embodiments of the polyether ester block copolymer resin composition satisfying the above properties is 0.01 to 0.05 parts by weight of the siloxane compound of Formula 3 and 0.03 to 0.05 parts by weight of the phosphorus compound of Formula 4 based on 100 parts by weight of the polyether ester block copolymer resin. 0.1 weight part mix | blends. The siloxane compound of the above-mentioned compounding ingredients increases the affinity between the polymers by coating the particle surface of the phosphorus compound to improve melt flow during extrusion molding. It can be combined with the end of, so that the affinity between the particles and the polymer is increased to make the melt flow uniform, and as a result, extrusion molding is possible.

It is preferable that the polyether ester block copolymer resin which becomes a main component of this composition is a block copolymer structure which has a hard segment repeating unit of Formula (1) and a soft segment repeating unit of Formula (2).

-O-D-O-C (O) -R-C (O)-

Wherein D is an aliphatic glycol having 2 to 8 carbon atoms or saturated alicyclic diol, and R is an ester forming component which can be derived from aromatic dicarboxylic acid, aliphatic dicarboxylic acid or alicyclic dicarboxylic acid.

-O-G-O-C (O) -R-C (O)-

In the above formula, G is a polyether component having a molecular weight of about 300 to 4000, and R is an ester-forming component which can be derived from aromatic dicarboxylic acid, aliphatic dicarboxylic acid or alicyclic dicarboxylic acid.

More preferably, in the formula (3), R is aliphatic such as terephthalic acid or its lower alkyl ester alone, or aromatic dicarboxylic acid such as isophthalic acid, old phthalic acid, naphthalenedicarboxylic acid form, adipic acid, sebacic acid, dimer acid or the like. Aliphatic dicarboxylic acid, such as dicarboxylic acid or cyclonucleic acid dicarboxylic acid, or a mixture thereof may be used. As D, an aliphatic glycol component having 2 to 8 carbon atoms is used, and 1.4-butanediol is mainly used, and ethylene is used here. Glycol, 1.2- or 1.3-propylene glycol, 1.5-pentanedi1.6-nucleic acid diol, 1.4-cyclonucleodimethanol, etc. can be mixed. In addition, in the repeating unit of Formula 2, R is the same as R of Formula 1, and G is a polyalkylene oxide glycol component having a molecular weight of 300-6000. A poly (tetramethylene oxide) glycol is mainly used. Polyethylene glycol or polypropylene glycol may be used alone or in a mixture.

On the other hand, it is preferable that the hard segment like the formula (3) is about 20 to 95% by weight of the entire polyether ester copolymer. The lower the hard segment content, the more rubber-like physical properties are. In addition, the physical properties of the final polymer are largely governed by the components of the polyether used. Poly (ethylene oxide) glycol is relatively more hydrophilic than poly (propylene oxide) glycol and poly (tetramethylene oxide) glycol. Although water resistance is lowered, it is advantageous in terms of oil resistance, and poly (propylene oxide) glycol and poly (tetramethylene oxide) glycol have excellent hydrophobicity and hydrolysis resistance since they are relatively hydrophobic than poly (ethylene oxide) glycol.

The thermoplastic polyether ester block copolymer has excellent flexibility and elastic recovery as rubber, but surpasses rubber in terms of low temperature impact resistance, chemical resistance and mechanical properties. Therefore, there is a characteristic that can exhibit the performance of both rubber side and plastic side. This superior performance and processability is due to the presence of thermoplastic crosslinks having excellent thermoplasticity instead of the low density crosslinking of rubber. However, since the ratio of the crosslinking decreases toward the flexible low hardness, problems such as heat resistance, weather resistance, thermal stability during processing, and melt flow during the extrusion molding process are particularly likely to occur.

In the present invention, the above-mentioned problems of the thermoplastic polyether ester block copolymer are solved by adding the siloxane compound of Formula 1 and the phosphorus compound of Formula 2. The siloxane compound of Formula 1 and the phosphorus compound of Formula 2 are preferably added during the melt polymerization of the thermoplastic polyether ester block copolymer. In particular, the phosphorus compound is preferably added in the transesterification step and the siloxane compound is added after the transesterification reaction.

For example, a melt polymerization process in which a terephthalate derivative, 1.4 butanediol and a poly (tetramethylene oxide) glycol having an average molecular weight of 1,000 are transesterified to remove an oligomer, and then polycondensed to produce a polyether ester block copolymer. In the present invention, the composition may be prepared by adding the siloxane compound of Formula 1 and the phosphorus compound of Formula 2. Specific examples of the method for producing such a composition will be described. Phosphorus-based compound 0.03-with respect to 100 parts by weight of terephthalate derivative, 1.4 butanediol and poly (tetramethylene oxide) glycol, polyether ester block copolymer resin in a conventional polyester reaction tube. 0.1 parts by weight of a catalyst, a thermal stabilizer, and other reactive ingredients were added, and a polyether ester block copolymer was removed by a transesterification reaction in which methanol or water was allowed to flow out as an equivalent of an acid component while heating to 200 to 300 ° C. 0.01 to 0.05 parts by weight of the siloxane compound is added to 100 parts by weight of resin, and the reaction tube temperature is heated to 250 to 280 ° C. while the pressure is gradually increased to 5 mmHg or less. Can be.

At this time, tetraalkyl titanate alone or a mixture of magnesium or calcium acetate may be used as the reaction catalyst, and titanate such as Mg [HTi (OR) ₆ ] ₂ generated from an alkoxide compound of an alkali earth metal and an ester compound of titanate. Inorganic titanate compounds such as complex compounds and lanthanum titanates, mixtures of calcium acetate and antimony trioxide, lithium and magnesium acetate also exhibit excellent polymerization catalyst performance.

In the present composition, the silonic acid-based compound of formula 1 is preferably 0.01 to 0.05 parts by weight based on 100 parts by weight of the polyether ester block copolymer, because the resin composition in which the siloxane-based compound is added at less than 0.01 part by weight This is because the higher the quality problems due to the decomposition of the polyether ester block copolymer resin due to the extruder wear and processing temperature rise, and if the weight exceeds 0.05 parts by weight because the problem is that the reforming effect rather deteriorated.

In addition, the phosphorus-based compound of Formula 2 is preferably 0.03 to 0.1 parts by weight based on 100 parts by weight of the polyether ester block copolymer, because of the problem that the extrusion property is poor when the content of the phosphorus compound is less than 0.03 and 0.1 parts by weight. This is because when the melt polymerization reaction is exceeded, the melt polymerization is delayed and cannot be used because the melt polymerization is delayed, and the color of the polymer after melt polymerization becomes poor.

Normally, the color of a polymer is evaluated by the b value measured by a colormeter. In general, the b value after extrusion molding is yellowish than the b value after melt polymerization, and when used for extrusion, the b value should be 6 or less. It cannot be used for extrusion molding due to the color change of the molded product after extrusion after 6 seconds.

Features and other advantages of the present invention as described above will become more apparent from the following examples. However, the present invention is not limited to the following examples.

<Example 1>

33.3 parts by weight of dimethyl terephthalate, 19.7 parts by weight of 1.4-butanediol, and an average molecular weight of poly (tetramethylene oxide) glycol, based on 100 parts by weight of the polyether ester block copolymer resin (PEL), in a reaction tube for preparing a polyester having a stirrer. 40.5 parts by weight, 0.05 parts by weight of sodium 2,2'-methylene bis- (4,6-di-tert-butylphenyl) phosphate as a phosphorus compound of formula 2, 0.3 parts by weight of tetrabutyl titanate, and Iganox-1010 as a heat resistant agent 0.2 parts by weight of a Shiva-Gaigi company was added, and the reaction tube was heated at 200 ° C. for 1 hour at atmospheric pressure, reacted for 1 hour and 30 minutes, and a methanol exchanged out of the tube. Before poly reaction transfer, 0.02 parts by weight of polydimethylsiloxane, 0.01 parts by weight of lithium acetate, and 0.03 parts by weight of tetrabutyl titanate are added as the siloxane-based compound of Formula 1, and then discharged into a starghetti shape after condensation polymerization under high temperature vacuum. By cutting, a polyether ester block copolymer resin composition chip was prepared. After drying the prepared chip in a vacuum dryer at 110 ° C. for 6 hours, the melt flow index was measured at a temperature of 250 ° C. and a load of 2160 g according to the measuring method of ASTM D-1238, and the color b value and extrusion productivity of the chip were also evaluated. It was. The results are shown in Table 1.

<Evaluation method>

  Melt Flow Index (MFI) was measured according to ASTM D-1238 and the conditions are as follows. -Measuring machine company and model: TINIUS OLSEN (USA, MP987)

   Temperature: 200 ℃, Load 2160g                     

   -Orifice diameter 2.0 mm

Chip color b was measured using a colormeter (Minolta CR-200, Japan).

<Examples 2-3 and Comparative Examples 1-4>

Example 1 except that the contents of polydimethylsiloxane (PDS) and sodium 2,2'-methylene bis- (4,6-di-tert-butylphenyl) phosphate (SP) were changed as shown in Table 1 The same procedure was repeated. The melt flow index and extrusion productivity of each example are shown in Table 1.

division Ingredient Content (parts by weight / 100 parts by weight) result Remarks PDS SP MFI (g / 10min) b value Extrusion productivity Example 1 0.02 0.05 18 4.5 Good Example 2 0.01 0.09 15 5.5 Good Example 3 0.04 0.04 17 4.8 Good Comparative Example 1 0.005 0.05 8 4.6 Bad Not uniformly molded Comparative Example 2 0.02 0.02 7 4.8 Bad Comparative Example 3 0.02 0.15 11 9.5 Bad b Defects and foreign substances in molding Comparative Example 4 0.007 0.05 19 4.7 Good Decomposition of PEL resin during molding

As described above, the polyether ester block copolymer resin composition of the present invention has excellent melt and flow properties suitable for extrusion molding and has excellent flexibility, elastic recovery ability, and heat resistance, which are inherent characteristics of the polyether ester block copolymer resin, and extruded. It is a very suitable material for automotive parts such as wire sheathing, power transmission boot, and cooling water circulation tube.

Claims (4)

Polyetherester block copolymer resin composition WHEREIN: The melt flow index (Melt Flow Index) measured on the conditions of the temperature of 200 degreeC, and the load of 2160g is 10-25g / 10min, The polyetherester block copolymer for extrusion molding characterized by the above-mentioned. Resin composition. In the polyether ester block copolymer resin composition, 0.01 to 0.05 parts by weight of the siloxane compound of Formula 1 and 0.03 to 0.1 parts by weight of the phosphorus compound of Formula 2 are contained based on 100 parts by weight of the polyether ester block copolymer resin. Polyetherester block copolymer resin composition (Formula 1)

(Wherein R, R ₁ , R ₁ ', R ₂ and R ₂ ' are the same or different hydrogen or alkyl groups and n is an integer from 10 to 100.) (Formula 2)

(Wherein R ₅ is hydrogen, methyl, ethyl, isopropyl, butyl or tertiary butyl, R ₆ is methylene or ethylene and M is sodium, potassium or lithium.) In preparing the polyetherester block copolymer resin composition according to claim 2, 0.01 to 0.05 weight of the siloxane compound of the general formula (1) based on 100 parts by weight of the polyetherester block copolymer resin during melt polymerization of the polyetherester block copolymer. And 0.03 to 0.1 parts by weight of the phosphorus compound represented by the formula (2) is added. The electric wire coating containing the polyether ester block copolymer resin composition of Claim 1 or 2.