CN101698742A - Halogen-free flame-resistant high-temperature-resistant flexible polyphenylether cable material and preparation method thereof - Google Patents

Abstract

The invention discloses a halogen-free flame-resistant high-temperature-resistant flexible polyphenylether cable material and a preparation method thereof. The polyphenylether cable material comprises the following raw materials in parts by mass: 30-60 parts of matrix resin A, 40-70 parts of matrix resin B, 10-30 parts of elastomer, 1-10 parts of functionalized polyphenylether, 1-10 parts of lubricant, 0.2-2 parts of cross linker, 5-30 parts of main flame retardant and 1-10 parts of auxiliary flame retardant. The invention uses the functionalized polyphenylether to enhance the flowability of the matrix resins, and uses the cross linker to effectively improve the compatibility of the matrix resin A and the matrix resin B with the elastomer, so that the polyphenylether cable material of the invention has the advantages of environmental protection, high temperature resistance, high toughness and favorable flame resistance.

Description

A kind of halogen-free flame retardant high temperature resistant flexible polyphenylene ether cable material and preparation method thereof

technical field

The invention relates to a halogen-free flame-retardant material, in particular to a halogen-free flame-retardant high-temperature-resistant flexible polyphenylene ether cable material.

Background technique

Wires and cables are widely used in all aspects of daily life. With the strengthening of environmental protection awareness, the international requirements for fire protection and environmental protection of wires and cables are getting higher and higher. Traditional flame-retardant cables use halogen flame-retardants, which will produce a large amount of irritating and corrosive gases in the event of a fire, endangering human health and hindering personnel from escaping. Cables used at high temperatures are often cross-linked to increase the service temperature of polymer cable jackets, but such cross-linked cables cannot be recycled, which is not conducive to environmental protection. Therefore, there is an urgent need to develop a recyclable, high-performance halogen-free flame-retardant and high-temperature-resistant cable material.

Polyphenylene ether has excellent comprehensive properties in a wide temperature range and is self-extinguishing. However, due to the high processing viscosity, high hardness and insufficient toughness of polyphenylene ether, it is not conducive to the application of cables. The addition of low viscosity and flexibility Good elastomers can prepare cable materials with excellent performance. The Chinese invention patent application with the patent publication number CN101358028A discloses a cable based on polyphenylene ether, which uses several compatibilizers to improve the interface between polyphenylene ether and elastomer, and uses a large amount of softening plasticizer Reduce the hardness of the blend, so that the obtained blend has low strength, poor heat resistance and aging resistance. Publication number CN101130616A Chinese invention patent application discloses a method for preparing halogen-free flame-retardant polyphenylene ether cable compound, using polystyrene polymer to increase the fluidity of polyphenylene ether, adding unsaturated rubber elastomer to reduce the hardness of the blend , Such a system contains a large number of unsaturated olefin chains, which will undoubtedly greatly reduce the heat resistance and aging resistance of the blend.

Contents of the invention

Aiming at the deficiencies of the prior art, the invention provides a recyclable, high-performance, halogen-free, flame-retardant, high-temperature-resistant flexible polyphenylene ether cable material.

Another object of the present invention is to provide a preparation method of the above-mentioned polyphenylene ether cable material.

The present invention uses low-molecular-weight functionalized polyphenylene ether to improve the fluidity of the cable material, uses dynamic cross-linking technology, adds a cross-linking agent to vulcanize matrix resin A and matrix resin B under high shear, and improves the two matrix The interfacial binding force of the resin increases the toughness and flexibility of the blend, and a halogen-free flame-retardant high-temperature polyphenylene ether cable material with excellent comprehensive performance is prepared.

The technical scheme that the present invention adopts for achieving the above object is:

A halogen-free flame-retardant and high-temperature-resistant flexible polyphenylene ether cable material is characterized in that, in terms of parts by mass, its raw material formula includes:

Matrix resin A: 30-60 parts

Matrix resin B: 40-70 parts

Elastomer: 10-30 parts

Functionalized polyphenylene ether: 1 to 10 parts

Lubricant: 1 to 10 parts

Cross-linking agent: 0.2 to 2 parts

Primary flame retardant: 5-30 parts

Auxiliary flame retardant: 1 to 10 parts

The base resin A is polyphenylene ether, preferably poly(2,6-dimethyl-1,4-phenylene) ether, and its intrinsic viscosity in chloroform at 25°C is 0.3-0.6dl/g;

The base resin B is EPDM rubber with a Mooney value of 20-40, wherein the ethylene content is 50%-70% of the total mass of the three monomers, and the third monomer conjugated diene is ethylidene norbornene Alkene (ENB) or dicyclopentadiene (DCPD), the weight content of which is 2% to 10% of the total weight of the three monomers;

Described elastomer is selected from styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), maleic anhydride grafted hydrogenated styrene - butadiene-styrene block copolymer (SEBS-g-MA) and/or maleic anhydride grafted ethylene-propylene-diene rubber (EPDM-g-MA);

The functionalized polyphenylene ether is maleic anhydride grafted polyphenylene ether (PPO-g-MA) or phosphated polyphenylene ether, and the characteristics of the polyphenylene ether measured in chloroform at 25°C before graft modification The viscosity number is 0.2～0.4dl/g.

The flame retardant is selected from resorcinol-bis(diphenyl phosphate) (RDP), bisphenol A-bis(diphenyl phosphate) (BDP) or pentaerythritol spirocyclic phosphate (PSDPP);

式中x、y为两结构单元的摩尔分数，x为0.2～0.4，y为0.6～0.8，R₁为甲基，R₂为苯基。The auxiliary flame retardant is polyorganosiloxane with a number average molecular weight of 1.0×10 ³ to 5.0×10 ³ and a structural formula of:

In the formula, x and y are the mole fractions of the two structural units, x is 0.2-0.4, y is 0.6-0.8, R ₁ is a methyl group, and R ₂ is a phenyl group.

The lubricant is selected from dimethyl silicone oil (DMSiO), methylphenyl silicone oil (MPhSiO), paraffin wax, amide wax, stearic acid esters or stearic acid soaps.

The crosslinking agent is selected from dicumyl peroxide (DCP), benzoyl peroxide (BPO), sulfur (S) or tetramethylthiuram disulfide (TT).

In addition, in order to improve the stability and applicability of the product, the raw material formula also includes processing aids, and the processing aids include antioxidants, metal oxides, metal deactivators and/or smoke suppressants. The antioxidant is selected from hindered phenols, hindered amines and/or phosphite antioxidants.

The preparation method of the halogen-free flame-retardant and high-temperature-resistant flexible polyphenylene ether cable material is characterized in that: each component is weighed according to the raw material formula, and the matrix resin B and the crosslinking agent are mixed in a high-speed mixer for 15 to 30 minutes, and then the Base resin A, elastomer, functionalized polyphenylene ether, lubricant, main flame retardant, auxiliary flame retardant and antioxidant, add to the high-speed mixer and mix for 15 to 30 minutes, and mix well; mix well Add the raw materials into the twin-screw extruder, the feeding speed is 20-60rpm/min, the screw speed is 100-400rpm/min, the screw length-to-diameter ratio is 33-45, the processing temperature is 200-280°C, after cooling, pelletize to obtain halogen-free Flame retardant and high temperature resistant flexible polyphenylene ether cable pellets.

The present invention has such advantages and beneficial effects as follows:

(1) The present invention uses low molecular weight functionalized polyphenylene ether to improve the fluidity of the material and the heat resistance of the material, and the change rate of strength and elongation at break is less than 15% after aging in hot air at 136°C for 168 hours.

(2) The present invention adopts dynamic vulcanization technology to improve the compatibility between polyphenylene ether and EPDM rubber, and improve the toughness of polyphenylene ether.

(3) The present invention utilizes the synergistic flame-retardant effect of organosilicon flame retardants and phosphoric acid ester flame retardants to reduce the amount of phosphoric acid esters in the resin, so that the prepared cables have good high temperature resistance and can make the flame retardant properties Passed UL1581VW-1 level combustion test.

Detailed ways

Below in conjunction with embodiment the present invention will be further described, but the scope of protection of the present invention is not limited to the scope that embodiment represents.

Example 1:

Mix 400g EPDM (Dow EPDM4725P) matrix resin B, 6g sulfur crosslinking agent and 10g zinc oxide in a high-speed mixer for 15 minutes, then add 600g PPO (Asahi Kasei S201A) matrix resin A, 300g SEBS (Kraton G1651) elastomer , 100g phosphated polyphenylene ether, 50g ethylene bis fatty acid amide lubricant, 50g RDP flame retardant, 30g auxiliary flame retardant and 10g antioxidant Songnox6280 were mixed in a high-speed mixer for 20 minutes. Put the mixed raw materials into the twin-screw extruder for extrusion, after cooling, pelletize to obtain the halogen-free flame-retardant high-temperature resistant flexible polyphenylene ether cable pellets, the extrusion feeding speed is 30rpm/min, and the screw speed is 400rpm/min , the screw aspect ratio is 40, the processing temperature is 200 °C in the first zone, 220 °C in the second area, 230 °C in the third area, 250 °C in the fourth area, 260 °C in the fifth area, 270 °C in the sixth area, 280 °C in the seventh area, 280 °C in the eighth area, and 280 °C in the ninth area. Zone 280°C, Ten Zone 270°C.

Example 2:

Mix 400g EPDM (Dow EPDM4725P) matrix resin B and 3g DCP crosslinking agent in a high-speed mixer for 20 minutes, then add 600g PPO (Asahi Kasei S201A) matrix resin A, 100g SEBS-g-MA (Kraton G1901) elastomer , 100g PPO-g-MA, 20g methyl phenyl silicone oil lubricant, 200g BDP flame retardant, 10g auxiliary flame retardant and 6g antioxidant 264 were mixed in a high-speed mixer for 30 minutes. Put the mixed raw materials into the twin-screw extruder for extrusion, after cooling, pelletize to obtain the halogen-free flame-retardant high-temperature resistant flexible polyphenylene ether cable pellets, the extrusion feeding speed is 30rpm/min, and the screw speed is 400rpm/min , the screw aspect ratio is 40, the processing temperature is 200°C in the first zone, 200°C in the second zone, 230°C in the third zone, 250°C in the fourth zone, 260°C in the fifth zone, 270°C in the sixth zone, 280°C in the seventh zone, 280°C in the eighth zone, and 280°C in the ninth zone. Zone 280°C, Zone 10 270°C.

Example 3:

Mix 500g EPDM (Dow EPDM4520) matrix resin B and 6g DCP crosslinking agent in a high-speed mixer for 20 minutes, then add 500g PPO (Asahi Kasei S201A) matrix resin A, 150g SEBS (KratonG1651) elastomer, 100g PPO-g -MA, 30g pentaerythritol stearate lubricant, 100g PSDPP flame retardant, 100g secondary flame retardant and 10g antioxidant 1076 were mixed in a high-speed mixer for 30 minutes. Put the mixed raw materials into the twin-screw extruder for extrusion, after cooling, pelletize to obtain the halogen-free flame-retardant high-temperature resistant flexible polyphenylene ether cable pellets, the extrusion feeding speed is 30rpm/min, and the screw speed is 400rpm/min , the screw aspect ratio is 40, the processing temperature is 200°C in the first zone, 200°C in the second zone, 230°C in the third zone, 250°C in the fourth zone, 260°C in the fifth zone, 270°C in the sixth zone, 280°C in the seventh zone, 280°C in the eighth zone, and 280°C in the ninth zone. Zone 280°C, Zone 10 270°C.

Example 4:

Mix 600g EPDM (Dow EPDM4725P) matrix resin B, 20g TT crosslinking agent and 20g zinc oxide in a high-speed mixer for 15 minutes, then add 400g PPO (Asahi Kasei S201A) matrix resin A, 200g SEBS-g-MA (Kraton G1901) elastomer, 10g PPO-g-MA, 50g ethylene bis fatty acid amide lubricant, 300g BDP flame retardant, 10g auxiliary flame retardant, 6g antioxidant 264 and 20g molybdenum trioxide smoke suppressant to a high-speed mixer Mix for 30 minutes. Put the mixed raw materials into the twin-screw extruder for extrusion, after cooling, pelletize to obtain the halogen-free flame-retardant high-temperature resistant flexible polyphenylene ether cable pellets, the extrusion feeding speed is 30rpm/min, and the screw speed is 400rpm/min , the screw length-to-diameter ratio is 40, the processing temperature is 200 °C in the first zone, 200 °C in the second area, 220 °C in the third area, 240 °C in the fourth area, 260 °C in the fifth area, 270 °C in the sixth area, 280 °C in the seventh area, 280 °C in the eighth area, and 280 °C in the ninth area. Zone 280°C, Ten Zone 270°C.

Example 5:

Mix 700g EPDM (Dow EPDM4725P) matrix resin B, 8g crosslinking agent sulfur and 20g zinc oxide in a high-speed mixer for 15 minutes, then add 300g PPO (Asahi Kasei S201A) matrix resin A, 100g SEBS (Kraton G1651) elastomer in turn , 100g PPO-g-MA, 100g pentaerythritol stearate lubricant, 200g RDP flame retardant, 30g auxiliary flame retardant, 6g antioxidant Songnox6280 and 6g metal deactivator MD1024 were mixed in a high-speed mixer for 20 minutes. Put the mixed raw materials into the twin-screw extruder for extrusion, after cooling, pelletize to obtain the halogen-free flame-retardant high-temperature resistant flexible polyphenylene ether cable pellets, the extrusion feeding speed is 30rpm/min, and the screw speed is 400rpm/min , the screw length-to-diameter ratio is 40, the processing temperature is 200 °C in the first zone, 200 °C in the second area, 220 °C in the third area, 240 °C in the fourth area, 260 °C in the fifth area, 270 °C in the sixth area, 280 °C in the seventh area, 280 °C in the eighth area, and 280 °C in the ninth area. Zone 280°C, Ten Zone 270°C.

Comparative example:

Add high-impact polystyrene according to the existing technology, do not adopt the comparative example of dynamic cross-linking technology, 400gEPDM (Dow's EPDM4725P) matrix resin B, 600g PPO (Asahi Kasei S201A) matrix resin A, 200gHIPS (A-TECH 1300 ), 100g SEBS-g-MA (Kraton G1901) elastomer, 20g pentaerythritol stearate lubricant, 150g BDP flame retardant and 10g antioxidant Songnox6280 were mixed in a high-speed mixer for 30 minutes. Put the mixed raw materials into the twin-screw extruder for extrusion, after cooling, pelletize to obtain the halogen-free flame-retardant high-temperature resistant flexible polyphenylene ether cable pellets, the extrusion feeding speed is 30rpm/min, and the screw speed is 400rpm/min , the screw aspect ratio is 40, the processing temperature is 200°C in the first zone, 200°C in the second zone, 230°C in the third zone, 250°C in the fourth zone, 260°C in the fifth zone, 270°C in the sixth zone, 280°C in the seventh zone, 280°C in the eighth zone, and 280°C in the ninth zone. Zone 280°C, Zone 10 270°C.

The properties of the blends of Examples 1-5 and Comparative Example are shown in Table 1. The examples in the table correspond to the above-mentioned embodiments.

Table 1

According to the results in Table 1, it can be seen that the halogen-free flame-retardant flexible polyphenylene ether cable pellets of the present invention can increase the tensile strength by 75%, the impact strength can be increased by 60%, and the heat resistance is excellent. It can be drawn a high temperature resistant cable of 105°C with good comprehensive performance, and can pass the vertical burning test of UL1581 VW-1.

The description of the above embodiments is only used to help understand the core idea and characteristics of the present invention, and its purpose is to allow those familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (6)

1. A halogen-free flame-retardant high-temperature-resistant flexible polyphenylene ether cable material, characterized in that, in parts by mass, its raw material formula includes: Matrix resin A: 30-60 parts Matrix resin B: 40-70 parts Elastomer: 10-30 parts Functionalized polyphenylene ether: 1 to 10 parts Lubricant: 1 to 10 parts Cross-linking agent: 0.2 to 2 parts Primary flame retardant: 5 to 30 parts Auxiliary flame retardant: 1 to 10 parts The base resin A is polyphenylene ether, preferably poly(2,6-dimethyl-1,4-phenylene) ether, and its intrinsic viscosity in chloroform at 25°C is 0.3-0.6dl/g; The base resin B is EPDM rubber with a Mooney value of 20-40, wherein the ethylene content is 50%-70% of the total mass of the three monomers, and the third monomer conjugated diene is ethylidene norbornene Dicyclopentadiene or dicyclopentadiene, the weight content of which is 2% to 10% of the total weight of the three monomers; Described elastomer is selected from styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, maleic anhydride grafted hydrogenated styrene-butadiene-benzene Ethylene block copolymer and/or maleic anhydride grafted EPDM rubber; The functionalized polyphenylene ether is maleic anhydride grafted polyphenylene ether or phosphated polyphenylene ether, and before graft modification, the intrinsic viscosity of the polyphenylene ether resin measured in chloroform at 25°C is 0.2-0.4 dl/g; The main flame retardant is selected from resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate) or pentaerythritol spirocyclic phosphate; The auxiliary flame retardant is polyorganosiloxane with a number average molecular weight of 1.0×10 ³ to 5.0×10 ³ and a structural formula of:

In the formula, x and y are the mole fractions of the two structural units, x is 0.2-0.4, y is 0.6-0.8, R ₁ is a methyl group, and R ₂ is a phenyl group. 2. The halogen-free flame-retardant high-temperature-resistant flexible polyphenylene ether cable material according to claim 1, wherein the lubricant is selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, paraffin wax, amide wax, hard Fatty acid esters or stearic acid soaps. 3. according to claim 1 according to claim 1, the halogen-free flame-retardant high-temperature-resistant flexible polyphenylene ether cable material is characterized in that, the crosslinking agent is selected from dicumyl peroxide, benzoyl peroxide Or sulfur or tetramethylthiuram disulfide. 4. The halogen-free flame-retardant and high-temperature-resistant flexible polyphenylene ether cable material according to claim 1, characterized in that, the halogen-free flame-retardant and high-temperature-resistant flexible polyphenylene ether cable material also includes a processing aid, and the processing aid Agents include antioxidants, metal oxides, metal deactivators and/or smoke suppressants. 5. The halogen-free flame-retardant high-temperature-resistant flexible polyphenylene ether cable material according to claim 4, wherein the antioxidant is selected from hindered phenols, hindered amines and/or phosphite antioxidants agent. 6. The preparation method of the halogen-free flame-retardant high-temperature-resistant flexible polyphenylene ether cable material according to claim 1, characterized in that: each component is weighed according to the raw material formula, and the matrix resin B and the crosslinking agent are first mixed in a high-speed mixer 15 to 30 minutes, then add matrix resin A, elastomer, functionalized polyphenylene ether, lubricant, primary flame retardant, secondary flame retardant and antioxidant to the high-speed mixer and mix for 15 to 30 minutes, Mix well; put the mixed raw materials into the twin-screw extruder, the feeding speed is 20-60rpm/min, the screw speed is 100-400rpm/min, the length-to-diameter ratio of the screw is 33-45, and the processing temperature is 200-280°C. Cool and pelletize to obtain the halogen-free flame retardant high temperature resistant flexible polyphenylene ether cable pellets.