KR102076210B1 - Thermoplastic elastomer copolymer, thermoplastic resin composition comprising the same and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic elastomer copolymer, a thermoplastic resin composition and a molded article comprising the same, and more specifically, (a) a low molecular weight polyalkylene glycol and (b) a high molecular weight polyalkylene glycol by weight ratio (a: b) soft monomers comprising from 1: 1.1 to 1: 5; And a hard monomer comprising a polyester. The present invention relates to a thermoplastic elastomer copolymer, a thermoplastic resin composition and a molded article comprising the same, by melt polymerization.
According to the present invention, a thermoplastic elastomer copolymer prepared by including aliphatic polyethers having different number average molecular weights at a specific mixing ratio during melt polymerization, and by including them, has excellent blow moldability while maintaining equivalent durability or higher, and has a low temperature. There is an effect of providing a thermoplastic resin composition and a molded article excellent in flexibility.

Description

Thermoplastic elastomer copolymer, thermoplastic resin composition and molded article comprising the same {THERMOPLASTIC ELASTOMER COPOLYMER, THERMOPLASTIC RESIN COMPOSITION COMPRISING THE SAME AND MOLDED ARTICLE COMPRISING THE SAME}

The present invention relates to a thermoplastic elastomer copolymer, a thermoplastic resin composition and a molded article comprising the same, and more particularly, to a thermoplastic elastomer copolymer prepared by including a aliphatic polyether having a different number average molecular weight during melt polymerization in a specific mixing ratio, and The present invention relates to a thermoplastic resin composition and a molded article excellent in blow moldability and excellent in flexibility at low temperature while maintaining the durability of equivalent or more.

Conventionally, chloroprene rubber has been widely used as a material for automobile parts, especially for constant velocity joint boots, but since the chloroprene rubber is poor in durability, it is lighter than chloroprene rubber in recent years. Thermoplastic elastomer resins having excellent fatigue resistance, chemical resistance, and ozone resistance are emerging as alternative materials.

The constant velocity joint boots are generally manufactured by extrusion blow molding, and since the thermoplastic elastomer resin used therein is produced through a blowing process in the molten state, the melt viscosity in the molten state and It is required to have a good melt tension and to maintain a constant thickness distribution of the molded part while blowing.

However, in the case of the blow molded article according to the blow molding, the molding temperature conditions are different according to the size of the molded article, and the difference in the melt viscosity and the melt tension of the thermoplastic elastomer resin occurs excessively according to the molding temperature. There is a limit to the application. In addition, the thermoplastic elastomer resin is deteriorated in flexibility at low temperatures, the problem of losing its properties due to the lack of elastic recovery.

US 2011-0071240 A1

In order to overcome the problems of the prior art, the present invention provides a thermoplastic elastomer copolymer prepared by including a specific mixing ratio of aliphatic polyethers having different number average molecular weights during melt polymerization, and by including the same, thereby maintaining blow resistance while maintaining equivalent or higher durability. An object of the present invention is to provide a thermoplastic resin composition excellent in moldability and excellent in flexibility at low temperature.

Moreover, an object of this invention is to provide the molded article containing the said thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a soft (a) low molecular weight polyalkylene glycol and (b) a high molecular weight polyalkylene glycol (a: b) 1: 1.1 to 1: 5 soft) monomers; And a hard monomer comprising polyester; to provide a melt polymerized thermoplastic elastomer copolymer.

In another aspect, the present invention provides a thermoplastic resin composition comprising 80 to 99% by weight of the thermoplastic elastomer copolymer, 1 to 10% by weight chain extender, and 0 to 10% by weight additive.

The present invention also provides a molded article comprising the thermoplastic resin composition.

According to the present invention, a thermoplastic elastomer copolymer prepared by including aliphatic polyethers having different number average molecular weights at a specific mixing ratio during melt polymerization, and by including them, has excellent blow moldability while maintaining equivalent durability or higher, and has a low temperature. There is an effect of providing a thermoplastic resin composition and a molded article excellent in flexibility.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have improved blow moldability and flexibility at a low temperature in a wide temperature range of a thermoplastic resin composition, when the thermoplastic elastomer copolymer is prepared by including aliphatic polyethers having different number average molecular weights in a specific mixing ratio. It was confirmed that the present invention was completed based on this.

Looking at the thermoplastic elastomer copolymer according to the present invention in detail.

The thermoplastic elastomer copolymer may include (a) a low molecular weight polyalkylene glycol and (b) a soft monomer comprising a high molecular weight polyalkylene glycol in a weight ratio (a: b) of 1: 1.1 to 1: 5; And a hard monomer comprising a polyester.

The thermoplastic elastomer copolymer may include, for example, a soft segment derived from the soft monomer; And it may include a hard segment (hard segment) derived from the hard monomer.

The low molecular weight polyalkylene glycol (a) may be, for example, polyalkylene glycol having a number average molecular weight of 500 to 1,400 g / mol, 700 to 1,300 g / mol, or 800 to 1,200 g / mol. b) High molecular weight polyalkylene glycols may be, for example, polyalkylene glycols having a number average molecular weight of 1,500 to 3,000 g / mol, 1,500 to 2,500 g / mol, or 1,800 to 2,300 g / mol, each of the above ranges Blow moldability and flexibility at low temperatures over a wide temperature range within the effect is excellent.

Examples of the polyalkylene glycols of (a) and (b) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-1,2-butylene glycol, and polypentylene glycol, respectively. Lycol, polyhexylene glycol, polyheptylene glycol, polyoctylene glycol, polynonylene glycol and polydecylene glycol may be at least one selected from the group consisting of, preferably polypropylene glycol It may be lycol or polytetramethylene glycol, in which case the mechanical and balance properties are excellent.

The (a) low molecular weight polyalkylene glycol and (b) high molecular weight polyalkylene glycol are, for example, 1: 1.1 to 1: 5, 1: 1.2 to 1: 3, or 1: 1.5 to 1. It can be included in 1: 2, the glass transition temperature is moved to a low temperature within this range is excellent in flexibility at low temperatures.

For example, the soft monomer may be included in an amount of 30 to 70 wt%, 40 to 60 wt%, or 45 to 55 wt% with respect to the thermoplastic elastomer copolymer, and has excellent effects in durability and blow moldability within this range. .

The polyester may be derived from, for example, an aromatic dicarboxylic acid or an ester forming derivative thereof and an aliphatic diol, and specifically, esterification of an aromatic dicarboxylic acid with an aliphatic diol or an aromatic dicarboxylic acid ester formation. It may be derived from trans esterification of derivatives and aliphatic diols.

The aromatic dicarboxylic acid or ester-forming derivative thereof may be, for example, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, It may be at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate, dimethyl 1,4-cyclohexane dicarboxylate, preferably dimethyl terephthalate may be used. In this case, there is an excellent effect of mechanical and physical properties balance.

The aliphatic diol may be, for example, a lower aliphatic diol, and in particular, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol may be one or more selected from the group consisting of.

The polyester may be at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polycyclohexylenedimethylene terephthalate.

The hard monomer may include, for example, 30 to 70% by weight, 40 to 60% by weight, or 45 to 55% by weight based on the thermoplastic elastomer copolymer, and excellent mechanical properties and flexibility at low temperatures within this range. It works.

The thermoplastic resin composition according to the present invention is characterized in that it comprises 60 to 99% by weight of the thermoplastic elastomer copolymer, 1 to 10% by weight chain extender, and 0 to 10% by weight of the additive.

For example, the thermoplastic elastomer copolymer may be included in an amount of 80 to 99 wt%, 85 to 99 wt%, or 90 to 99 wt% with respect to the thermoplastic resin composition.

The chain extender increases the melt viscosity and the melt tension of the thermoplastic resin composition, and serves to increase the molecular weight by extending the chain of the thermoplastic elastomer copolymer during the reaction extrusion, for example, glycidyl group-modified ethylene-octene air It may be coalescing.

The glycidyl group-modified ethylene-octene copolymer may be, for example, an ethylene-octene rubber-glycidyl methacrylate (EOR-GMA) copolymer obtained by graft polymerization of glycidyl methacrylate to an ethylene-octene copolymer. have.

The glycidyl group-modified ethylene-octene copolymer may have, for example, a melt index of 3 g / 10 min or less, or 0.1 to 3 g / 10 min, and excellent mechanical properties within this range.

The glycidyl group of the glycidyl group-modified ethylene-octene copolymer may be included in an amount of 10 to 30% by weight, 15 to 30% by weight, or 20 to 25% by weight relative to the glycidyl group-modified ethylene-octene copolymer. There exists an effect excellent in melt viscosity and melt tension in this range.

The glycidyl group-modified ethylene-octene copolymer may be included, for example, in an amount of 1 to 10% by weight, 1 to 5% by weight, or 1 to 3% by weight based on the thermoplastic resin composition. The amount of change in melt viscosity and melt tension in the temperature range is small, there is an effect of excellent blow moldability.

The additive may be at least one selected from the group consisting of, for example, a hindered phenolic antioxidant, an amine antioxidant, a lubricant, and carbon black.

The hindered phenolic antioxidant is, for example, [3- [3- (4-hydroxy-3,5-di-butyl-phenyl) propanoyloxy] -2,2-bis [3- (4- Hydroxy-3,5-di-butyl-phenyl) propanoyloxymethyl] propyl] 3- (4-hydroxy-3,5-di-butyl-phenyl) propanoate ([3- [3 -(4-hydroxy-3,5-ditert-butyl-phenyl) propanoyloxy] -2,2-bis [3- (4-hydroxy-3,5-ditert-butyl-phenyl) propanoyloxymethyl] propyl] 3- (4 -hydroxy-3,5-ditert-butyl-phenyl) propanoate), and the amine-based antioxidant is, for example, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine (4,4'- (α, α-dimethylbenzyl) diphenylamine).

As another example, the additives may be used as flame retardants, lubricants, hydrolysis stabilizers, metal inactivators, pigments, colorants, antistatic agents, conductivity giving agents, EMI shielding agents, magnetizing agents, crosslinking agents, antibacterial agents, processing aids, and abrasion resistant wear agents. It may further comprise one or more selected from the group consisting of.

For example, the additive may be included in an amount of 0 to 10 wt%, 0.1 to 5 wt%, or 0.1 to 3 wt% with respect to the thermoplastic resin composition.

For example, the thermoplastic resin composition may have a melt index (230 ° C., 10 kg) of 5 g / 10 min or more, 5 to 20 g / 10 min, or 8 to 14 g / 10 min.

For example, the thermoplastic resin composition may have a tensile elongation of 770% or more, 800% or more, or 800 to 900%.

The thermoplastic resin composition may have, for example, a kefir ley viscosity retention of 230 ° C. to 250 ° C. of 50% or more, 70% or more, or 70 to 90%, and excellent blow moldability within a wide temperature range within this range. It works.

For example, the thermoplastic resin composition may have a glass transition temperature of less than -30 ° C, -35 ° C or less, or -45 to -35 ° C, and has excellent flexibility at low temperatures within this range.

The molded article according to the present invention includes the thermoplastic resin composition.

The molded article may be, for example, a member for automobiles, and in particular, may be a member for constant velocity joint boots.

Hereinafter, preferred examples are provided to aid in understanding the present invention, but the following examples are merely to illustrate the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.

[Production example]

Preparation Example 1 (TPEE 1)

40-70 parts by weight of dimethyl terephthalate, 20-40 parts by weight of 1,4-butanediol and polytetramethylene glycol having a number average molecular weight of 1,000 g / mol and polytetramethylene glycol having a number average molecular weight of 2,000 g / mol 49.7 parts by weight of a polytetramethylene glycol mixture in which the call was mixed in a weight ratio of 1: 1.5 was placed in a transesterification reactor, and 0.1 to 0.5 parts by weight of a tetrabutyl titanate (TBT) catalyst was added. Thereafter, the reaction was carried out at 200 to 250 ° C. for 2 to 4 hours, and the reaction was terminated at the point of methanol theoretical detection amount.

Subsequently, 100 parts by weight of the oligomer obtained from the reaction was transferred to a polycondensation reactor, and the melt polymerization reaction was performed at 220 to 250 ° C. for 2 to 4 hours.

Preparation Example 2 (TPEE 2)

In Preparation Example 1, except that the same amount of polytetramethylene glycol having a number average molecular weight of 2,000 g / mol instead of the polytetramethylene glycol mixture was added in the same manner as in Preparation Example 1.

Preparation Example 3 (TPEE 3)

In Preparation Example 1, except that 40 to 60 parts by weight of polytetramethylene glycol having a number average molecular weight of 1,400 g / mol instead of the polytetramethylene glycol mixture was carried out in the same manner as in Preparation Example 1. It was.

EXAMPLE

Examples 1 and 2, Comparative Examples 1 and 2

The thermoplastic elastomer copolymers (TPEE 1 to 3) prepared in Preparation Examples 1 to 3, ethylene-octene rubber (EOR-GMA) and additives glycidyl methacrylate graft polymerized as a chain extender are shown in Table 1 below. After mixing to the content (% by weight) described, using a twin-screw extruder (twin-screw extruder) melted and kneaded in a temperature section of 200 to 270 ℃, and then pelletized by drying at 80 ℃ for at least 4 hours, then room temperature ( After standing for 1 day at 20 to 26 ℃), a specimen for measuring the physical properties was prepared using an injection machine.

[Test Example]

The physical properties of the thermoplastic resin composition specimens obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

How to measure

* Melt Index (Melt Index, g / 10 min): Measured according to the standard measurement ISO1133 (230 ℃, 10 kg conditions) using the specimen.

* Shore D: Measured by Shore D type according to the standard measurement ISO868 using the specimen.

* Tensile Strength and Tensile Elongation (MPa and%): Tensile strength (MPa) and tensile elongation (%) were respectively measured according to the standard measurement ISO527-1 / -2 using the specimen.

Capillary shear rate (Pas): Using a test piece, the keppery shear viscosity of 230 ° C. and 250 ° C. was measured at a shear rate of 50 to 3,000 1 / s, respectively.

* Viscosity retention (%): The kefir lean shear viscosity measured at 230 ° C. was divided by the petroleum shear viscosity measured at 250 ° C. and expressed as a percentage.

* Glass transition temperature (Tg, ℃): measured by the peak value of the tangent delta using Dynamic Mechanical Analysis (DMA).

Flexural modulus and flexural strength (MPa): The flexural modulus and flexural strength were respectively measured according to the standard measurement ISO787 using specimens.

division Example Comparative example One 2 One 2 TPEE 1 96.0 95.0 - - TPEE 2 - - 93.0 - TPEE 3 - - - 95.5 Chain extender 1.5 2.5 4.5 2.0 additive 2.5 2.5 2.5 2.5 * Properties Melt index 14 8 4 12 Hardness 37 37 36 35 The tensile strength 39 39 40 39 Tensile elongation 875 857 762 804 Keplerary Shear Viscosity (230 ° C) 1,100 1,290 1,960 1,221 Keplerary Shear Viscosity (250 ° C) 900 1,040 830 613 Viscosity retention 82 81 42 50 Glass transition temperature -40 -40 -30 -50 Flexural modulus - 72 70 66 Flexural strength - 4.9 4.7 4.5

* TPEE 1: thermoplastic elastomer copolymer prepared from Preparation Example 1

* TPEE 2: thermoplastic elastomer copolymer prepared from Preparation Example 2

* TPEE 3: thermoplastic elastomer copolymer prepared from Preparation Example 3

* Chain Extender: Ethylene-octene rubber (EOR-GMA) glycidyl methacrylate is graft polymerized (manufactured by K & A TRADD, product name KT20)

* Additives: Hindered phenolic antioxidant (BASF, product name IR1010), amine antioxidant (Jiansu Feiya Chemical Industry company, product name Naugard445), lubricant (Incroslip company, product name EBO) and carbon black masterbatch (NPK) Manufacture, product name M40C)

As shown in Table 1, in Examples 1 and 2 manufactured according to the present invention, blow moldability in a wide temperature range due to less tensile strength and elongation change after aging, while maintaining equivalent mechanical properties or durability, that is, durability It was excellent in the low glass transition temperature, excellent flexibility at low temperatures, high retention rate of the keppery shear viscosity was confirmed that the excellent melt viscosity and melt tension.

On the other hand, in Comparative Example 1 containing polyalkylene glycol alone having a number average molecular weight of 2,000 g / mol, the melt index and hardness were lowered, the glass transition temperature was relatively high, and the retention of the kefir foliar viscosity was extremely poor. It was confirmed that, in the case of Comparative Example 2 containing a polyalkylene glycol having a number average molecular weight of 1,400 g / mol alone, the hardness was lowered, it was confirmed that the keplerary shear viscosity retention is poor.

From this, the present inventors prepared thermoplastic elastomer copolymers containing aliphatic polyethers having different number average molecular weights in specific mixing ratios, thereby improving blow moldability and flexibility at low temperatures over a wide temperature range, and including chain extenders. It was confirmed that the thermoplastic resin composition having improved melt viscosity and melt tension could be realized.

Claims (15)

a soft monomer comprising (a) a low molecular weight polyalkylene glycol and (b) a high molecular weight polyalkylene glycol in a weight ratio (a: b) of 1: 1.5 to 1: 5; And a hard monomer comprising a polyester; and a thermoplastic elastomer copolymer characterized in that the polymer is melt polymerized. The method of claim 1,
The low molecular weight polyalkylene glycol (a) is a thermoplastic elastomer copolymer, characterized in that the number average molecular weight of 500 to 1,400 g / mol. The method of claim 1,
The high molecular weight polyalkylene glycol (b) is a thermoplastic elastomer copolymer, characterized in that the number average molecular weight of 1,500 to 3,000 g / mol. The method of claim 1,
The polyalkylene glycols of (a) and (b) are polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-1,2-butylene glycol, polypentylene glycol, respectively. Thermoplastic elastomer copolymer, characterized in that at least one selected from the group consisting of polyhexylene glycol, polyheptylene glycol, polyoctylene glycol, polynonylene glycol and polydecylene glycol. The method of claim 1,
Wherein said polyester is derived from aromatic dicarboxylic acids or their ester forming derivatives and aliphatic diols. The method of claim 1,
The thermoplastic elastomer copolymer is 30 to 70% by weight, and the hard monomer is 30 to 70% by weight relative to the thermoplastic elastomer copolymer. A thermoplastic resin composition comprising 80 to 99 wt% of the thermoplastic elastomer copolymer according to claim 1, 1 to 10 wt% of a chain extender, and 0 to 10 wt% of an additive. The method of claim 7, wherein
The chain extender is a thermoplastic resin composition, characterized in that the glycidyl group-modified ethylene-octene copolymer. The method of claim 8,
The glycidyl group-modified ethylene-octene copolymer is an ethylene-octene rubber-glycidyl methacrylate (EOR-GMA) copolymer obtained by graft polymerization of glycidyl methacrylate to an ethylene-octene copolymer. Thermoplastic resin composition. The method of claim 7, wherein
The additive is a thermoplastic resin composition, characterized in that at least one selected from the group consisting of hindered phenolic antioxidant, amine antioxidant, lubricant and carbon black. The method of claim 7, wherein
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the melt index (230 ℃, 10 kg) is 5 g / 10 min or more. The method of claim 7, wherein
The thermoplastic resin composition has a tensile elongation of 770% or more. The method of claim 7, wherein
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the retention rate of the kepillary viscosity of 230 ℃ to 250 ℃ 50% or more. A molded article comprising the thermoplastic resin composition according to claim 7. The method of claim 14,
The molded article, characterized in that the automobile member.