KR950008897B1 - Poly ether ester block copolymer resin composition - Google Patents

Abstract

The copolymer composition enhances working properties such as melt strength. The copolymer comprises A)60-00wt.% of polyether ester copolymer which is polymerized of polyetherester block copolymer composed of hard segment of formula(I) and segment of (II), and a crosslinking agent; and B)polyether ester block copolymer resin with 1-40wt.% of ethylene/propylene compd. The above cross linking agent contains prim. or sec. amine compd. essentially, and is selected from dimethylamine, diethylamine, hexamethylene bis(aminoacetic acid), trypsin, D or D,L-serin, D,L-treonin hemihydrate, D,L-aspaltic acid, 2-aminoadipic acid, and tris(hydroxymethyl)aminomethane.

Description

Polyetherester Block Copolymer Resin Composition

The present invention relates to a polyetherester block copolymer resin composition having improved processing characteristics.

In general, the polyether ester block copolymer is used as a substitute for the conventional rubber material because of its excellent flexibility and elastic recovery ability, and is particularly promising for automotive parts because it has excellent moldability and excellent heat resistance compared to vulcanized rubber.

In particular, the bellows type boot to protect the power transmission joint of the vehicle is not only close to the engine but also a high-speed rotation part, so there are many problems that need to be frequently replaced when using vulcanized rubber lacking heat resistance. Research on the polyether ester block copolymer resin composition is actively progressing.

However, the polyether ester block copolymer resin has excellent heat resistance and softness characteristics in itself, but has a disadvantage of low melt strength due to the polyether component added to improve the rubber properties of the copolymer. Unsuitable for processing requiring higher melt strength, such as molding.

Various methods have been proposed in order to solve the limitation of the molding process of such a polyether ester block copolymer.

U.S. Patent No. 4,013,624 discloses a method for preparing a polyetherester block copolymer resin having improved melt strength by copolymerizing a crosslinking agent with a polyfunctional group having 3 to 6 hydroxy groups and a carboxyl group, but in a polyether ester tube It is difficult to discharge the low-molecular-weight volatile reaction product generated during the polycondensation reaction out of the reaction system due to the high melt viscosity at, thereby increasing the degree of polymerization and separating bubbles.

A method for improving the melt strength of a polyetherester block copolymer by adding 0.2 to 20% by weight of a metal salt compound of an ethylene / carboxylic acid copolymer after preparing the polyetherester block copolymer is disclosed in US Pat. No. 4,010,222. However, the polyetherester block copolymer prepared by this method has low compatibility between the polyetherester polymer and the ethylene / carboxylic acid copolymer, thereby lowering the synergistic effect of the melt strength and adding the amount of the ethylene / carboxylic acid copolymer. If there is more, the rubber properties of the block copolymer is reduced.

In addition, a method of using a crosslinking agent added to a polyether ester block copolymer in addition to a hydroxy group and a carboxyl group is disclosed in US Pat. No. 4,914,178, but there is a problem in that the melt strength improvement effect is insufficient.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a polyether ester block copolymer resin composition having a high effect of improving the melt strength without deteriorating rubber properties.

In order to achieve the above object, the present invention provides (A) a polyetherester block copolymer composed of a hard segment represented by the following structural formula (I) and a segment represented by the structural formula (II) and a primary or secondary amine 60 to 99% by weight of polyether ester copolymer polymerized with a crosslinking agent containing a compound as an essential component

(In the above formula (I), R is a terephthalic acid or a lower alkyl esterified product thereof, or an aromatic dicarboxylic acid adipic acid, sebacic acid, dimer acid or the like such as isophthalic acid, old phthalic acid, naphthalenedicarboxylic acid form, etc.). Aliphatic dicarboxylic acids, such as the form, or cycloaliphatic dicarboxylic acid, such as cycloaliphatic, dicarboxylic acid mixtures can be used, D is an aliphatic glycol component having 2 to 8 carbon atoms are used, mainly 1.4-butanediol Ethylene glycol, 1,2- or 1.3-propylene glycol, 1.5-pentanediol, 1.6-nucleic acid diol, 1.4-cyclonucleodimethanol, and the like can be mixed and used in the formula (II). R is the same as that of the structural formula (I), G is the polyalkylbene oxide glycol component whose molecular weight is 300-6000, The poly (tetramethylene oxide) glycol is mainly used, Groups may be the polyethylene glycol or propylene glycol polreu used alone or in a mixture form.)

(B) The polyether ester block copolymer resin composition which melt-mixed 1-40 weight% of ethylene / propylene compounds is provided.

In this invention, a crosslinking agent is added in 0.1-1.0 mol% with respect to the said Formula R component in the mixture of the primary or secondary amine alone or with the compound which consists of a hydroxyl group or a carboxyl group.

Said crosslinking agent is dimethylamine, diethylamine, nucleomethylenebis (aminoacetic acid), trypsin, D or D, L-serine, D, L- threonine hemihydrate, D, L-asphatic acid, 2-amino Compounds having amine groups such as adipic acid, tris (hydroxymethyl) aminomethane, or the like or hydroxy groups such as nuxaglycerol, trimellitic acid, trimellitic anhydride, pentaerythritol, glycerin acid, gluconic acid, and glutheptoninic acid It can be used in combination with a crosslinking agent consisting of only.

When the content of the crosslinking agent is less than 01. mol% with respect to the R component, it is not expected to improve the melt viscosity. When the crosslinking agent is more than 10.mol%, the melt viscosity is excessively increased, making it difficult to discharge volatile reaction products in the reaction system, resulting in bubbles or poor polymerization. do.

In this invention, the polyether ester copolymer superposed | polymerized with the said crosslinking agent melt-mixes the ethylene-propylene compound further 1-40 weight%, and its melt viscosity further raises.

The melt viscosity of the final resin composition is affected by the amount of the ethylene / propylene compound added. Preferable addition amount is 1 to 40 weight%, More preferably, it is 3 to 25 weight%. In addition, the dispersed state of the ethylene / propylene compound is advantageous to increase the melt viscosity as the ethylene / propylene component is uniformly dispersed into small domains in the polyether ester resin.

If the content of ethylene / propylene is 3% by weight or less, it is difficult to expect a desired improvement in melt viscosity. If the content of ethylene / propylene is 25% by weight or more, the melt viscosity may be too low, resulting in poor workability or reduced mechanical properties.

The polyether ester block copolymer resin composition prepared according to the present invention has a polyether ester block copolymer resin having a polyether ester block copolymer resin composition obtained by heat-melting and mixing a metal salt of a conventional ethylene / carboxylic acid copolymer. The effect of improving melt strength is great without compromising the inherent superior properties.

The polyetherester block copolymer resin composition produced by this invention has a melting point sufficient to be processed into a hose, tube, sheet, or hollow container or boot, which can be produced by extrusion molding, or a hollow container or boot, which can be produced by extrusion molding. Has a degree.

Next, a preferred embodiment of this invention is presented.

However, these examples are only provided to more easily understand the present invention, and the present invention is not limited to these examples.

Example 1

33.0% by weight of dimethyl terephthalate, 26.8% by weight of 1,4-butanediol, 40.0% by weight of poly (tetramethylene oxide) glycol having an average molecular weight of 1000, 0.1% by weight of tetrabutyl titanate, and aganox in an ester reaction tube equipped with a stirrer. 0.1 wt% of 1010 (Ciba-Gage, Switzerland) and 0.3 mol% of 2-amino adipic acid were added to dimethyl terephthalate to raise the temperature of the reaction tube to 200 ° C. for 1 hour at 1 ° C., and then to 1 at 200 ° C. The reaction was carried out for 30 minutes to allow methanol to flow out of the reaction tube.

When the outflow of methanol was completed, the pressure was slowly reduced for 1 hour to lower the pressure in the tube to 100 mmHg and to raise the temperature of the reaction tube to 250 ° C.

The polycondensation reaction was carried out at 250 ° C. for 1 hour, and nitrogen was added to granulate the polyether ester block copolymer at a pressure of 1.5 kg / cm 2.

The polyetherester block copolymer was heated and dried at 110 ° C. for 6 hours to remove moisture, followed by 95% by weight of the polyetherester block copolymer, an ethylene / propylene compound (trade name: Axle V A 1803, USA Exxon Petroleum). 5% by weight and 0.5% by weight of Iganox-1010 (Shiba-Gage, Switzerland) with respect to the initial amount of the resin is added to a twin-screw thermomelting kneader, and the temperature of the kneader is 150 ° C, 180 ° C, The polyether ester block copolymer resin composition of this invention which was desired by melt-kneading to 200 degreeC, 200 degreeC, and 200 degreeC was produced.

The polyether ester block copolymer resin composition was vacuum dried at 110 ° C. for 6 hours, and then a test specimen was manufactured in an injection molding machine. The molarity was measured by the following method, and the results are shown in Table 2 below.

Example 2

Except that 88% by weight of the polyether ester block copolymer in Example 1, 12% by weight of the ethylene / propylene compound in the same manner as in Example 1, the results are shown in Table 2.

Example 3

In Example 1, the polyether ester block copolymer was treated in the same manner as in Example 1, except that 90 wt% of T ₂ of Table 1 and 10 wt% of the ethylene / propylene compound were used. The results are shown in Table 2.

Example 4

Except that the polyetherester block copolymer in Example 1 to 80% by weight as T ₂ of Table 1, and 20% by weight of the ethylene / propylene compound in the same manner as in Example 1 The results are shown in Table 2.

Example 5

Except that the polyetherester block copolymer in Example 1 as T ₃ of Table 1 and 85% by weight, 15% by weight of the ethylene / propylene compound was treated in the same manner as in Example 1 and the results Table 2 shows.

Example 6

Except that the polyetherester block copolymer in Example 1 as T ₃ of Table 1 and 75% by weight, 25% by weight of the ethylene / propylene compound in the same manner as in Example 1 was the result Table 2 shows.

Comparative Example 1

Except that the polyetherester block copolymer in Example 1 as T ₁ of Table 1 99% by weight, ethylene / propylene compound 1% by weight was treated in the same manner as in Example 1 and the results Table 2 shows.

Comparative Example 2

Except that the polyetherester block copolymer in Example 1 as T ₁ in Table 1 60% by weight, 40% by weight of the ethylene / propylene compound in the same manner as in Example 1 and the results Table 2 shows.

Comparative Example 3

Except that the polyetherester block copolymer in Example 1 as T ₄ of Table 1 88%, 12% by weight of the ethylene / propylene compound in the same manner as in Example 1 and the results Table 2 shows.

[Assessment Methods]

1. Tensile strength: measured by ASTM D-638 method and expressed in units of kg / ㎠.

2. Elongation: measured by ASTM D-258 method and expressed in%.

3. Impact strength: measured by ASTM D-258 method and expressed in kg · ㎝ / ㎝ unit.

4. Flexural modulus: measured by ASTM D-790 method and expressed in kg / cm 2 unit.

5. Melt viscosity: Measured by a viscometer (Model name: Rheometrics RDS-770) at 25 ° C., and expressed in poise units.

As shown in the results of Table 1 above, when no crosslinking agent was added (T), the melt viscosity was 920, compared to 2700 to 3800 poises of the polyether ester copolymer having a composition of T to T using the crosslinking agent as in the present invention. It can be seen that the desired purpose of improving the melt viscosity of the polyetherester copolymer by the addition of the crosslinking agent of this invention was achieved.

Furthermore, when 5 to 25% by weight of an ethylene / propylene compound is added to the polyether ester copolymer to which the crosslinking agent is added (Examples 1 to 6), the flexural modulus is not impaired without damaging the original mechanical properties of the polyether ester block copolymer. It can be seen from Table 2 that the melt viscosity can be further improved.

Claims (5)

In the polyetherester block copolymer resin composition with improved melt viscosity, (A) a polyetherester block copolymer comprising a hard segment represented by the following structural formula (I) and a segment represented by the structural formula (II), and 1 60-99 weight% of polyether ester copolymers which superposed | polymerized the crosslinking agent which makes a primary or secondary amine compound an essential component, (In the above formula (I), R is a form of terephthalic acid or its lower alkyl ester alone or aromatic dicarboxylic acid adipic acid, sebacic acid, dimer acid, such as isophthalic acid, old phthalic acid, naphthalenedicarboxylic acid form, etc.) Aliphatic dicarboxylic acids such as aliphatic or cyclohexane dicarboxylic acid, such as cycloaliphatic dicarboxylic acid, and mixtures with dicarboxylic acid may be used, D is an aliphatic glycol component having 2 to 8 carbon atoms are used mainly 1.4-butanediol Ethylene glycol, 1,2- or 1.3-propylene glycol, 1.5-pentanediol, 1.6-nucleic acid diol, 1.4-cyclonucleic acid dimethanol and the like can be mixed, and R in the formula (II) The same as in the formula (I), G is a polyalkylbenoxide glycol component having a molecular weight of 300 to 6000 is used, mainly poly (tetramethylene oxide) glycol, A polyethylene glycol or polypropylene glycol can be used alone or in a mixture form.) (B) Polyether ester block copolymer copolymer composition which melt-mixed 1-40 weight% of ethylene / propylene compounds. The composition according to claim 1, wherein the crosslinking agent is added in an amount of 0.1 to 1.0 mol% based on the above R component. The crosslinking agent according to claim 1 or 2, wherein the crosslinking agent is dimethylamine, diethylamine, hexamethylene bis (aminoacetic acid), trypsin, D or D, L-serine, D, L-threonine hemidate, D, L- A composition comprising an amine compound selected from aspartic acid, 2-aminoadipic acid and tris (hydroxymethyl) aminomethane. The composition according to claim 3, wherein the crosslinking agent is further added with at least one compound selected from hexaglycerol, trimellitic acid, trimellitic anhydride, pentaerythritol, glycerin acid, gluconic acid and gluheptoninic acid. The composition of claim 1, wherein the ethylene / propylene compound is added in an amount of 3 to 25% by weight.