CN115895251A - Halogen-free flame-retardant reinforced PPO/PPA alloy material and preparation method thereof - Google Patents
Halogen-free flame-retardant reinforced PPO/PPA alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN115895251A CN115895251A CN202211743122.0A CN202211743122A CN115895251A CN 115895251 A CN115895251 A CN 115895251A CN 202211743122 A CN202211743122 A CN 202211743122A CN 115895251 A CN115895251 A CN 115895251A
- Authority
- CN
- China
- Prior art keywords
- ppo
- ppa
- halogen
- free flame
- alloy material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 110
- 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 title claims abstract description 93
- 239000000956 alloy Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 56
- 239000000314 lubricant Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims description 64
- 239000011347 resin Substances 0.000 claims description 64
- 238000002156 mixing Methods 0.000 claims description 59
- -1 hypophosphite nitrogen-phosphorus Chemical compound 0.000 claims description 27
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 26
- 239000012760 heat stabilizer Substances 0.000 claims description 24
- 150000001879 copper Chemical class 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004677 Nylon Substances 0.000 claims description 13
- 229920001778 nylon Polymers 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 239000004595 color masterbatch Substances 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001125 Pa alloy Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Abstract
The invention discloses a halogen-free flame-retardant reinforced PPO/PPA alloy material and a preparation method thereof. The halogen-free flame-retardant reinforced PPO/PPA alloy material comprises the following raw materials in percentage by mass: 10-25% of PPO, 20-30% of PPA, 13-16% of halogen-free flame retardant, 1-4% of compatilizer, 25-40% of glass fiber, 0.2-0.5% of coupling agent, 0.1-0.4% of antioxidant and 0.3-1% of lubricant. The halogen-free flame-retardant reinforced PPO/PPA alloy material provided by the invention has higher CTI (600V), higher GWIT (850 ℃/2.0 mm) and excellent flame retardant property, the flame retardant grade can reach 0.8mmV0, and the halogen-free flame-retardant reinforced PPO/PPA alloy material has higher mechanical property and heat resistance compared with the traditional PPO alloy.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT and a preparation method thereof.
Background
The PPO has excellent comprehensive properties such as excellent heat resistance and low temperature resistance, outstanding mechanical property and electrical insulation property, excellent dimensional stability, high rigidity, small creep, and good chemical stability and self-extinguishing property, the thermal deformation temperature can reach 260 ℃ after being reinforced by glass fiber, the continuous use temperature can reach 200-240 ℃, but the PPO has high melt viscosity, poor fluidity and difficult processing, so that the surface has more floating fibers after being reinforced by the glass fiber, and the appearance is influenced. The PS is a thermoplastic plastic which is colorless and transparent, has lower relative density, low melt viscosity, good fluidity, better processing performance, good corrosion resistance, free coloring and excellent electrical performance, and can blend the high-viscosity PPO and the high-fluidity low-viscosity PS by utilizing the compatibilization and blending technology, thereby greatly improving the fluidity of the alloy and the processing performance of the PPO. Similarly, conventional PPO/PA6 and PPO/PA66 alloys, both of which improve the processing properties of PPO. Therefore, PPO/PS and PPO/PA alloys have become the mainstream of PPO alloy modification.
In order to prevent fire accidents caused by fire on internal plastic parts during the use of household appliances, another flame retardant evaluation method of the International Electrotechnical Commission (IEC) of the european union, the glowing filament flame retardant test standard (IEC 60695) is receiving increasing attention. The IEC organization requires in the safety standard for household and similar appliances (IEC 60335): the flame retardant property of the plastic part used by the long-term unattended electric appliance must meet the requirements of no fire in the UL94V0 grade and 30S of 750 ℃ glow wire contact material or the burning time less than or equal to 5S. The GWIT temperature of 850 ℃ and the Glow Wire Flammability Index (GWFI) of 960 ℃ are also required for specific parts such as connectors, contact switches, motors, and breaker housings. Although PPO has better electrical property and flame retardance, the addition of PS and conventional PA6 or PA66 can reduce the GWIT value and the flame retardance of the alloy material, but the high-temperature nylon semi-aromatic polyamide PPA material has better rigidity, water absorbability and flame retardance compared with the conventional PA6 and PA66 because the molecular chain contains a benzene ring structure, and is beneficial to improving the flame retardance, the mechanical property and the heat resistance of the PPO alloy.
The existing bromine system has a halogen flame retardant to occupy most proportion of modified plastics, and can produce a large amount of smog and toxic corrosive gas when burning for having halogen flame retardant, causes secondary damage to environment and human body, and the smog that produces when the halogen-free flame retardant burns is less, and is less to environmental pollution, is the inevitable trend of future flame retardant development.
Disclosure of Invention
The invention mainly aims to provide a halogen-free flame-retardant reinforced PPO/PPA alloy material and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the above object, the embodiment of the present invention adopts a technical solution comprising:
the embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT, which comprises the following raw materials in percentage by mass: 10-25% of PPO, 20-30% of PPA, 13-16% of halogen-free flame retardant, 1-4% of compatilizer, 25-40% of glass fiber, 0.2-0.5% of coupling agent, 0.1-0.4% of antioxidant and 0.3-1% of lubricant.
The embodiment of the invention also provides a preparation method of the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT, which comprises the following steps:
mixing and stirring PPO, PPA, a halogen-free flame retardant, a compatilizer, a lubricant and an antioxidant uniformly according to a proportion to form a first mixed system;
extruding the first mixed system, adding glass fiber and a coupling agent, and melting and blending to form a second mixed system;
and extruding and granulating the second mixed system to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material.
Compared with the prior art, the invention has the following beneficial effects:
the halogen-free flame-retardant reinforced PPO/PPA alloy material has higher CTI (600V), higher GWIT (850 ℃/2.0 mm) and excellent flame retardant property, the flame retardant grade can reach 0.8mmV0, and the halogen-free flame-retardant reinforced PPO/PPA alloy material has higher mechanical property and heat resistance compared with the traditional PPO alloy.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, and mainly through adding PPA component to replace the traditional polystyrene PS and the conventional nylon PA6/PA66 alloy material, and through the coordination with other component distribution ratios, the prepared alloy material has the advantages of high CTI (600V), high GWIT (850 ℃/2.0 mm) and excellent flame retardant property, the flame retardant grade can reach 0.8mmV0, and the alloy material has higher mechanical property and heat resistance compared with the traditional PPO alloy. The technical solution, its implementation and principles will be further explained as follows.
One aspect of the embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 10-25% of PPO, 20-30% of PPA, 13-16% of halogen-free flame retardant, 1-4% of compatilizer, 25-40% of glass fiber, 0.2-0.5% of coupling agent, 0.1-0.4% of antioxidant and 0.3-1% of lubricant.
In some preferred embodiments, the PPA component is added to replace the traditional polystyrene PS and the conventional nylon PA6/PA66 alloy material, the high-temperature nylon semi-aromatic polyamide PPA material is semi-aromatic polyamide taking terephthalic acid or phthalic acid as a raw material, and compared with the common PA66, the PPA material has higher heat resistance due to the benzene ring structure in the molecule, the thermal deformation temperature is as high as 270 ℃ or above, the continuous use temperature can reach 180 ℃, and the water absorption is lower; the creep resistance, the fatigue resistance, the chemical resistance and the flame retardant property are better, so that the PPO alloy material has higher mechanical property and heat resistance; in addition, the content of the PPO selected in the invention is 10-25%, and the copolymer in the range has proper mechanical property and good fluidity.
In some preferred embodiments, the halogen-free flame retardant is a high-temperature-resistant organic aluminum hypophosphite nitrogen-phosphorus flame retardant, and the thermal decomposition temperature of the flame retardant is more than 390 ℃; preferably, the high-temperature resistant organic aluminum hypophosphite nitrogen-phosphorus flame retardant can comprise at least one of HR8866S, TMF-900FR, FR30 or OP 1230 and the like, but is not limited to the above; the invention adopts the high-temperature resistant organic aluminum hypophosphite nitrogen-phosphorus flame retardant, the thermal decomposition temperature is higher than 390 ℃, compared with the traditional bromine-containing halogen flame retardant, the smoke generation is smaller, the toxic gas is less, the yellowing resistance is better, the glow wire ignition temperature is higher, the GWIT index can reach 850 ℃/2.0mm, and the CTI index can reach more than 500V.
In some preferred embodiments, the compatibilizer is PPO-g-MAH, (maleic anhydride grafted PPO) with a grafting ratio of 2% to 4%; the PPO-g-MAH adopted by the invention has an active group MAH, and after the PPO-g-MAH is added, the PPO and the PPA have good compatibility, so that the comprehensive performance of the material can be improved.
In some preferred embodiments, the glass fiber is a hydrolysis-resistant glass fiber specially used for nylon, the diameter of the glass fiber is 10-13 μm, and the hydrolysis rate is 0.2-0.5%. (ii) a Preferably, the hydrolysis-resistant glass fiber specially used for nylon can comprise at least one of E7CS10-03-568H, ECS-03-568H, ECS HP-3-H or ECS301X1-3-H, and the like, but is not limited thereto; the added glass fiber adopts the hydrolysis-resistant glass fiber special for nylon, has excellent hydrolysis resistance, and can greatly improve the mechanical strength, heat resistance and dimensional stability of the material.
In some preferred embodiments, the coupling agent is a silane coupling agent b, and preferably, the silane coupling agent may include at least one of but is not limited to alkenyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, and the like; the silane coupling agent forms a bridge with silanol group molecules on the surface of the glass fiber through hydrolysis reaction, so that the resin and the glass fiber interface have stronger binding power, and the combination of the resin and the glass fiber interface is enhanced.
In some preferred embodiments, the antioxidant is an organocopper-based heat stabilizer, which may include, but is not limited to, at least one of Finner-336, SH3360, or SH 3381; compared with common hindered phenol and phosphite antioxidants, the high-temperature-resistant hindered phenol/phosphite antioxidant can remarkably improve the thermal stability of the material in a high-temperature environment, has excellent anti-yellowing and high-temperature degradation protection, and enables the material to keep high mechanical properties for a long time so as to resist embrittlement and mechanical property reduction of the material under severe conditions.
In some preferred embodiments, the lubricant is a nylon-specific high molecular weight hyperbranched resin lubricant having a molecular weight of 4000 to 8000, which may include, but is not limited to, at least one of C100, 160H, CYD-C610, CYD-701, or the like; the hyperbranched resin lubricant can penetrate into the inside of a molecular chain, reduces the acting force among the molecular chains under the condition of not damaging the original polymer molecular chain, drives the molecular chain to move rapidly, reduces the processing temperature, improves the melt index, reduces the floating fiber on the surface of a product, improves the appearance of a material, is not easy to volatilize and degrade under the high-temperature condition, can improve the overall fluidity of the material, and has little influence on the performance.
In some preferred embodiments, the tracking resistance index of the halogen-free flame-retardant reinforced PPO/PPA alloy material is 500V-600V, the glow wire ignition temperature GWIT is 775-850 ℃/2.0mm, the glow wire flammability index GWFI is 800-1000 ℃/2.0mm, the UL94 flame retardant rating is 0.8mm-2mmV0 grade, the tensile strength is 150-200MPa, the bending strength is 210-300MPa, and the unnotched impact strength is 50-80KJ/m 2 The heat distortion temperature HDT is 235 to 275 ℃.
In some more preferable embodiments, the tracking resistance index of the halogen-free flame-retardant reinforced PPO/PPA alloy material is above 550V, the glow wire ignition temperature GWIT is 850 ℃/2.0mm, the glow wire flammability index GWFI is 960 ℃/2.0mm, the UL94 flame retardant rating is 0.8mmV0 grade, the tensile strength reaches 192MPa, the bending strength reaches 295MPa, and the unnotched impact strength reaches 76KJ/m 2 The heat distortion temperature HDT reaches 271 ℃.
Another aspect of the embodiment of the present invention provides a preparation method of the aforementioned halogen-free flame retardant reinforced PPO/PPA alloy material with high CTI and high GWIT, including:
weighing the raw materials in proportion;
uniformly stirring PPO, PPA, a halogen-free flame retardant, a compatilizer, a lubricant and an antioxidant to form a first mixed system;
extruding the first mixed system, adding glass fiber and a coupling agent, and carrying out melt blending to form a second mixed system;
and extruding and granulating the second mixed system to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and GWIT.
In some preferred embodiments, the preparation method of the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT specifically comprises the following steps: adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, feeding the mixture into the co-rotating parallel double-screw extruder for melt blending, and adding glass fiber and a coupling agent from a glass fiber port at the middle section of the co-rotating double-screw extruder in the process of melt blending to form a second mixed system;
and extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT.
In some more preferred embodiments, the co-rotating parallel twin screw extruder has a speed of 350 to 400RPM, a current of 40 to 46A, and an extrusion temperature of 290 to 310 ℃.
According to the high CTI high GWIT halogen-free flame-retardant reinforced PPO/PPA alloy material provided by the embodiment of the invention, the PPA component is added to replace the traditional polystyrene PS and conventional nylon PA6/PA66 alloy materials, and the molecular chain of the high-temperature nylon semi-aromatic polyamide PPA material contains a benzene ring structure, so that the PPO alloy material has higher mechanical property and heat resistance; high-temperature-resistant nitrogen-phosphorus halogen-free flame retardant is added to replace the traditional bromine-containing halogen flame retardant, so that a large amount of smoke and toxic gas are avoided, and higher CTI index and glow wire resistance can be obtained; meanwhile, the special organic copper salt heat stabilizer is added into the system, and compared with the traditional hindered phenol and phosphite antioxidant, the material has better high-temperature thermal stability, excellent anti-yellowing and high-temperature degradation protection, so that the material can keep higher mechanical property for a long time; in addition, by adding the high-molecular-weight and non-volatile dendritic polymer lubricant, compared with the traditional organic small-molecular lubricant, the high-molecular-weight and non-volatile dendritic polymer lubricant can avoid the damage of polymer chain segments, is not easy to volatilize and degrade under the high-temperature condition, can improve the overall fluidity of the material, and has little influence on the performance.
The present invention will be described in more detail with reference to examples, which are not intended to limit the present invention. All variations that may be suggested or derived from the present disclosure are to be considered within the scope of the present invention.
Example 1
The embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 25% of PPO resin, 30% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, 2% of PPO-g-MAH compatilizer, 10-03-568H 25% of glass fiber E7CS, 25% of silane coupling agent KH7920.3%, organic copper salt heat stabilizer SH33600.3%, high molecular weight hyperbranched resin lubricant 160H 0.8% and color master batch 0.6%, and the organic copper salt heat stabilizer is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) PPO resin, PPA resin, organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, PPO-g-MAH compatilizer, high molecular weight hyperbranched resin lubricant and organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, adding the first mixed system into the co-rotating parallel double-screw extruder for melt blending, and adding glass fibers and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT; wherein the rotating speed of the co-rotating parallel twin-screw extruder is 360RPM, the current is 40A, and the extrusion temperature is 310 ℃.
Example 2
The embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 20% of PPO resin, 30% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus halogen-free flame retardant TMF-900FR, 2% of PPO-g-MAH compatilizer, 10-03-568H 30% of alkali-free glass fiber E7CS, 7920.3% of silane coupling agent, 3242% of organic copper salt heat stabilizer SH33600.3%, 0.8% of high molecular weight hyperbranched resin lubricant 160H and 0.6% of color master batch, and the PPO resin is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) The PPO resin, the PPA resin, the organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, the PPO-g-MAH compatilizer, the high molecular weight hyperbranched resin lubricant and the organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, adding the first mixed system into the co-rotating parallel double-screw extruder for melt blending, and adding glass fibers and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, the current is 46A, and the extrusion temperature is 300 ℃.
Example 3
The embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 15% of PPO resin, 30% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus halogen-free flame retardant TMF-900FR, 2% of PPO-g-MAH compatilizer, 10-03-568H 35% of alkali-free glass fiber E7CS, 7920.3% of silane coupling agent, 3242% of organic copper salt heat stabilizer SH33600.3%, 0.8% of high molecular weight hyperbranched resin lubricant 160H and 0.6% of color master batch, and the PPO resin is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) The PPO resin, the PPA resin, the organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, the PPO-g-MAH compatilizer, the high molecular weight hyperbranched resin lubricant and the organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, adding the first mixed system into the co-rotating parallel double-screw extruder for melt blending, and adding glass fibers and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, the current is 44A, and the extrusion temperature is 300 ℃.
Example 4
The embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 10% of PPO resin, 30% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus halogen-free flame retardant TMF-900FR, 2% of PPO-g-MAH compatilizer, 40% of alkali-free glass fiber E7CS10-03-568H, 40% of silane coupling agent KH7920.3, 3242% of organic copper salt heat stabilizer SH33600.3, 0.8% of high molecular weight hyperbranched resin lubricant 160H and 0.6% of color master batch, and the organic copper hypophosphite nitrogen phosphorus halogen-free flame retardant is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) PPO resin, PPA resin, organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, PPO-g-MAH compatilizer, high molecular weight hyperbranched resin lubricant and organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, adding the first mixed system into the co-rotating parallel double-screw extruder for melt blending, and adding glass fibers and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, the current is 43A, and the extrusion temperature is 300 ℃.
Example 5
The embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 20% of PPO resin, 25% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, 2% of PPO-g-MAH compatilizer, 35% of alkali-free glass fiber E7CS10-03-568H, 35% of silane coupling agent KH7920.3, 3242% of organic copper salt heat stabilizer SH33600.3, 0.8% of high molecular weight hyperbranched resin lubricant 160H and 0.6% of color master batch, and the organic aluminum hypophosphite nitrogen phosphorus flame retardant is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) The PPO resin, the PPA resin, the organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, the PPO-g-MAH compatilizer, the high molecular weight hyperbranched resin lubricant and the organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, feeding the first mixed system into the co-rotating parallel double-screw extruder for melt blending, and adding glass fiber and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, the current is 44A, and the extrusion temperature is 300 ℃.
Example 6
The embodiment of the invention provides a halogen-free flame-retardant reinforced PPO/PPA alloy material, which comprises the following raw materials in percentage by mass: 25% of PPO resin, 20% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, 2% of PPO-g-MAH compatilizer, 35% of alkali-free glass fiber E7CS10-03-568H, 35% of silane coupling agent KH7920.3, 3242% of organic copper salt heat stabilizer SH33600.3, 0.8% of high molecular weight hyperbranched resin lubricant 160H and 0.6% of color master batch, and the PPO resin is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) The PPO resin, the PPA resin, the organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, the PPO-g-MAH compatilizer, the high molecular weight hyperbranched resin lubricant and the organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, adding the first mixed system into the co-rotating parallel double-screw extruder for melt blending, and adding glass fibers and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material with high CTI and high GWIT; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, the current is 44A, and the extrusion temperature is 300 ℃.
Comparative example 1
The PPO/PA66 alloy material provided by the invention comprises the following raw materials in percentage by mass: 12% of PPO resin, 30% of PA66 resin, 16% of brominated polystyrene flame retardant, 3% of antimony trioxide, 35% of alkali-free glass fiber E7CS10-03-568H, 2% of PPO-g-MAH compatilizer, 2% of silane coupling agent KH7920.3, 33600.3% of organic copper salt heat stabilizer, 0.8% of high molecular weight hyperbranched lubricant 160H and 0.6% of color master batch, and the high molecular weight hyperbranched lubricant is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) Adding PPO resin, PA66 resin, a brominated flame retardant, antimony trioxide, a PPO-g-MAH compatilizer, a high molecular weight hyperbranched lubricant and an organic copper salt heat stabilizer into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and forming a first mixing system after uniformly mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, feeding the mixture into the co-rotating parallel double-screw extruder for melt blending, and adding alkali-free glass fiber and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain a PPO/PA66 alloy material; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, and the extrusion temperature is 300 ℃.
Comparative example 2
The PPO/PPA alloy material provided by the invention comprises the following raw materials in percentage by mass: 15% of PPO resin, 30% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, 35% of alkali-free glass fiber E7CS10-03-568H, 2% of PPO-g-MAH compatilizer, 2% of silane coupling agent KH7920.3, 3242% of phosphite antioxidant S-92280.3%, 0.8% of high molecular weight hyperbranched lubricant 160H and 0.6% of color master batch, and the PPO resin is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) PPO resin, PPA resin, organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, PPO-g-MAH compatilizer, high molecular weight hyperbranched lubricant and phosphite ester antioxidant are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, feeding the mixture into the co-rotating parallel double-screw extruder for melt blending, and adding alkali-free glass fiber and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain a PPO/PPA alloy material; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, and the extrusion temperature is 300 ℃.
Comparative example 3
The PPO/PPA alloy material provided by the invention comprises the following raw materials in percentage by mass: 15% of PPO resin, 30% of PPA resin, 16% of organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, 35% of alkali-free glass fiber E7CS10-03-568H, 2% of PPO-g-MAH compatilizer, 2% of silane coupling agent KH7920.3%, organic copper salt heat stabilizer SH33600.3%, organic small molecular lubricant TAF 0.8% and color master batch 0.6%, and the organic aluminum hypophosphite nitrogen phosphorus flame retardant is prepared by the following steps:
(1) Weighing the raw materials in proportion;
(2) The PPO resin, the PPA resin, the organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, the PPO-g-MAH compatilizer, the organic micromolecule lubricant and the organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after the mixture is uniformly mixed;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, feeding the mixture into the co-rotating parallel double-screw extruder for melt blending, and adding alkali-free glass fiber and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain a PPO/PPA alloy material; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, and the extrusion temperature is 300 ℃.
Comparative example 4
The PPA/PA66 alloy material provided by the invention comprises the following raw materials in percentage by mass: 30% of PPA resin, 17% of PA66 resin, 16% of organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, 35% of alkali-free glass fiber E7CS10-03-568H, 2% of PPO-g-MAH compatilizer, 2% of silane coupling agent KH7920.3%, organic copper salt heat stabilizer SH33600.3%, high molecular weight hyperbranched resin lubricant 160H 0.8% and color master batch 0.6%, and the preparation method comprises the following steps:
(1) Weighing the raw materials in proportion;
(2) The PPA resin, the PA66 resin, the organic aluminum hypophosphite nitrogen phosphorus flame retardant TMF-900FR, the PPO-g-MAH compatilizer, the high molecular weight hyperbranched resin lubricant and the organic copper salt heat stabilizer are put into a high-speed stirrer with the rotating speed of 300RPM for mixing for 5min, and a first mixing system is formed after uniform mixing;
(3) Adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, adding the first mixed system into a first section of cylinder of the double-screw extruder, feeding the mixture into the co-rotating parallel double-screw extruder for melt blending, and adding alkali-free glass fiber and a coupling agent into a glass fiber port of a fifth section of cylinder of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
(4) Extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain a PPA/PA66 alloy material; wherein the rotating speed of the co-rotating parallel double-screw extruder is 360RPM, and the extrusion temperature is 300 ℃.
The proportions of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 1:
table 1:
the above examples and comparative examples were subjected to performance tests, and the results are shown in table 2:
table 2:
as shown in Table 2, the test results of the example 3 and the comparative example 1 show that compared with the organic aluminum hypophosphite nitrogen-phosphorus halogen-free flame retardant, the CTI of the bromine flame retardant is obviously lower, the CTI of the bromine flame retardant can reach 600V, and the CTI of the bromine flame retardant is generally about 250V. And under the condition of the same addition amount of the flame retardant, the glow wire ignition temperature GWIT value and the heat distortion temperature HDT of the comparative example 1 are both lower.
As can be seen from the test results of example 3 and comparative example 2 in Table 2, the mechanical properties, heat resistance and tensile strength retention after 1000-hour aging at 150 ℃ of comparative example 2 are low. Compared with an organic copper salt heat stabilizer, the traditional phosphite ester antioxidant has poor long-term anti-thermal-oxidative aging effect.
As can be seen from the test results of example 3 and comparative example 3 in Table 2, the mechanical properties, heat resistance and tensile strength retention after 1000 hours aging at 150 ℃ of comparative example 3 were all low. Compared with a high molecular weight hyperbranched lubricant, the traditional organic small molecular lubricant has poor temperature resistance and has greater influence on the mechanical property and the heat resistance of materials.
As can be seen from the test results of example 3 and comparative example 4 in Table 2, the mechanical properties and heat resistance of comparative example 4 are reduced to some extent, and the glow wire ignition temperature GWIT value is also reduced. The PPO/PPA alloy can better improve the mechanical property, heat resistance and flame retardant property of the material.
After the PPA component is introduced, compared with the traditional PS, PA6 and PA66 alloy, the halogen-free flame-retardant reinforced PPO/PPA alloy material disclosed by the invention has the advantages that the mechanical properties and heat resistance such as tensile strength, bending modulus, impact strength and the like are greatly improved, compared with the performance of a comparative material, the flame retardant property is better, the vertical combustion performance can reach 0.8mm V0 level, the glow wire ignition temperature GWIT is also improved to 850 ℃, and the tracking resistance index CTI can reach 600V.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. The halogen-free flame-retardant reinforced PPO/PPA alloy material is characterized by comprising the following components in percentage by mass: 10-25% of PPO, 20-30% of PPA, 13-16% of halogen-free flame retardant, 1-4% of compatilizer, 25-40% of glass fiber, 0.2-0.5% of coupling agent, 0.1-0.4% of antioxidant and 0.3-1% of lubricant.
2. The halogen-free flame-retardant reinforced PPO/PPA alloy material according to claim 1, characterized in that: the PPA is semi-aromatic polyamide prepared by using terephthalic acid or phthalic acid as a raw material, and has a heat distortion temperature of more than 270 ℃ and a continuous use temperature of more than 180 ℃.
3. The halogen-free flame-retardant reinforced PPO/PPA alloy material as claimed in claim 1, wherein: the halogen-free flame retardant is a high-temperature-resistant organic aluminum hypophosphite nitrogen-phosphorus flame retardant, and the thermal decomposition temperature of the halogen-free flame retardant is higher than 390 ℃; preferably, the organic aluminum hypophosphite nitrogen-phosphorus flame retardant comprises at least one of HR8866S, TMF-900FR, FR30 or OP 1230.
4. The halogen-free flame-retardant reinforced PPO/PPA alloy material as claimed in claim 1, wherein: the compatilizer is PPO-g-MAH, and the grafting rate of the compatilizer is 2% -4%.
5. The halogen-free flame-retardant reinforced PPO/PPA alloy material as claimed in claim 1, wherein: the glass fiber is a special hydrolysis-resistant glass fiber for nylon, the diameter of the glass fiber is 10-13 mu m, and the hydrolysis rate is 0.2-0.5%; preferably, the hydrolysis-resistant glass fiber specially used for nylon comprises at least one of E7CS10-03-568H, ECS-03-568H, ECS HP-3-H or ECS301X 1-3-H.
6. The halogen-free flame-retardant reinforced PPO/PPA alloy material according to claim 1, characterized in that: the coupling agent is a silane coupling agent, preferably, the silane coupling agent comprises at least one of vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris (beta-methoxyethoxy) silane;
and/or the antioxidant is an organic copper salt heat stabilizer, preferably, the organic copper salt heat stabilizer comprises at least one of Finner-336, SH3360 or SH 3381;
and/or the lubricant is a special high-molecular-weight hyperbranched resin lubricant for nylon, and the molecular weight of the lubricant is 4000-8000; preferably, the nylon-dedicated high molecular weight hyperbranched resin lubricant comprises at least one of C100, 160H, CYD-C610 or CYD-701.
7. The halogen-free flame-retardant reinforced PPO/PPA alloy material as claimed in claim 1, wherein: the tracking resistance index of the halogen-free flame-retardant reinforced PPO/PPA alloy material is 500V-600V, and the ignition temperature of a glow wire isGWIT is 775-850 deg.C/2.0 mm, glow wire flammability index GWFI is 800-1000 deg.C/2.0 mm, UL94 flame retardant rating is 0.8-2 mmV0 grade, tensile strength is 150-200MPa, bending strength is 210-300MPa, unnotched impact strength is 50-80KJ/m 2 The heat distortion temperature HDT is 235-275 ℃.
8. The preparation method of the halogen-free flame-retardant reinforced PPO/PPA alloy material as set forth in any one of claims 1-7, characterized by comprising the following steps:
mixing and stirring PPO, PPA, a halogen-free flame retardant, a compatilizer, a lubricant and an antioxidant uniformly according to a proportion to form a first mixed system;
extruding the first mixed system, adding glass fiber and a coupling agent, and carrying out melt blending to form a second mixed system;
and extruding and granulating the second mixed system to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material.
9. The preparation method according to claim 8, comprising: adding the first mixed system into a feeding hopper of a co-rotating parallel double-screw extruder, feeding the mixture into the co-rotating parallel double-screw extruder for melt blending, and adding glass fibers and a coupling agent from a glass fiber port at the middle section of the co-rotating double-screw extruder in the melt blending process to form a second mixed system;
and extruding the second mixed system by a co-rotating parallel double-screw extruder, cooling by a water tank, and cutting into granular granules by a granulator to obtain the halogen-free flame-retardant reinforced PPO/PPA alloy material.
10. The method of claim 9, wherein: the rotating speed of the co-rotating parallel double-screw extruder is 350-400RPM, the current is 40-46A, and the extrusion temperature is 290-310 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211743122.0A CN115895251A (en) | 2022-12-26 | 2022-12-26 | Halogen-free flame-retardant reinforced PPO/PPA alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211743122.0A CN115895251A (en) | 2022-12-26 | 2022-12-26 | Halogen-free flame-retardant reinforced PPO/PPA alloy material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115895251A true CN115895251A (en) | 2023-04-04 |
Family
ID=86497003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211743122.0A Pending CN115895251A (en) | 2022-12-26 | 2022-12-26 | Halogen-free flame-retardant reinforced PPO/PPA alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115895251A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130132004A (en) * | 2012-05-25 | 2013-12-04 | 주식회사 삼양사 | Halogen-free flame retardant polyester resin composition with good mechanical properties and molded article thereof |
| CN108587145A (en) * | 2018-04-23 | 2018-09-28 | 广东聚石化学股份有限公司 | A kind of 6 composite material and preparation method of high glow-wire high CTI value halogen free flame-retardant fiberglass reinforced PA |
| CN110054892A (en) * | 2019-04-09 | 2019-07-26 | 深圳市富恒新材料股份有限公司 | A kind of fire-retardant enhancing PPA/PPO material of high-rigidity and low-warpage and preparation method thereof |
| CN115322566A (en) * | 2022-09-16 | 2022-11-11 | 无锡腾达精密模塑有限公司 | PA 66-based composite material for motor bearing retainer and preparation method thereof |
-
2022
- 2022-12-26 CN CN202211743122.0A patent/CN115895251A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130132004A (en) * | 2012-05-25 | 2013-12-04 | 주식회사 삼양사 | Halogen-free flame retardant polyester resin composition with good mechanical properties and molded article thereof |
| CN108587145A (en) * | 2018-04-23 | 2018-09-28 | 广东聚石化学股份有限公司 | A kind of 6 composite material and preparation method of high glow-wire high CTI value halogen free flame-retardant fiberglass reinforced PA |
| CN110054892A (en) * | 2019-04-09 | 2019-07-26 | 深圳市富恒新材料股份有限公司 | A kind of fire-retardant enhancing PPA/PPO material of high-rigidity and low-warpage and preparation method thereof |
| CN115322566A (en) * | 2022-09-16 | 2022-11-11 | 无锡腾达精密模塑有限公司 | PA 66-based composite material for motor bearing retainer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李登辉等: ""不同抗氧体系的玻纤增强PA66 的热氧老化性能"", 工程塑料应用, vol. 48, no. 11, pages 106 - 111 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2036253C (en) | Thermoplastic resin composition | |
| CN103408915B (en) | A kind of high rigidity polycarbonate composite material and preparation method thereof | |
| CN108624006B (en) | High-fluidity glass fiber reinforced flame-retardant PC/PBT alloy material and preparation method thereof | |
| CN109721836B (en) | Flame-retardant shading low-shrinkage polypropylene composite material and preparation method thereof | |
| CN113105727B (en) | Weather-resistant high-glowing filament polyester composite material and preparation method thereof | |
| CN105440628A (en) | Enhanced flame retardant PC/PPO composite material and preparation method thereof | |
| CN110791049B (en) | Flame-retardant reinforced polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN113637306A (en) | Low-temperature-resistant flame-retardant antistatic PC/PBT alloy and preparation method thereof | |
| CN110776729B (en) | Flame-retardant polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN110643167B (en) | Flame-retardant reinforced polyphenyl ether/polyamide 66 composition and preparation method thereof | |
| CN114933773B (en) | Cold-resistant halogen-free flame-retardant polypropylene material and preparation method and application thereof | |
| CN115895251A (en) | Halogen-free flame-retardant reinforced PPO/PPA alloy material and preparation method thereof | |
| CN113881216B (en) | Wear-resistant flame-retardant modified polyurethane cable material and preparation method thereof | |
| CN112876841B (en) | Halogen-free flame-retardant long glass fiber reinforced nylon 12 material with high RTI value as well as preparation method and application thereof | |
| CN112898764B (en) | Conductive POK/CNT (Poly-Acrylonitrile-Ketone-PolyKetone)/CNT (carbon nano tube) composition as well as preparation method and equipment thereof | |
| CN110760177B (en) | Conductive polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| JPH1121447A (en) | Flame-retardant polyamide resin composition and its production | |
| CN114836017A (en) | PBT-PC composite material and preparation method and application thereof | |
| CN110724374B (en) | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof | |
| CN114015223A (en) | PC/PBT alloy material and preparation method and application thereof | |
| CN109280346B (en) | High-impact glass fiber reinforced halogen-free flame-retardant POK/PBT alloy and preparation method thereof | |
| CN111712544A (en) | Thermoplastic resin composition and molded article obtained by molding same | |
| CN115558290B (en) | Halogen-free flame-retardant glass fiber reinforced nylon material and preparation method and application thereof | |
| CN116444973B (en) | Flame-retardant polycarbonate material and preparation method and application thereof | |
| CN115160757A (en) | Flame-retardant glass fiber reinforced PC material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |