KR100221717B1 - Polyphenylene ether thermoplastic resin composition and its preparation process - Google Patents

Abstract

The polyphenylene ether thermoplastic resin composition of the present invention comprises (A) 5 to 95 parts by weight of a polyphenylene ether resin or a mixture of a vinyl aromatic polymer and a polyphenylene ether resin; (B) 1 to 50 parts by weight of a vinyl aromatic polymer; (C) 0 to 2 parts by weight of an organic peroxide to the component (B); (D) 0.01 to 30 parts by weight of a reactive monomer having an epoxy group to the component (B); (E) 5 to 95 parts by weight of a polyamide resin; And (F) 0 to 40 parts by weight of a styrene-based impact stiffener, wherein the components (A) and (F) are introduced into the first region using an extruder divided into three or more regions, (B), (C), and (D), and injecting the component (E) in a third region.

Description

[Title of the Invention]

Polyphenylene ether-based thermoplastic resin composition and method for producing the same

DETAILED DESCRIPTION OF THE INVENTION [

[0001]

The present invention relates to a polyphenylene ether thermoplastic resin composition. More particularly, the present invention relates to a polyphenylene ether-based thermoplastic resin composition comprising a polyphenylene ether and a polyamide as a base and including a vinyl aromatic polymer, an organic peroxide, a reactive monomer, and a styrene-based impact modifier, .

BACKGROUND OF THE INVENTION [

A mixture of a polyphenylene ether resin or a polyphenylene ether resin and a polystyrene resin has excellent mechanical properties and electrical properties in a high temperature range and is widely used in various fields such as automobile parts, electric and electronic parts. However, the polyphenylene ether resin has a disadvantage that the solvent resistance is poor and the workability is very poor.

The polyamide resin is excellent in chemical resistance and workability, but has a disadvantage in that heat resistance and impact resistance are not good, and therefore, its use as an engineering plastic resin is limited. Therefore, there have been many studies on the methods to overcome the shortcomings of these two resins.

U.S. Patent No. 3,379,792 discloses a resin composition in which 0.1 to 25% of a polyamide resin is added to a polyphenylene ether resin. However, when the content of the polyamide resin is 20% or more, there is a disadvantage in that the physical properties of the molded article are remarkably deteriorated due to the phase separation phenomenon because there is no compatibility between the two resin components.

U.S. Patent No. 4,315,086 discloses a resin composition comprising 100 parts by weight of a resin composition comprising 5 to 95% by weight of a polyphenylene ether resin and 95 to 5% by weight of a polyamide resin, (a) a liquid diene polymer, (b) , And (c) a polymer having a carbon-carbon double bond or a triple defect and having one of a tartaric acid, anhydride, acid amide, imide, carboxylic acid ester, amino or hydroxyl group 0.01 to 30 parts by weight of a compound is contained.

U.S. Patent No. 4,943,399 discloses a process for producing polyphenylene ether (a ₁ ), a vinyl aromatic polymer (a ₂ ), an α, β-unsaturated dicarboxylic acid or its derivative, an amide group and a polymerizable double bond at the same time (A ₃ ), a polymerizable monomer (a ₄ ), and a free radical initiator (a ₅ ) selected from the group consisting of a monomer having a polymerizable double bond and a polymerizable double bond with a lactam group, (B), the unmodified polyphenylene ether resin (C), the vinyl aromatic copolymer (D), the impact reinforcement (E), and the polypropylene resin And another additive (F) is added thereto to prepare a polyphenylene ether resin composition.

European Patent No. 046,040 discloses a composition comprising (a) a polyphenylene ether resin, (b) a copolymer composed of a vinyl aromatic polymer and an?,? - unsaturated dicarboxylic acid anhydride or an imide polymer thereof, and (c) And optionally (d) an impact reinforcing material having improved heat resistance, oil resistance, and impact resistance.

International Patent Application No. PCT / US86 / 01511 discloses a process for the preparation of a compound having at least one carbon-carbon double bond or triple bond in the molecule under the absence of a free-radical initiator and which comprises a carboxylic acid, acid anhydride, acid amide, imide, Or a functional group having at least one functional group out of a hydroxyl group is mixed with a polyphenylene ether in a molten state. However, this method is disadvantageous in that the resin composition using an unsaturated carboxylic acid such as maleic anhydride or a polyphenylene ether resin modified with the unsaturated carboxylic anhydride greatly changes the natural color of the resin during the extrusion process.

Accordingly, the present inventors have found that a method for improving the compatibility of a polyphenylene ether resin and a polyamide resin, using an appropriate continuous manufacturing process in an extruder and using a polyphenylene ether resin, a polyamide resin, a vinyl aromatic polymer, an organic peroxide, And a styrene-based impact reinforcing material, which are excellent in natural color and mechanical properties.

[Object of the invention]

An object of the present invention is to provide a resin composition comprising a polyphenylene ether resin and a polyamide resin as a base and including a vinyl aromatic polymer, an organic peroxide, a reactive monomer and a styrene-based impact reinforcement, And to provide a polyphenylene ether-based thermoplastic resin composition having improved properties.

Another object of the present invention is to provide a polyphenylene ether resin composition which is excellent in impact resistance, heat resistance, chemical resistance and workability and which does not discolor natural colors intensively during the extrusion process.

It is still another object of the present invention to provide a process for producing a polyphenylene ether thermoplastic resin composition having improved compatibility between a polyphenylene ether resin and a polyamide resin.

[Summary of the Invention]

The polyphenylene ether thermoplastic resin composition of the present invention comprises (A) 5 to 95 parts by weight of a polyphenylene ether resin or a mixture of a vinyl aromatic polymer and a polyphenylene ether resin; (B) 1 to 50 parts by weight of a vinyl aromatic polymer; (C) 0 to 2 parts by weight of an organic peroxide per 100 parts by weight of the polymer (B); (D) 0.01 to 30 parts by weight of a reactive monomer having an epoxy group per 100 parts by weight of the polymer (B); (E) 5 to 95 parts by weight of a polyamide resin; And (F) 0 to 40 parts by weight of a styrene-based impact stiffener, wherein the components (A) and (F) are charged in a first region using an extruder divided into three or more regions, ), (C) and (D), and injecting the component (E) in a third region.

DETAILED DESCRIPTION OF THE INVENTION

(A) a polyphenylene ether resin, (B) a vinyl aromatic polymer, (C) an organic peroxide, (D) a reactive monomer containing an epoxy group, (E) a polyamide resin, and (F) The styrenic impact stiffener will be described in detail below.

[(A) polyphenylene ether resin]

In the present invention, a polyphenylene ether resin may be used alone, or a mixture of a polyphenylene ether resin and a vinyl aromatic polymer may be used.

Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl- (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ) Ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and a poly (2,6-dimethyl-1,4-phenylene) Triethyl-1, 4-phenylene) ether. Among these, copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6- , 4-phenylene) ether are preferable, and poly (2,6-dimethyl-1,4-phenylene) ether is more preferable.

The degree of polymerization of the polyphenylene ether is not particularly limited, but in consideration of thermal stability and workability of the resin composition, it is preferable that the intrinsic viscosity is 0.2 to 0.8 dl / g when measured in chloroform solvent at 25 캜. The polyphenylene ether may be used alone, or two or more compounds may be mixed in an appropriate ratio.

The polyphenylene ether resin has good compatibility with the vinyl aromatic polymer. Therefore, in the present invention, a mixture of a polyphenylene ether resin and a vinyl aromatic polymer can also be used. Vinyl aromatic polymers include polystyrene, high impact polystyrene, polychlorostyrene, poly alpha-methylstyrene, and polyt-butylstyrene, which may be used alone or as a mixture of two or more. Of these, polystyrene or high-impact polystyrene is preferable, and it is more preferable to use polystyrene in consideration of thermal stability and light stability of the final resin composition. The molecular weight of the vinyl aromatic polymer is not particularly limited. However, considering the thermal stability and workability of the resin composition, the weight average molecular weight is preferably 20,000 to 500,000.

The polyphenylene ether resin or the mixture of the vinyl aromatic polymer and the polyphenylene ether resin is used in an amount of 5 to 95 parts by weight based on the whole resin composition.

[(B) Vinyl aromatic polymer]

The vinyl aromatic polymer used as the component (B) in the present invention is as described in the component (A) above.

The vinyl aromatic polymer of the present invention is used in the form of a modified vinyl aromatic polymer in which an organic peroxide (C) and a reactive monomer (D) containing an epoxy group are melt-kneaded and graft-reacted.

The vinyl aromatic polymer is used in an amount of 1 to 50 parts by weight, preferably 3 to 30 parts by weight. If the vinyl aromatic polymer is used in an amount of 3 parts by weight or less, the effect of improving the compatibility of the resin composition is hardly obtained. If the vinyl aromatic polymer is used in an amount of 30 parts by weight or more, the heat resistance of the resin composition is lowered.

[(C) organic peroxide]

Examples of the organic peroxide used in the present invention include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, p-ethane hydroperoxide, t-butylcumylperoxide, dicumylperoxide, 2,5- Butylperoxybenzoate, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbamate, t-butylperoxyisobutyrate, t-butylperoxybenzoate, Borate, methyl ethyl ketone peroxide, cyclohexanone peroxide, etc. These may be used singly or in combination of two or more. Of these, dicumyl peroxide is preferably used in consideration of reactivity and processability.

The organic peroxide can be used in an amount of up to 2 parts by weight based on 100 parts by weight of the vinyl aromatic polymer of the component (B), and when mixed more than that, the thermal stability and physical properties of the final resin composition are significantly lowered due to decomposition of the resin .

[(D) reactive monomer]

Examples of the reactive monomer having an epoxy group used in the present invention include glycidyl esters such as glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate and glycidyl itagonate, Glycidyl ethers such as glycidyl methacrylate, glycidyl acrylate, and aryl glycidyl ether are preferable, and glycidyl methacrylate, glycidyl methacrylate, More preferred is a creylate.

The method for producing the modified vinyl aromatic polymer in which the reactive monomer having an epoxy group of the present invention is grafted to the vinyl aromatic polymer (B) is not particularly limited, but a vinyl aromatic polymer, an organic peroxide, and a reactive It is preferable that the monomers are blended and then grafted in a melt-kneaded state using a Banbury mixer or a vented extruder.

The reactive monomer containing an epoxy group is preferably used in an amount of 0.01 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the vinyl aromatic polymer of the component (B). When the amount is less than 1 part by weight, the effect of improving the compatibility of the final resin composition is scarcely produced.

[(E) Polyamide resin]

The polyamide resin which is the constituent component (E) of the present invention is at least one selected from the group consisting of polycaprolactam (nylon 6), poly (11-aminoundecanoic acid) (nylon 11), polylauryl lactam (nylon 12), polyhexamethylene adipate Amide (nylon 6,6), polyhexethylene azel amide (nylon 6,9), polyhexethylene sebacamide (nylon 6,10), polyhexethylene dodecanodiamide (nylon 6,12) Chain nylon 6 / 6,10, nylon 6 / 6,6, nylon 6/12, etc. may be used singly or two or more of them may be mixed in an appropriate ratio.

Considering the mechanical properties and heat resistance of the resin composition, the polyamide resin used in the present invention has a melting point of 200 DEG C or higher and a relative viscosity (measured at 25 DEG C by adding 1 wt% of a polyamide resin to m-cresol) .

The polyamide resin is used in an amount of 5 to 95 parts by weight based on the whole resin composition.

[(F) Styrenic Impact Reinforcement]

The styrene type impact modifier as the constituent component (F) of the present invention is derived from a vinyl aromatic monomer, and AB or ABA type diblock or radial block copolymer can be used.

AB or ABA type diblock or radialtest block copolymers are copolymers of vinyl aromatic monomers and hydrogenated, partially hydrogenated or unhydrogenated unsaturated diene blocks, examples of which are AB diblock type block copolymers Include polystyrene-polybutadiene (SBR), polystyrene-polyisoprene, polyalpha methylstyrene-polybutadiene copolymers and their hydrogenated forms. These AB diblock copolymers are widely known commercially and include SOLPRENE and K-RESIN from PHILLIPS, and KRATON D and KRATON G from SHELL. Examples of block copolymers of the ABA terblock type include polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), polyalpha methylstyrene-polybutadiene- Isoprene-poly (alpha methylstyrene), and hydrogenated forms of these copolymers. Such ABA terblock copolymers are also widely known commercially. Representative examples thereof include CARIFLEX, KRATON D and KRATON G from SHELL and SEPTON from KURARAY.

The styrene-based impact stiffener is used in an amount of 0 to 40 parts by weight based on the whole resin composition.

The method for producing the polyphenylene ether thermoplastic resin composition of the present invention is as follows.

In the production of the thermoplastic resin composition of the present invention, a single-screw or twin-screw extruder can be used. Considering the SELF-PURGING characteristic and the residence time distribution in the extruder of the resin, CO- It is preferable to use a twin-screw extruder.

The compressor used in the present invention has a jacket so that the temperature of the respective barrels can be adjusted. There is no particular restriction on the screw design of the extruder, and a conveyor element, a kneading element and a mixing element may be used, and in order to control the residence time and kneading degree in the extruder, You can use a BACKWARD-CONVEYING ELEMENT. The extruder used in the present invention is divided into three regions or more.

In the production process of the polyphenylene ether resin composition of the present invention, a polyphenylene ether-based resin (A) and a styrene-based impact reinforcement (F) are first charged into a first region of an extruder to form a polyphenylene ether- . At this time, the length of the first region of the extruder is preferably 3 to 30 D, more preferably 5 to 20 D. (D represents the diameter of the extruder screw.)

In order to smoothly supply the resin, it is preferable to attach the transfer element to the first region of the extruder, after which the kneading element and the mixing element can be attached. Thus, one or more reverse transport elements may be attached to the end of the first region of the extruder to control the residence time. The barrel temperature of the first region of the extruder is preferably 240 to 330 ° C.

In the production process of the present invention, the vinyl aromatic polymer (B), the organic peroxide (C) and the reactive monomer (D) are introduced into the second region of the extruder. In order to blend the polyphenylene ether-based mixture prepared in the first region of the extruder with the required composition, they were weighed in an appropriate ratio and then extruded in a molten state using a secondary extruder consisting of a barrel capable of temperature control, (FEEDING) to the first half of the second region of the extruder. The diameter of the extruder screw is preferably smaller than the diameter of the main extruder screw. The length of the extruder is preferably 5 to 40 D, more preferably 10 to 35 D desirable. When the length is 10 D or less, the reaction between the graft copolymer and the reactive monomer does not sufficiently proceed to improve the compatibility of the resin composition of the present invention. When the length is more than 35 D, excessive heat is applied to the resin, Appearance color and physical properties may be deteriorated. The barrel temperature of the secondary extruder is preferably 150-230 ° C.

The length of the second region of the extruder in which the polyphenylene ether-based mixture introduced in the first region of the extruder and the modified vinyl aromatic polymer supplied from the auxiliary extruder are kneaded is preferably 5 to 30 D , And more preferably 10 to 20 D. The kneading element and the mixing element may be attached to the second region of the extruder, and at least one reverse transport element may be attached to the end portion of the extruder to control the residence time. The barrel temperature of the second region of the main extruder is preferably in the same range as the barrel temperature of the first region. The residence time in this region is preferably 0.1 to 10 minutes, more preferably 0.3 to 5 minutes.

In the production process of the present invention, the polyamide resin as the component (E) is introduced in the third region of the extruder. In order to blend the mixture extruded in the second region of the extruder with the required composition, they are metered in an appropriate ratio and fed to the first half of the third region of the extruder using a SIDE-FEEDER. At this time, the polyamide resin (E) may be supplied in the form of pellets or in a molten state using a secondary extruder.

The length of the third region of the main extruder in which the mixture of the polyphenylene ether resin and the modified vinyl aromatic polymer extruded in the second region of the extruder and the polyamide resin fed from the auxiliary feeder in the manufacturing process of the present invention is 5 To 30 D, and more preferably 7 D to 25 D. The kneading element, the mixing element and the reverse transfer element can also be used in the third region of the extruder, and a vent portion can be installed to remove volatiles, and a vacuum device is introduced for effective removal of volatiles . The barrel temperature of the third region of the main extruder is also preferably used in the same range as the barrel temperatures of the first region and the second region.

Specifically, when an inorganic filler such as glass fiber, carbon fiber, talc, silica, mica, or alumina is added to the thermoplastic resin composition of the present invention, mechanical strength And heat distortion temperature, which may be supplied together with the resin of the constituent components (A) to (F), but it is also possible that after the third region of the extruder, one or more extruders (Fourth region) is further provided and supplied through the auxiliary supply unit, and the size and design of these regions are preferably based on the second region or the third region of the extruder.

The thermoplastic resin composition of the present invention can be produced by using other ultraviolet absorbers, antioxidants, flame retardants, lubricants, dyes and pigments.

The present invention will be further illustrated by the following examples. The following examples are only illustrative examples of the present invention and are not intended to limit or limit the scope of protection of the present invention.

[Example]

[(A) Polyphenylene ether (PPE) resin]

The polyphenylene ether resin (A-1) used in the examples of the present invention was P401 of Asahi Kasei Co., Ltd., and the polystyrene (A-2) was HR-2390 of Cheil Industries,

[(B) Vinyl aromatic polymer]

In the examples of the present invention, HF-2660, a product of Korea Cheil Industries Co., Ltd., was used as the vinyl aromatic polymer.

[(C) organic peroxide]

The organic peroxide used in the examples of the present invention was dicumyl peroxide from Aldrich, USA.

[(D) reactive monomer]

The reactive monomer used in the examples of the present invention was glycidyl methacrylate.

[(E) Polyamide resin]

In the examples of the present invention, two types of polyamide resins (E-1) and (E-2) were used. (E-1) is nylon 6 (trade name; KN-171) of KOLON Co. Ltd of Korea, and (E-2) is nylon 66 (trade name: 21SP) of Monsanto Corporation.

[(F) Styrenic Impact Reinforcement]

The styrene-based impact stiffener used in the present invention is KRATON G 1651 of Shell Company, USA.

[Example 1-4]

In Example 1-4 of the present invention, a resin composition was prepared using a biaxial extruder having ψ = 40 mm divided into three regions.

The length of the first region of the extruder was 12 D, and the screw under the feeding device for feeding the weighed solid resin in the weighing scale was designed as a CON-VEING ELEMENT. The temperature of the first 3 D portion was kept below 30 ° C, then the scoop portion (4 D) was heated to 240 ° C. and the remaining screw portion (6 D) was held at 280-290 ° C. A kneading screw element was designed in the middle of the first region of the extruder and a reverse transport element was introduced at the end.

The length of the second region of the extruder was 10 D, the front portion was equipped with a device for supplying resin, and all the remaining portions were sealed. The components (B), (C) and (D) were fed to the feeder through a secondary extruder and the temperature of the screw was maintained at 280 占 폚. In the middle, a mixing screw element was designed.

As a secondary extruder, a twin screw extruder having a screw diameter of 30 mm and a length of 17 D was used, and the extruder barrel temperature was heated to 200 ° C. In the front part of the secondary extruder, the materials to be extruded were weighed in a weighing scale and the end was connected to the resin feeding device in front of the second area of the main extruder.

The length of the third region of the extruder was 15 D, the front portion was equipped with a device for supplying resin, a vacuum belt device was installed at the middle portion for removing volatiles, and all the remaining portions were sealed. The polyamide resin as component (E) was fed in the form of pellets through the auxiliary feed unit in front of the third zone of the extruder and the temperature of the screw was maintained at 280 占 폚. A kneading screw element was installed in front of the intermediate vent device, and a mixing screw element was designed after that.

In Example 1-4, a resin composition was prepared in the form of pellets while varying the kind and content of each component by the composition and processing method as shown in Table 1. The pellets were dried at a temperature of 80 ° C for 6 hours, The specimens were prepared by injection molding at 230-320 ℃ and mold temperature of 60-90 ℃.

(Unit: parts by weight)

The specimens prepared according to Examples 1-4 had Izod impact strength (1/4, 1/8 notch) according to ASTM D 256, tensile strength and tensile elongation according to ASTM D 638, heat distortion temperature according to ASTM D 648 1/4, load of 4.6 kg), and whiteness was measured with a colorimeter. The measurement results are shown in Table 2.

[Comparative Example]

The following comparative examples are the same as those of the examples and the process steps are modified.

[Comparative Examples 2A, 3A, 4A]

COMPARATIVE EXAMPLES 2A, 3A and 4A are comparative examples for comparison with Examples 2, 3 and 4 of the present invention, wherein the components (A), (B), (C), (D) (F) were weighed, mixed at the same time, and extruded.

[Comparative Examples 2B, 3B, 4B]

Comparative Examples 2B, 3B and 4B are also comparative examples for comparison with Examples 2, 3 and 4 of the present invention, in which the component (A) is introduced in the first region of the extruder and the components (B) And (D) were added in the second region, and (E) and (F) were simultaneously injected in the third region.

[Comparative Examples 2C, 3C, 4C]

Comparative Examples 2C, 3C and 4C are also comparative examples for comparison with Examples 2, 3 and 4, in which components (B), (C) and (D) were extruded in advance and made into pellets, The components (A) and (F) were mixed and charged into the first region of the extruder, and the mixture was again introduced into the third region of the extruder (E).

At this time, the extrusion, injection and physical properties were measured in the same manner as in Example 1-4, and 0.2 parts by weight of the antioxidant and the heat stabilizer were added, respectively. The measurement results are shown in Table 3.

As shown in the results of Table 3, when the components are extruded at the same time, the overall physical properties are significantly deteriorated (Comparative Examples 2A, 3A and 4A), and when the impact reinforcement F is injected in the third region like the polyamide E , And the impact strength and the heat resistance are significantly deteriorated (Comparative Examples 2A, 3B, and 4B). Also, when the pellets of vinyl aromatic polymer containing epoxy group are used, the overall physical properties are generally excellent, but it can be seen that the natural color is significantly changed as compared with the use of the modified vinyl aromatic polymer in a molten state by using a secondary extruder. (Comparative Examples 2C, 3C and 4C).

Claims (5)

(A) 5 to 95 parts by weight of a polyphenylene ether resin; (B) 1 to 50 parts by weight of a vinyl aromatic polymer; (C) 0 to 2 parts by weight of an organic peroxide to the component (B); (D) 0.01 to 30 parts by weight of a reactive monomer containing an epoxy group to the component (B); (E) 5 to 95 parts by weight of a polyamide resin; And (F) 0 to 40 parts by weight of a styrene-based impact modifier; (A) and (F) are fed into a first region of an extruder having a barrel temperature of 240 to 330 占 폚 and a length of 3 to 30 占 폚 in the production of a polyphenylene ether-based thermoplastic resin composition comprising step; (B), (C) and (D) into a second region of an extruder of length 5 to 30 D, with the components in said first region not being cooled; And injecting the component (E) into a third region of the extruder, the length of which is 5 to 30 D, with the components in the second region not being cooled; Wherein the polyphenylene ether-based thermoplastic resin composition is a polyphenylene ether-based thermoplastic resin composition. The method for producing a polyphenylene ether thermoplastic resin composition according to claim 1, wherein the polyphenylene ether resin further comprises a vinyl aromatic polymer. The method according to claim 1, wherein the reactive monomer containing an epoxy group is selected from the group consisting of glycidyl methacrylate, glycidyl ethacrylate, glycidyl itagonate, aryl glycidyl ether, 2-methylaryl glycidyl ether Wherein the polyphenylene ether-based thermoplastic resin composition is at least one selected from the group consisting of polyphenylene ether-based thermoplastic resin compositions and polyphenylene ether-based thermoplastic resin compositions. The method according to claim 10, wherein the components (B), (C), and (D) charged in the second region are introduced into the main extruder after reacting in a melted state in the secondary extruder Based thermoplastic resin composition. A polyphenylene ether-based thermoplastic resin composition produced by any one of claims 1 to 4.