KR102163716B1 - Thermoplastic elastomer resin composition for reactive extrusion - Google Patents

Abstract

The present invention relates to a thermoplastic elastomer resin composition for reaction extrusion, and more particularly, a thermoplastic polyester elastomer (TPEE) resin, a reactive additive that reacts with a TPEE resin during reaction extrusion, and the reactivity of a TPEE resin and a reactive additive. It includes a catalyst to increase and realizes the mechanical properties of existing blow molding materials, and at the same time, it is possible to solve the change in melt viscosity and mold deposition and injection defects caused by injection molding of the existing material. It relates to a thermoplastic elastomer resin composition for reaction extrusion that can be used for blow molding applications including constant velocity joint boots.

Description

Thermoplastic elastomer resin composition for reactive extrusion {Thermoplastic elastomer resin composition for reactive extrusion}

The present invention relates to a thermoplastic elastomer resin composition for reaction extrusion, and more particularly, a thermoplastic polyester elastomer (TPEE) resin, a reactive additive that reacts with a TPEE resin during reaction extrusion, and the reactivity of a TPEE resin and a reactive additive. It includes a catalyst to increase and realizes the mechanical properties of existing blow molding materials, and at the same time, it is possible to solve the change in melt viscosity and mold deposition and injection defects caused by injection molding of the existing material. It relates to a thermoplastic elastomer resin composition for reaction extrusion that can be used for blow molding applications including constant velocity joint boots.

Thermoplastic Polyester Elastomer (TPEE) resins are used in various forms throughout industries such as electric and electronic, biomaterials and automobiles based on excellent heat resistance, chemical resistance and durability, and are replacing existing materials.

In particular, thermoplastic polyester elastomer resins are used for constant velocity joint boots, gearbox bellows, air ducts, etc. in automobile parts. Since these blow molding products are produced through a blow process in a molten state, the molten resin must have excellent melt viscosity and melt tension, and the parison shape must be maintained during extrusion blown. In order to realize the properties of such a blow molding material, there is a method of using a reactive additive. When using reactive additives, it is possible to impart excellent heat resistance to molded products as well as to realize physical properties for blow molding.

However, in the case of using reactive additives during reaction extrusion, there is a problem that unreacted reactive additives remain in the product, and the remaining reactive additives affect the viscosity after production, and in the case of blow molding, the mold will gradually change. It accumulates, eventually causing mold deposition in proportion to the production volume. In addition, due to the materials deposited in the mold, problems of lowering workability, such as occurrence of injection defects and an increase in the number of times of cleaning the mold, are caused.

An object of the present invention is to provide a thermoplastic elastomer resin composition for reaction extrusion that can realize the mechanical properties of the existing blow molding material and solve the change in melt viscosity and mold deposition and injection defects caused by the injection molding of the existing material. To provide.

The present invention to solve the above technical problem, (1) a thermoplastic polyester-based elastomer resin; (2) a reactive additive that reacts with the thermoplastic polyester elastomer resin during reaction extrusion; And (3) a catalyst for increasing the reactivity of the thermoplastic polyester-based elastomer resin and the reactive additive; containing, it provides a thermoplastic elastomer resin composition for reaction extrusion.

According to another aspect of the present invention, a molded article is provided, characterized in that it is manufactured by processing the thermoplastic elastomer resin composition of the present invention.

The thermoplastic elastomer resin composition for reaction extrusion of the present invention can produce high-viscosity products suitable for blow molding, and can prevent mold deposition by reducing outgas, which is a problem of reaction extrusion, and prevent injection defects due to mold deposition, etc. While it can improve the workability of blow molding, it can realize the mechanical properties of existing blow molding materials, so it is very suitable for production of blow molding products, especially constant velocity joint boots and gearbox bellows.

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

The thermoplastic elastomer resin composition for reaction extrusion of the present invention includes a thermoplastic polyester elastomer (TPEE) resin.

The TPEE resin usable in the present invention is a thermoplastic block copolymer having a hard hard segment and a soft soft segment.

In one embodiment, the hard segment includes a polymerization unit derived from an aromatic dicarboxyl compound and a diol, and the soft segment includes a polymerization unit derived from a polyalkylene oxide.

As the aromatic dicarboxylic compound, an aromatic dicarboxylic acid, an aromatic dicarboxylate, or a combination thereof may be used, and more specifically, terephthalic acid (TPA), isophthalic acid, IPA), 1,5-dinaphthalenedicarboxylic acid (1,5-NDCA), 2,6-dinaphthalene dicarboxylic acid (2,6-dinaphthalenedicarboxylic acid, 2,6- NDCA), dimethyl terephthalate (DMT), dimethyl isophthalate, or a combination thereof may be used. Preferably dimethyl terephthalate is used.

As the diol, a cyclic aliphatic diol or a linear aliphatic diol having 2 to 8 carbon atoms may be used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, One selected from 1,4-cyclohexanedimethanol or a combination thereof may be used, and 1,4-butanediol may be preferably used. Preferably, the cyclic aliphatic diol may have 3 to 10 carbon atoms.

Polyoxyalkylene glycol may be used as the polyalkylene oxide, and more specifically, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol glycol, PTMEG) or a combination thereof may be used. Preferably polyoxytetramethylene glycol is used.

In addition, in order to improve the stability of TPEE strands during TPEE production by increasing the melt tension of TPEE, and thereby increase productivity, a branching agent may be additionally used in the production of TPEE. As such a branching agent, glycerol, pentaerythritol, neopentylglycol, or a combination thereof may be used, and glycerol is preferably used. In addition, the preparation of TPEE can be carried out in the presence of a suitable catalyst (eg, tetra-n-butoxy titanium, TBT).

In general, TPEE that can be used in the present invention can be prepared through melt polymerization consisting of two steps of an oligomerization reaction and a polycondensation reaction after introducing the above-described components into a reactor. The oligomerization reaction is carried out at 140 to 215°C for 3 to 4 hours, and the polycondensation reaction proceeds by stepwise decompression from 760 torr to 0.3 torr at 210 to 250°C for 4 to 5 hours to prepare a branched elastomer. do.

The soft segment content in 100% by weight of TPEE that can be used in the present invention may vary, for example, may be in the range of 5 to 75% by weight, and in particular, considering blow molding processability, mechanical strength, flexibility, etc., 30 to 70 It is preferably% by weight. If the soft segment content in TPEE is too small, it is difficult to expect flexibility due to high hardness, whereas if it is too much, it is difficult to expect high heat resistance.

TPEE that can be used for reaction extrusion in the present invention preferably has an intrinsic viscosity of 1.3 to 2.0 dl/g, and more preferably may have an intrinsic viscosity of 1.3 to 1.8 dl/g. In addition, TPEE that can be used for reaction extrusion preferably has a Shore hardness of D-30 to D-60, more preferably may have a Shore hardness of D-40 to D-55.

In one embodiment, the thermoplastic elastomer resin composition for reaction extrusion of the present invention may contain 94 to 99 parts by weight of the thermoplastic elastomer resin, more specifically 95 to 99 parts by weight, based on 100 parts by weight of the composition. More specifically, it may be included in an amount of 95 to 98 parts by weight. If the content of the thermoplastic elastomer resin in 100 parts by weight of the thermoplastic elastomer resin composition for reaction extrusion of the present invention is less than 94 parts by weight, there may be a problem in that the basic physical properties of TPEE cannot be reproduced due to excessive additive content, and if it exceeds 99 parts by weight, insufficient additive content Due to this, there may be a problem that the decomposition of TPEE occurs.

The thermoplastic elastomer resin composition for reaction extrusion of the present invention includes a reactive additive that reacts with the TPEE resin during reaction extrusion.

The reactive additive reacts with the TPEE resin to increase the melt tension of the composition, thereby enabling blow molding.

As the reactive additive, at least one selected from the group consisting of compounds having at least one functional group selected from an isocyanurate group, an isocyanate group, a carbodiimide group and an epoxy group may be used. Preferably, the reactive additive compound has the functional group at the terminal.

In one embodiment, as the reactive additive, a compound containing two or more isocyanate groups, such as hexamethylene diisocyanate, isopron diisocyanate, toluene diisocyanate, 4,4-cyclohexanebismethylisocyanate, 4,4' -Dicyclohexylmethane diisocyanate, methylene diphenyl diisocyanate, or a mixture of two or more of them may be used, but the present invention is not limited thereto.

In another embodiment, as the reactive additive, a compound having an isocyanurate group and an isocyanate group together, such as hexamethylene diisocyanate-isocyanurate, isopron diisocyanate-isocyanurate, toluene diisocyanate-isocylate Anurate, 4,4-cyclohexanebismethylisocyanate-isocyanurate, 4,4′-dicyclohexylmethanediisocyanate-isocyanurate, methylenediphenyldiisocyanate-isocyanurate, or two or more of these Mixtures may be used, but are not limited thereto.

In one embodiment, the thermoplastic elastomer resin composition for reaction extrusion of the present invention may contain 0.1 to 5 parts by weight of the reactive additive, more specifically 0.2 to 4 parts by weight, based on 100 parts by weight of the composition. Specifically, it may be included in an amount of 0.3 to 3 parts by weight. If the content of the reactive additive in 100 parts by weight of the thermoplastic elastomer resin composition for reaction extrusion of the present invention is less than 0.1 parts by weight, the effect of the reactive additive may not be obtained, and the flowability of the resin may be too high, and if it exceeds 5 parts by weight, the reactive additive Due to the excessive reaction of, there may be problems in processing due to low flowability.

The thermoplastic elastomer resin composition for reaction extrusion of the present invention includes a catalyst for increasing the reactivity of the TPEE resin and the reactive additive. As such a catalyst, a metal, organometallic, or organic catalyst may be used.

In one embodiment, as a catalyst for increasing the reactivity of the TPEE resin and the reactive additive, an organic catalyst such as 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4. 0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, N-heterocyclic carbene, diphenyl phosphate, triphenyl phosphate, methanesulfonic acid, triflic acid Alternatively, a mixture of two or more of them may be used, but is not limited thereto.

In another embodiment, as a catalyst for increasing the reactivity of the TPEE resin and the reactive additive, an organometallic catalyst such as dibutyl tin dilaurate, dibutyl tin diacetate, tin dioctoate, or a mixture of two or more thereof may be used. It is not limited thereto.

In one embodiment, the thermoplastic elastomer resin composition for reaction extrusion of the present invention may contain 0.1 to 5 parts by weight of the catalyst based on 100 parts by weight of the reactive additive, and more specifically 0.5 to 1.5 parts by weight, even more Specifically, it may be included in an amount of 0.75 to 1 part by weight. If the catalyst content per 100 parts by weight of the reactive additive is less than 0.1 parts by weight, the role of the catalyst may be insignificant and there may be a problem that there is no difference from the reaction without a catalyst. If it exceeds 5 parts by weight, the resin may be decomposed due to excessive introduction of the metal catalyst. There may be problems.

The thermoplastic elastomer resin composition for reaction extrusion of the present invention may further include one or more additives commonly used for reaction extrusion of an elastomer resin in addition to the above components. Examples of such additives include, but are not limited to, antioxidants, thermal stabilizers, light stabilizers, lubricants, reinforcing agents (eg, silicone resins), lubricants, and the like. Examples of antioxidants include hindered amin antioxidants, hindered phenol antioxidants, phosphite antioxidants, amide antioxidants, thioester antioxidants. Antioxidants or combinations thereof, and more specifically 4,4'bis(α, α-diphenylbenzyl) diphenyl amine (Naugard 445 from Chemtura) and octadecyl-3-(3,5-di -tert-butyl-4-hydroxyphenyl)-propionate (Ciba's irganox 1076, etc. may be exemplified, but are not limited thereto. These additives are based on 100 parts by weight of the composition, in total 0.1 to 4 parts by weight, For each additive, it is generally used in an amount of 0.05 to 1 part by weight.

In one embodiment, in the thermoplastic elastomer resin composition of the present invention, the difference between the melt index (g/10min) after drying for 4 hours and the melt index (g/10min) after drying for 30 minutes is 5 or less (eg, 1 to 5), , More preferably, it may be 4 or less, even more preferably, 3 or less.

There is no particular limitation on the conditions for reaction-extrusion of the thermoplastic elastomer resin composition of the present invention, and may be appropriately selected depending on the equipment used and other process factors. According to an embodiment of the present invention, the temperature of the extruder hopper for mixing and introducing raw materials is 140 to 160°C, the temperature of the rest of the extruder is 180 to 240°C, and the feed rate is 5 Reaction extrusion may be performed by setting the rotation speed of the screw to 150 to 350 rpm at ~20kg/hr, but is not limited thereto.

The thermoplastic elastomer resin composition of the present invention is suitable for molding processing such as blow, extrusion, injection, etc., and is particularly suitable for blow molding, and the engine room is narrowed according to the recent automobile development trend of miniaturization and weight reduction, and the use of turbo engine is increased. Because it has the high heat resistance and high durability required for this, it is a material for various automobile parts such as constant velocity joint boots (CVJB), gearbox bellows, air ducts, intercooler pipes, dashboard skins, buttons, etc. As can be used very suitably.

Accordingly, according to another aspect of the present invention, a molded article is provided, characterized in that it is manufactured by processing the thermoplastic elastomer resin composition of the present invention described above, and preferably, a molded article manufactured by blow molding is provided.

Hereinafter, the present invention will be described in more detail through examples. However, the scope of the present invention is not limited to these examples.

[Example]

Preparation Example 1: Preparation of TPEE of Shore Hardness D-40

Dimethyl terephthalate (DMT) 34.60 parts by weight, 1,4-butanediol 25.0 parts by weight, 40.20 parts by weight of polyoxytetramethylene glycol (PTMEG) having a molecular weight of 2,000, and 0.065 parts by weight of glycerol were put into an oligomerization reactor and tetra-n as a catalyst for TPEE production. -Butoxy titanium (TBT) was added in an amount of 0.025 parts by weight. After raising the temperature of the reactor from 140° C. to 215° C. for 120 minutes, it was reacted for an additional 120 minutes while maintaining 215° C. The reaction was terminated when the reaction rate reached 99% or more by converting the amount of methanol, which is the reaction effluent, into the reaction rate. Thereafter, 0.04 parts by weight of TBT as a catalyst and 0.07 parts by weight of a heat stabilizer (Irganox 1010) were added to the reactor, the temperature was raised from 215°C to 250°C for 120 minutes, and then reacted for an additional 120 minutes while maintaining 250°C. At this time, the pressure was reduced from 760 torr to 0.3 torr for 1 hour, and the remaining 3 hours were under a vacuum condition of 0.3 torr or less, but the final depressurization was adjusted to 0.3 torr or less to prepare TPEE of Shore Hardness-D 40. The intrinsic viscosity of the prepared TPEE was measured in a solvent of phenol/tetrachloroethane (TCE) = 50/50, and it was 1.7 dl/g.

Examples 1 to 6 and Comparative Example 1

The TPEE and other raw materials prepared in Preparation Example 1 were put into a twin-screw extruder hopper according to the composition shown in Table 1 below, melt-kneaded and extruded in the twin-screw extruder, and then cooled in a cooling tank, and then pellet tie. And prepared into pellets.

The temperature of the extruder was 150℃ for the hopper part and 190~230℃ for the rest of the extrusion. Twin screw (L/D=40) was used, the diameter of the die was 26phi, and the kneading block was 2 Dogs were used. The feed rate of TPEE resin was 10 to 12 kg/hr, and the rotation speed of the extruder screw was 150 to 200 rpm.

-Catalyst: dibutyltindilaurate

-Reactive additive 1: methylenediphenyldiisocyanate

-Reactive additive 2: hexamethylene diisocyanate-isocyanurate

-Silicone resin: MB50-010 from Dow Corning

-Thermal stabilizer: ADEKA's PEP36

-Antioxidant 1: Naugard 445 from Chemtura

-Antioxidant 2: irganox 1076 from Ciba

Physical properties were confirmed by measuring the following items for the prepared thermoplastic polyester-based elastomer resin composition, and the results are shown in Table 2 below.

(1) Tensile strength: evaluated according to ASTM D638.

(2) Tensile elongation: evaluated in accordance with ASTM D638.

(3) Modulus: evaluated according to ASTM D638.

(4) Melt index: According to ASTM D1238, it was measured after staying for 3 minutes at 230°C and a load of 10.0 kg.

(5) Mold immersion: After 100 injections, evaluation was made by visually observing the part immersed in the cross section of the injection machine fixing part.

As can be seen from Table 2, the compositions of Examples 1 to 6, compared to Comparative Example 1, exhibited the same level of mechanical properties (tensile strength, tensile elongation, modulus), while the difference in melt index according to drying time was remarkably There was little, and no mold deposition occurred.

Therefore, the thermoplastic elastomer resin composition for reaction extrusion of the present invention realizes the mechanical properties of the existing blow molding material, and at the same time, it is possible to solve the change in melt viscosity and mold deposition and injection defects caused by the injection molding of the existing material. .

Claims (8)

(1) thermoplastic polyester elastomer resin;
(2) a reactive additive that reacts with the thermoplastic polyester elastomer resin during reaction extrusion; And
(3) a catalyst for increasing the reactivity of the thermoplastic polyester elastomer resin and the reactive additive; and,
The thermoplastic polyester-based elastomer resin is a thermoplastic block copolymer comprising a polymerization unit derived from an aromatic dicarboxylic compound and a diol compound as a hard segment, and a polymerization unit derived from a polyalkylene oxide as a soft segment,
The reactive additive is one or two or more selected from the group consisting of compounds having one or more functional groups selected from an isocyanurate group, an isocyanate group, a carbodiimide group, and an epoxy group,
The catalyst is a metal, organometallic, or organic catalyst,
The difference between the melt index (g/10min) after drying for 4 hours and the melt index (g/10min) after drying for 30 minutes is 5 or less,
Thermoplastic elastomer resin composition for reaction extrusion. The method of claim 1, wherein the reactive additive is hexamethylene diisocyanate, isopron diisocyanate, toluene diisocyanate, 4,4-cyclohexanebismethylisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylenediphenyldi Isocyanate, hexamethylenediisocyanate-isocyanurate, isoprondiisocyanate-isocyanurate, toluenediisocyanate-isocyanurate, 4,4-cyclohexanebismethylisocyanate-isocyanurate, 4,4' -Dicyclohexylmethane diisocyanate-isocyanurate and methylenediphenyldiisocyanate-isocyanurate one or more selected from the group consisting of, a thermoplastic elastomer resin composition for reaction extrusion. The method of claim 1, wherein the catalyst is 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-tri Azabicyclo[4.4.0]dec-5-ene, N-heterocyclic carbene, diphenylphosphate, triphenylphosphate, methanesulfonic acid, triflic acid, dibutyltindilaurate, dibutyltindiacetate and tindiocto One or two or more selected from the group consisting of eight, a thermoplastic elastomer resin composition for reaction extrusion. A molded article manufactured by processing the thermoplastic elastomer resin composition for reaction extrusion of any one of claims 1 to 3. delete delete delete delete