CN102234419A - Halogen-free flameproof polyphenylene ether resin composition and preparation method thereof - Google Patents
Halogen-free flameproof polyphenylene ether resin composition and preparation method thereof Download PDFInfo
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- CN102234419A CN102234419A CN2011101170468A CN201110117046A CN102234419A CN 102234419 A CN102234419 A CN 102234419A CN 2011101170468 A CN2011101170468 A CN 2011101170468A CN 201110117046 A CN201110117046 A CN 201110117046A CN 102234419 A CN102234419 A CN 102234419A
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- halogen
- ether resin
- free flame
- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001955 polyphenylene ether Polymers 0.000 title abstract 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 42
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 36
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 36
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 27
- 239000003112 inhibitor Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 5
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 3
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920006132 styrene block copolymer Polymers 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000003963 antioxidant agent Substances 0.000 abstract 2
- 230000003078 antioxidant effect Effects 0.000 abstract 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 230000009970 fire resistant effect Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a halogen-free flameproof polyphenylene ether resin composition which comprises the following components in parts by weight: 100 parts of polyphenylene ether resin, 0.5-5 parts of compatilizer, 1-10 parts of compatilizer, 5-40 parts of polystyrene resin, 5-30 parts of halogen-free fire retardant, and 0.1-2 parts of antioxidant and lubricant. The halogen-free fire retardant is added into the polyphenylene ether resin composition, compared with traditionally used bromine fire retardants, the halogen-free fire retardant is safer and more reliable; the compatibility of various components in the formula is relatively good; simultaneously, by the synergistic action of the lubricant and the antioxidant, the processing flow property of the halogen-free flameproof polyphenylene ether resin and the dispersing property of the fire retardant in the composition can be improved. The prepared halogen-free flameproof polyphenylene ether resin has high impact strength, flexural strength and tensile strength, good fire resistant degree, and high flow property. In addition, the invention further relates to a preparation method of the halogen-free flameproof polyphenylene ether resin composition.
Description
[technical field]
The present invention relates to polymeric material field, relate in particular to a kind of halogen-free flame-retardant polyphenyl ether resin composition and preparation method thereof.
[background technology]
Polyphenylene oxide (PPE) resin is the high-strength engineering plastic that grows up the sixties in last century, has good mechanical property, and electrical property and resistance toheat are mainly used in aspects such as electronic apparatus, automobile, office equipment and industrial machinery.But the fire retardant that uses in traditional PPE resin combination mostly is brominated flame retardant, because brominated flame retardant can produce a large amount of brominated toxic and harmfuls in combustion processes, thereby brings great harm to human health.
[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.
Claims (10)
1. a halogen-free flame-retardant polyphenyl ether resin composition is characterized in that, comprises each component 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;
0.1～2 part of oxidation inhibitor and lubricant.
2. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1 is characterized in that, 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.
3. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1 is characterized in that, comprises that also parts by weight are 1～40 part glass fibre.
4. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1 is characterized in that, described compatilizer is a maleic anhydride graft polyphenylene oxide.
5. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1, it is characterized in that described 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.
6. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1 is characterized in that, described fire retardant is at least a in triphenylphosphate and the dihydroxyphenyl propane two (diphenyl phosphoester).
7. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1, it is characterized in that described 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.
8. halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 1, it is characterized in that, described oxidation inhibitor is 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), tris phosphite (2, the 4-di-tert-butyl-phenyl) at least a and in four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described lubricant is at least a in ethylene bis stearamide, tetramethylolmethane stearate and the polyethylene wax.
9. the preparation method of a halogen-free flame-retardant polyphenyl ether resin composition is characterized in that, 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.
10. the preparation method of halogen-free flame-retardant polyphenyl ether resin composition as claimed in claim 9 is characterized in that, comprises 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.
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