[summary of the invention]
Based on this, be necessary to provide a kind of safer halogen-free flame-retardant polyphenyl ether resin composition.
A kind of halogen-free flame-retardant polyphenyl ether resin composition comprises each components of following parts by weight:
100 parts of polyphenylene oxide resins;
0.5~5 part of compatilizer;
1~10 part of toughner;
5~40 parts of polystyrene resins;
5~30 parts of halogen-free flame retardantss; And
0.1~2 part of oxidation inhibitor and lubricant.
In preferred embodiment, this halogen-free flame-retardant polyphenyl ether resin composition comprises each component of following parts by weight:
100 parts of polyphenylene oxide resins;
0.5~3 part of compatilizer;
4~5 parts of toughner;
6~15 parts of polystyrene resins;
12~15 parts of halogen-free flame retardantss; And
0.2~0.4 part of oxidation inhibitor and lubricant.
In preferred embodiment, comprise that also parts by weight are 1~40 part glass fibre.
In preferred embodiment, compatilizer is a maleic anhydride graft polyphenylene oxide.
In preferred embodiment, toughner is at least a in styrene-butadiene copolymer, hydrogenated styrene-butadienecopolymer, styrene isoprene styrene block copolymer (SIS), styrene-ethylene-propylene-based block copolymer and vinylbenzene-[ethene-(ethylene-propylene)]-styrene block copolymer.
In preferred embodiment, fire retardant is at least a in triphenylphosphate and the dihydroxyphenyl propane two (diphenyl phosphoester).
In preferred embodiment, anti-dripping agent is ptfe micropowder, polytetrafluoroethylene granule and is at least a in the tetrafluoroethylene master batch of carrier with acrylonitritrile-styrene resin, acrylonitrile-styrene-butadienecopolymer or polystyrene resin.
In preferred embodiment, oxidation inhibitor is 4, at least a in 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), tris phosphite (2, the 4-di-tert-butyl-phenyl) and four [β-(3, the 5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Lubricant is at least a in ethylene bis stearamide, tetramethylolmethane stearate and the polyethylene wax.
By in above-mentioned polyphenyl ether resin composition, adding halogen-free flame retardants, than the brominated flame retardant that tradition is used, safety and reliability; And the consistency of each component is better in the prescription, can improve the processing flowability of halogen-free flame-retardant polyphenylene oxide resin simultaneously under the synergy of lubricant and oxidation inhibitor, improve the dispersing property of fire retardant in composition, the shock strength of prepared halogen-free flame-retardant polyphenylene oxide resin, bending strength and tensile strength height, fire-retardant degree well, mobile high.
In addition, also be necessary to provide a kind of preparation method of safer halogen-free flame-retardant polyphenyl ether resin composition.
A kind of preparation method of halogen-free flame-retardant polyphenyl ether resin composition comprises the steps:
Each component of following parts by weight is provided:
100 parts of polyphenylene oxide resins,
0.5~5 part of compatilizer,
1~10 part of toughner,
5~40 parts of polystyrene resins,
5~30 parts of halogen-free flame retardantss, and
0.1~2 part of oxidation inhibitor and lubricant;
Above-mentioned each component is stirred, and place twin screw extruder, screw speed 40~45Hz, wherein twin screw extruder Zhong Ge district is provided with temperature and is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts;
Extrude, granulation, promptly get the halogen-free flame-retardant polyphenyl ether resin composition.
In preferred embodiment, comprise that also extruding the back is the step of 1~40 part glass fibre at adding of screw extrusion press fine hole place's adding parts by weight.
This preparation method's principle is simple, and cost is low, and is not high to equipment requirements, and the flame retardant type acrylonitrile-styrene-butadiene resin composition properties that makes is better, can wide popularization and application.
[embodiment]
Mainly with Comparative Examples the halogen-free flame-retardant polyphenyl ether resin composition is described in further detail in conjunction with specific embodiments below.
The halogen-free flame-retardant polyphenyl ether resin composition of one embodiment comprises each components of following parts by weight:
100 parts of polyphenylene oxide resins;
0.5~5 part of compatilizer;
1~10 part of toughner;
5~40 parts of polystyrene resins;
5~30 parts of halogen-free flame retardantss; And
0.1~2 part of oxidation inhibitor and lubricant.
Preferably, this halogen-free flame-retardant polyphenyl ether resin composition comprises each component of following parts by weight:
100 parts of polyphenylene oxide resins;
0.5~3 part of compatilizer;
4~5 parts of toughner;
6~15 parts of polystyrene resins;
12~15 parts of halogen-free flame retardantss; And
0.2~0.4 part of oxidation inhibitor and lubricant.
Further preferred, comprise also in this halogen-free flame-retardant polyphenyl ether resin composition that parts by weight are 1~40 part glass fibre.
Wherein, polyphenylene oxide (PPE) resin and polystyrene resin can be powdery, granular or powdery and granulous mixture.
Compatilizer is maleic anhydride graft polyphenylene oxide (GPPS).
Toughner is at least a in styrene-butadiene copolymer (SBS), hydrogenated styrene-butadienecopolymer (SEBS), styrene isoprene styrene block copolymer (SIS) (SIS), styrene-ethylene-propylene-based block copolymer (SEPS) and vinylbenzene-[ethene-(ethylene-propylene)]-styrene block copolymer (SEEPS).
Fire retardant is at least a in (BDP) of triphenylphosphate (TPP) and dihydroxyphenyl propane two (diphenyl phosphoester).
Anti-dripping agent is ptfe micropowder, polytetrafluoroethylene granule and is at least a in the tetrafluoroethylene master batch of carrier with acrylonitritrile-styrene resin, acrylonitrile-styrene-butadienecopolymer or polystyrene resin.
Oxidation inhibitor is 4, at least a in 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), tris phosphite (2, the 4-di-tert-butyl-phenyl) and four [β-(3, the 5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Lubricant is at least a in ethylene bis stearamide (EBS), tetramethylolmethane stearate (PETS) and polyethylene (PE) wax.
By in above-mentioned polyphenyl ether resin composition, adding halogen-free flame retardants, than the brominated flame retardant that tradition is used, safety and reliability; And the consistency of each component is better in the prescription, can improve the processing flowability of halogen-free flame-retardant polyphenylene oxide resin simultaneously under the synergy of lubricant and oxidation inhibitor, improve the dispersing property of fire retardant in composition, the shock strength of prepared halogen-free flame-retardant polyphenylene oxide resin, bending strength and tensile strength height, fire-retardant degree well, mobile high.
A kind of preparation method of above-mentioned halogen-free flame-retardant polyphenyl ether resin composition comprises the steps:
Each component of following parts by weight is provided:
100 parts of polyphenylene oxide resins,
0.5~5 part of compatilizer,
1~10 part of toughner,
5~40 parts of polystyrene resins,
5~30 parts of halogen-free flame retardantss, and
0.1~2 part of oxidation inhibitor and lubricant;
Above-mentioned each component is stirred, and place twin screw extruder, screw speed 40~45Hz, wherein twin screw extruder Zhong Ge district is provided with temperature and is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts;
Extrude, granulation, promptly get the halogen-free flame-retardant polyphenyl ether resin composition.
Preferably, comprise that also extruding the back is the step of 1~40 part glass fibre at adding of screw extrusion press fine hole place's adding parts by weight.
This preparation method's principle is simple, and cost is low, and is not high to equipment requirements, and the flame retardant type acrylonitrile-styrene-butadiene resin composition properties that makes is better, can wide popularization and application.
Below be embodiment and Comparative Examples part:
Embodiment one
The set of dispense ratio of according to the form below get the raw materials ready (1 part=100 gram):
The PPE resin |
100 parts |
Compatibilizer C X-1 (the emerging product of Japanese bright dipping company product) |
0.5 part |
Toughner SBS |
5 parts |
Polystyrene resin (GPPS) |
11 parts |
Fire retardant BDP |
15 parts |
Other auxiliary agent |
0.2 part |
Pouring each component of getting material ready into stirrer stirs, and place twin screw extruder, screw speed 42Hz, temperature is set is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts, extrude, add place, fine hole at screw rod simultaneously and add 20 parts of glass fibre by weight proportion, granulation promptly gets halogen-free flame-retardant PPE resin.
The performance test results:
Embodiment two
The set of dispense ratio of according to the form below get the raw materials ready (1 part=100 gram):
The PPE resin |
100 parts |
Compatibilizer C X-1 |
1.5 part |
Toughner SEBS |
4 parts |
Polystyrene resin (GPPS) |
15 parts |
Fire retardant TPP |
12 parts |
Other auxiliary agent |
0.3 part |
Pouring each component of getting material ready into stirrer stirs, and place twin screw extruder, screw speed 42Hz, temperature is set is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts, extrude, add place, fine hole at screw rod simultaneously and add 10 parts of glass fibre by weight proportion, granulation promptly gets halogen-free flame-retardant PPE resin.
The performance test results:
Embodiment three
The set of dispense ratio of according to the form below get the raw materials ready (1 part=100 gram):
The PPE resin |
100 parts |
Compatibilizer C X-1 |
3 parts |
Toughner SIS |
5 parts |
Polystyrene resin (GPPS) |
6 parts |
Fire retardant BDP |
14 parts |
Other auxiliary agent |
0.4 part |
Pouring each component of getting material ready into stirrer stirs, and place twin screw extruder, screw speed 42Hz, temperature is set is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts, extrude, add place, fine hole at screw rod simultaneously and add 30 parts of glass fibre by weight proportion, granulation promptly gets halogen-free flame-retardant PPE resin.
The performance test results:
Embodiment four
The set of dispense ratio of according to the form below get the raw materials ready (1 part=100 gram):
The PPE resin |
100 parts |
Compatibilizer C X-1 (the emerging product of Japanese bright dipping company product) |
5 parts |
Toughner SBS |
10 parts |
Polystyrene resin (GPPS) |
40 parts |
Fire retardant BDP |
30 parts |
PETS |
0.8 part |
Oxidation inhibitor 168 |
0.8 part |
Antioxidant 1010 |
0.4 part |
Pouring each component of getting material ready into stirrer stirs, and place twin screw extruder, screw speed 42Hz, temperature is set is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts, extrude, add place, fine hole at screw rod simultaneously and add 40 parts of glass fibre by weight proportion, granulation promptly gets halogen-free flame-retardant PPE resin.
The performance test results:
In other optional embodiment, oxidation inhibitor 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol) can adopt tris phosphite (2, the 4-di-tert-butyl-phenyl) or four [β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester substitutes, or the mixture replacing of any two or three in these three kinds of oxidation inhibitor.
Comparative example one (not adding compatilizer)
The set of dispense ratio of according to the form below get the raw materials ready (1 part=100 gram):
The PPE resin |
100 parts |
Toughner SBS |
5 parts |
Polystyrene resin (GPPS) |
11 parts |
Fire retardant BDP |
15 parts |
Other auxiliary agent |
0.2 part |
Pouring each component of getting material ready into stirrer stirs, and place twin screw extruder, screw speed 42Hz, temperature is set is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts, extrude, add place, fine hole at screw rod simultaneously and add 30 parts of glass fibre by weight proportion, granulation promptly gets the halogen-free flame-retardant PPE resin that does not contain compatilizer.
The performance test results:
Comparative example two (not adding oxidation inhibitor)
The set of dispense ratio of according to the form below get the raw materials ready (1 part=100 gram):
The PPE resin |
100 parts |
Compatibilizer C X-1 |
3 parts |
Toughner SIS |
5 parts |
Polystyrene resin (GPPS) |
6 parts |
Fire retardant BDP |
14 parts |
EBS |
0.2 part |
Pouring each component of getting material ready into stirrer stirs, and place twin screw extruder, screw speed 42Hz, temperature is set is: 220 ℃ in a district, 240 ℃ in two districts, 260 ℃ in three districts, 260 ℃ in four districts, 260 ℃ in five districts, extrude, add place, fine hole at screw rod simultaneously and add 20 parts of glass fibre by weight proportion, granulation promptly gets the halogen-free flame-retardant PPE resin that does not contain oxidation inhibitor.
The performance test results:
Compare with embodiment one to three, there is not oxidation inhibitor in the prescription, the melting index of halogen-free flame-retardant PPE resin slightly improves, as seen the PPE resin has had partly degraded, performances such as shock strength, bending strength and tensile strength all have reduction, illustrate that the oxidation inhibitor that uses has significant help to the mechanical property of PPE.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.