KR101512508B1 - Polyphenyl ether elastomer composition - Google Patents

Abstract

Disclosed is a polyphenyl ether elastomer composition which comprises the following components in parts by weight: polyphenyl ether 10 to 46, polystyrene 3 to 5, high impact polystyrene 3 to 5, polyolefin elastomer 6 to 13, hydrogenated styrene-butadiene block copolymer 13 ~ 23, low density polyethylene 6 ~ 16, low density polyethylene graft polystyrene copolymer 5 ~ 8, phosphate flame retardant 18 ~ 20. Compared with the prior art, the composition of the present invention is used as a wire and cable coating material, and has flame retardancy equal to or higher than that of PVC, flexibility and mechanical strength, balance of flame retardancy and mechanical properties, It has relatively good chemical resistance, resistance to gasoline and other organic solvents, as well as being environmentally friendly.

Description

Polyphenyl ether elastomer composition < RTI ID = 0.0 >

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition, particularly a polyphenyl ether elastomer composition, which is mainly used as a covering material for electric wires and cables.

In the past, polyvinyl chloride resins have already been widely used as insulation coating materials for electric wires and cables. In recent years, however, people have become increasingly aware of the environmental and human health hazards caused by the use of large amounts of polyvinyl chloride (PVC), and dioxins are extremely dangerous to health when burned. The application regulations on polyvinyl chloride have also become more stringent in recent years and have begun to prohibit the use of polyvinyl chloride materials in many products in some countries. Among the resins for electric or electric wires, halogen-containing flame retardants, which have been conventionally used, have already reduced the possibility of fire. However, resins containing halogen compounds can release corrosive hydrogen halide gas during processing and, once ignited, release toxic gases and cause fatal injuries.

A common solution is to use halogen-free materials. In recent years, researchers and product development engineers have already developed halogen-free wires to produce polyvinyl chloride or halogen-free wire sheathing materials, Halogen-free flame-retardant electrical cable materials are used. In general, halogen-free flame retardant electrical cable materials are halogen-free flame retardants such as magnesium hydroxide, aluminum hydroxide or phosphorous-nitrogen compounds added to the polyolefin resin mixture. To ensure that the material achieves sufficient flame retardant performance, the product must be accompanied by a large amount of the flame retardant added via the VW-1 combustion test as defined by the US Safety Detection Laboratory Standard (abbreviated to UL standard). The addition of such a large amount of flame retardant deteriorates the mechanical and physical properties of the material, and significantly deteriorates the index of flexibility, tensile strength and elongation of the material.

Chinese patent 101107318A discloses a flexible thermoplastic composition for use in a wire cable of some sort. The composition comprises polyphenyl ether, a styrene block copolymer and a phosphate flame retardant. Polyphenyl ether resins have excellent mechanical properties, high strength, high heat resistance, excellent electrical performance and dimensional stability, and more importantly, they have good flame retardant performance as a component of wire and cable composites. Therefore, the composition has satisfactory flame retardancy even without containing a large amount of flame retardant. The patent has solved the problem of balancing the mechanical properties and flame retardancy of the material very well. However, the melt viscosity of the polyphenyl ether and the styrene block copolymer in the above composition is very large, which makes material processing difficult. On the other hand, polyphenyl ether is a kind of amorphous thermoplastic resin which is relatively poor in resistance to an organic solvent such as an aromatic hydrocarbon or a paraffinic hydrocarbon, and styrene block copolymer has a similar problem, and the rubber phase in the structure is likely to be eroded into organic solvent . Thus, the wires made from the composition are unsuitable for use in an environment in contact with the oil material.

Chinese patent 1711317A discloses a resin composition used for a wire and a cable covering material. The composition comprises a polyphenyl ether resin, a syndiotactic polystyrene, an olefin elastomer, a hydrogenated styrene block copolymer and a halogen-free flame retardant. Among them, the addition of a large amount of syndiotactic polystyrene significantly lowers the melting point and the processing temperature of the polystyrene, effectively solving the workability problem of the polyphenyl ether-containing composition, and the high crystallinity of the syndiotactic polystyrene is also attributable to the solvent resistance of the composition, Thereby significantly improving the resistance. However, addition of a large amount of this also causes a serious decrease in the elongation at break of the composition, so that the use of the product is limited.

Chinese patent 1930230A discloses a kind of flexible polyaryl ether composition and its product. The composition includes polyphenyl ether, a plasticizer, a styrene block copolymer, a polyolefin and a polyolefin elastomer. When the composition is used as a wire cable material, it has excellent processability and mechanical properties. However, since a relatively high content of the polyolefin or polyolefin elastomer and polyphenyl ether in the composition is a two-phase system which is incompatible with each other, the delamination phenomenon of interlaminar delamination tends to occur in the molded article.

Chinese patent 101080466A discloses a kind of flexible (arylene ether) composition and its products. The composition includes polyphenyl ether, polypropylene, styrene block copolymer, and flame retardant. The composition is excellent in mechanical properties and processability, and has relatively good oil resistance. However, since the composition has a relatively high hardness, flexibility is insufficient and the application range is limited.

It is an object of the present invention to provide an elastomeric composition of polyphenyl ether to overcome the deficiencies present in the prior art. The composition is used for a covering material of a wire cable and has a flame retardancy equal to or higher than that of PVC, a flexibility and a mechanical strength, a balance of flame retardancy and excellent mechanical properties, excellent processing performance, excellent chemical resistance, And other organic solvents as well as being environmentally friendly.

The object of the present invention is achieved through the following technical solutions.

The present invention relates to a polyphenyl ether elastomer composition comprising the following components, expressed in parts by weight:

Polyphenyl ether 10 to 46,

Polystyrene 3 to 5,

High impact polystyrene 3-5,

Polyolefin elastomers 6 to 13,

Hydrogenated styrene-butadiene block copolymers 13 to 23,

Low density polyethylene 6 to 16,

Low density polyethylene graft polystyrene copolymer 5 to 8,

Phosphate flame retardant 18-20

Preferably, the polyphenyl ether is poly (2,6-dimethyl-1,4-phenylene ether) and the intrinsic viscosity of the poly (2,6-dimethyl-1,4-phenylene ether) 0.0 > dl / g < / RTI > as measured in chloroform.

Preferably, the polystyrene is a general-purpose polystyrene as a random copolymer, and the high-impact polystyrene is a polybutadiene-grafted high-impact-strength polystyrene produced by a bulk suspending method or a bulking method.

Preferably, the polyolefin elastomer is an ethylene-butylene copolymer thermoplastic elastomer.

Preferably, the content of styrene in the hydrogenated styrene-butadiene block copolymer is 13 to 40% by weight.

Preferably, the low density polyethylene is a thermoplastic plastic obtained by free radical polymerization of ethylene at a high pressure, and the melt index of the low density polyethylene is 0.3 to 20 g / 10 min as measured at 190 캜 and 2.16 kg.

Preferably, the content of polystyrene in the low density polyethylene graft polystyrene copolymer is 30% by weight.

Preferably, the phosphate flame retardant is bisphenol A bisdiphenyl phosphate or resorcinol bisdiphenyl phosphate.

Preferably, the polyphenyl ether elastomer composition further comprises at least one of an antioxidant, an ultraviolet absorber, and an inorganic filler.

Preferably, the polyphenyl ether elastomer composition comprises 0.5 parts by weight of an antioxidant and 0.2 parts by weight of an ultraviolet absorber.

Compared with the prior art, the present invention has the following advantages: The composition of the present invention does not contain a halogen, has flame retardancy and excellent mechanical properties, and has extremely excellent processability, heat resistance and flexibility. Among them, in the case of flame retardancy, the composition generally has a flammability rating of UL95 (3.2 mm) VO, besides the composition also has a relatively good chemical resistance, resistance to gasoline and other organic solvents.

Hereinafter, the present invention will be described with reference to specific examples. It is to be understood that the following examples are illustrative of the present invention only and are not intended to limit the scope of the present invention in any way.

The polyphenyl ether elastomer composition of the present invention comprises the following components and is expressed in parts by weight: polyphenyl ether 10 to 46, polystyrene 3 to 5, high impact polystyrene 3 to 5, polyolefin elastomer 6 to 13, hydrogenated styrene-butadiene block Copolymers 13 to 23, low density polyethylene 6 to 16, low density polyethylene graft polystyrene copolymer 5 to 8, phosphate flame retardant 18 to 20.

Among them, the polyphenyl ether is a known poly (2,6-dimethyl-1,4-phenylene ether), and is a thermoplastic resin formed by oxidation-coupling polymerization of 2,6- 2,6-dihydroxyphenol was synthesized by using toluene and phenol as raw materials. Polyphenyl ether has excellent mechanical strength, heat resistance and excellent electrical insulation. The main disadvantages are poor melt flowability and difficult molding, typically improving processing fluidity by mixing resins such as PS, PA, and elastomers.

The polystyrene is a random copolymerized general-purpose polystyrene, which is referred to as GPPS, and is defined as a polymer synthesized by free radical polymerization of a styrene monomer. The most important characteristic of polystyrene is that it is easy to form because of its excellent thermal stability and melt flowability. On the other hand, polystyrene is fully compatible with polyphenyl ether and can sufficiently lower the melt processing temperature of polyphenyl ether. In the market, polystyrene mixed modified polyphenyl ether is already on the market, and can be used if the composition ratio is fully understood.

The high-impact polystyrene is known as graft-type high-impact polystyrene, and is referred to as HIPS, and is a polybutadiene graft-type high-impact polystyrene produced by the bulk suspension method or the bulk method.

The polyolefin elastomer is an ethylene-butylene copolymer thermoplastic elastomer (EBR) obtained by random copolymerization of ethylene and butylene having four carbon atoms, and using a well-known titanium catalyst and a metallocene catalyst, for example, Catalytic polymerization, gas phase polymerization and solution polymerization.

The molecular chain of the hydrogenated styrene-butadiene block copolymer is saturated, the double bonds in the butadiene block are removed through hydrogenation, and the hydrogenated block copolymer includes styrene block A and block B of butadiene. A and B may be of a block type structure such as A-B, A-B-A, A-B-A-B-A.

The low density polyethylene is a thermoplastic plastic obtained by free radical polymerization of ethylene at a high pressure and has a melt index of 0.3 to 20 g / 10 mm when measured under the conditions of 190 캜 and 2.16 kg.

The low density polyethylene grafted polystyrene copolymer (LDPE-graft-PS) serves as a compatibilizer, the main chain is a molecular chain of low density polyethylene, and the side chain is a molecular chain of polystyrene.

The phosphate flame retardant includes bisphenol A bis (diphenylphosphate) (BDP), resorcinol bis (diphenylphosphate) (RDP).

According to the present invention, the polyphenyl ether elastomer composition permits mixing of an appropriate amount of one or more additives such as antioxidants, ultraviolet absorbers, inorganic fillers (talc, calcium carbonate, magnesium hydroxide, zinc sulfide, etc.) .

There is no limitation on the production method of the polyphenyl ether elastomer composition. For example, a twin-screw extruder, a single screw extruder, an airtight mixer, and an open mixer, and those skilled in the art will be able to make the composition of the present invention using such a device relatively skillfully.

Examples 1 to 4

The specific components contained in the polyphenyl ether elastomer compositions of Examples 1 to 4 are shown in Table 1, and the content by weight is as shown in Table 2. In Table 2, "P" indicates acceptance and "NP" indicates rejection.

PPE045 Poly 2,6-dimethyl-1,4-phenylene ether, intrinsic viscosity measured at 25 ° C in chloroform: 0.45 dl / g. Product name: PP0045, Lansing Chemical Co., Ltd. PPE025 Poly 2,6-dimethyl-1,4-phenylene ether, intrinsic viscosity measured at 25 ° C in chloroform: 0.25 dl / g. PPE050 Poly 2,6-dimethyl-1,4-phenylene ether, intrinsic viscosity measured at 25 ° C in chloroform: 0.50 dl / g. GPPS General purpose polystyrene, Product name: PG22. Manufactured by Taiwan Chi Mei Co., Ltd. HIPS High impact polystyrene, product name: HIPS8250. Taiyuan (Taiwan) Manufacturing EBR Ethylene-butylene copolymer thermoplastic elastomer (product name: ENGAGE 7387, produced by DOW CHEMICAL) SBES1657 Hydrogenated styrene-butadiene block copolymer, styrene content 13%, produced by KRATON POLYMERS SEBS 6936 Hydrogenated styrene-butadiene block copolymer, styrene content 40%, produced by KRATON POLYMERS YH-503 Hydrogenated styrene-butadiene block copolymer, styrene content of 33%, petroleum chemical production of China Petroleum Co., LDPE 1080D (MI) of 0.3 g / 10 min measured at 190 占 폚 under 2.16 kg of low-density polyethylene, produced by Yangfu Petrochemical-BASF Co., Ltd. LDPE 1C7A (MI) of 0.3 g / 10 min measured at 190 占 폚 under 2.16 kg of low-density polyethylene, produced by Yangfu Petrochemical-BASF Co., Ltd. LDPE M7020S Density polyethylene having a melt index (MI) of 20 g / 10 min as measured at 190 占 폚 and 2.16 kg, produced by Asahi Kasei Corporation of Japan. LDPE-graft-PS MODIPER A1100, manufactured by Nippon Oil & Co., Ltd., in which the weight percentage of polystyrene is 30% BDP Bisphenol A bis (diphenyl phosphate), produced by Changchun Chemical Co., Taiwan Product name: FP-600 RDP Resorcinol-bis (diphenylphosphate), manufactured by Asahi R & D Co., Ltd. Product name: Fyrolflex RDP Antioxidant Phenolic antioxidant, a product of Ciba Co., Ltd. Product name: AO 1076 Ultraviolet absorber Bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, ultraviolet absorber produced by Ciba, product name: UV 770

Comparative Examples 5 to 8

The polyphenyl ether elastomer compositions of Comparative Examples 5 to 8 contain the specific components shown in Table 1. The corresponding weight parts are shown in Table 2. In Table 2, "P" indicates acceptance and "NP" indicates rejection.

Example 9, performance comparison experiment

The compositions of Examples 1 to 4 and Comparative Examples 5 to 8 were prepared using a twin-screw extruder having a diameter of 35 mm, the melt temperature was set at 240 to 260 ° C, and the shaft rotation speed was set at 280 rpm. Particles of the obtained composition were sintered at a temperature of 250 ° C, and a performance comparison experiment was conducted with the molded specimen. A specific performance test program is as follows: The tensile strength and elongation at break were measured according to the ASTM D638 method. The shore hardness was measured according to the ASTM D2240 method. The melt flow rate (MFI) of the melt was measured under the conditions of 250 캜 and 5 kg according to the ASTM D1238 method. The flexural modulus was measured according to ASTM D790. According to the UL94 method, a sample with a thickness of 3.2 mm was evaluated for flame retardancy. Chemical resistance was measured according to ISO 6722, and the chemical used was gasoline. The experimental results are shown in Table 2.

One 2 3 4 5 * 6 * 7 * 8* PPE045 46 35 35 42 35 35 PPE025 23.5 PPE050 10 GPPS 3 4 4 5 4 4 8 4 HIPS 3 4 5 5 4 4 4 EBR 6 7 11 13 7 7 7 14 SBES1657 13 17 17 17 17 17 SEBS 6936 21 YH-503 23 LDPE 1080D 10 16 LDPE 1C7A 6 LDPE M7020S 7 13 7 7 LDPE-graft-PS 5 6 7 8 6 6 6 BDP 18 20 20 13 20 20 RDP 18.5 20 AO 1076 0 0.5 0 0.5 0.5 0.5 0.5 0.5 UV 770 0 0.2 0 0.2 0.2 0.2 0.2 0.2 ASTM Hardness 60D 55D 93A 87A 57D 59D 57D 52D MFI 2.5 4.1 10.5 28.0 5.7 2.7 5.2 6.7 The tensile strength 27 23 20 15 22 24 23 22 Elongation at break 99 150 187 235 56 112 132 158 Flexural modulus 1100 750 187 110 880 960 820 690 Flammability UL94 V0 V0 V1 V1 V0 Non-graded V0 V0 Gasoline resistance P P P P P P P NP

As can be seen from Table 2, when Example 2 and Comparative Examples 5 to 8 are compared, Comparative Example 5 has an unacceptably low elongation, and the compatibilizer LDPE-Graft-PS can be used to increase the elongation at break . In Comparative Example 6, the flame retardant effect was unsatisfactory because the amount of the flame retardant used was insufficient. Comparative Example 7 demonstrates that using a single GPPS, the elongation is significantly lower than that of Example 2, and the flexibility is lowered by increasing the flexural modulus. Comparative Example 8 failed to pass the resistance test for gasoline, demonstrating that crystalline LDPE plays an important role in the resistance of the composition to gasoline.

When the above composition is used as a wire cable covering material, it has flame retardancy, flexibility and mechanical strength equal to or higher than that of PVC, and has a balance of flame retardancy and mechanical properties, and thus has excellent processing characteristics, , Is resistant to gasoline and other organic solvents as well as environmentally friendly.

Claims (10)

A polyphenyl ether elastomer composition comprising parts by weight of:
Polyphenyl ether 10 to 46;
Polystyrene 3-5;
High impact polystyrene 3-5;
Polyolefin elastomers 6-13;
Hydrogenated styrene-butadiene block copolymers 13 to 23;
Low density polyethylene 6 ~ 16;
Low density polyethylene graft polystyrene copolymer 5 to 8; And
Phosphate flame retardant 18-20,
The high-impact polystyrene is a polybutadiene graft-type polystyrene. The method according to claim 1,
The polyphenyl ether is poly 2,6-dimethyl-1,4-phenylene ether. When measured in chloroform at 25 ° C, the intrinsic viscosity of the poly 2,6-dimethyl- 0.5 dl / g. ≪ / RTI > The method according to claim 1,
Wherein the polystyrene is a general-purpose polystyrene (GPPS) which is a random copolymer, and the high-impact polystyrene is a polybutadiene graft-type high-impact-strength polystyrene which is produced through a bulk suspending method or a bulking method. The method according to claim 1,
Wherein the polyolefin elastomer is an ethylene-butylene copolymer thermoplastic elastomer. The method according to claim 1,
Wherein the content of styrene in the hydrogenated styrene-butadiene block copolymer is 13 to 40% by weight. The method according to claim 1,
Wherein the low density polyethylene is a thermoplastic plastic obtained by free radical polymerization of ethylene at a high pressure and the low density polyethylene has a melt index of 0.3 to 20 g / 10 min as measured at 190 DEG C and 2.16 kg. The method according to claim 1,
Wherein the content of polystyrene in the low density polyethylene graft polystyrene copolymer is 30% by weight. The method according to claim 1,
Wherein the phosphate flame retardant is bisphenol A bisdiphenyl phosphate or resorcinol bisdiphenyl phosphate. The method according to claim 1,
Wherein the polyphenyl ether elastomer composition further comprises at least one of an antioxidant, an ultraviolet absorber, and an inorganic filler. 10. The method of claim 9,
Wherein the polyphenyl ether elastomer composition comprises 0.5 parts by weight of an antioxidant and 0.2 parts by weight of an ultraviolet absorber.