CN103160108A - Halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as well as preparation and application for same - Google Patents
Halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as well as preparation and application for same Download PDFInfo
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Abstract
The invention discloses a halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy. The halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy is prepared from the components in the following parts by weight: 20-80 parts of polyphenylene oxide, 10-40 parts of polyamide 6, 5-35 parts of compatilizer, 5-20 parts of flame retardant, 5-15 parts of toughener, 0.2-0.5 parts of antioxidant, 0.2-0.7 parts of lubricant, and 3-35.5 parts of auxiliaries. The invention further discloses a preparation method for the halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy and an application for the halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as an extruded profile material. The halogen-free flame-retardant PPO/PA6 (polyphenylene oxide/polyamide 6) blend alloy disclosed by the invention is excellent in corrosion resistance and insulativity, great in strength, toughness, flame retardance and wear resistance, light in weight, and capable of replacing a steel plate or a special engineering plastic, thus realizing the purpose of replacing steel by plastic. Moreover, the halogen-free flame-retardant PPO/PA6 blend alloy can be popularized to extruded profiles and used as a component in large equipment such as special electronic and electrical products, as well as is wide in applications and capable of greatly reducing cost.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of halogen-free fire-retardant polyphenyl ether/nylon 6(PPO/PA6) blend alloy and preparation method thereof and application.
Background technology
Along with the progress of society, the development of science and technology, people's life are more and more convenient, and people are also more and more higher to the attention rate of environment simultaneously.Polyphenylene oxide (PPO) is a kind of thermoplastic engineering plastic of excellent performance, has following advantage: the Physical and mechanical properties that (1) is good.The mechanical strength that density is little, nontoxic, higher, creep resistance is good, molding shrinkage is low; (2) good resistance toheat.Second-order transition temperature (T
g) the highest in thermoplastics, approximately 210 ℃, approximately 260 ℃ of fusing points, it can non-stop run in the temperature range of 160-190 ℃, and the creep resistant under high temperature is comparatively excellent in thermoplastic engineering plastic; (3) good electrical property.In the PPO molecular structure, without strong polar group, electric performance stablity can keep good electrical property in temperature and range of frequency widely.Its specific inductivity and tangent of the dielectric loss angle are minimum in engineering plastics, are subjected to hardly the impact of temperature, humidity and frequency; (4) difficult combustion, have self-extinguishing.Its oxygen index is 29%, and flame retardant resistance is good; (5) good resistance to acids and bases, proof stress relax and fatigue performance and good dimensional stability.Wherein high creep resistance can be its most outstanding characteristics, so PPO is particularly suitable for making the industrial structural part that bears long-duration load.But PPO also has some shortcomings, as poor solvent resistance, goods, stress cracking, notched Izod impact strength occurs easily low etc.The PPO photostabilization is poor, uses for a long time product easy to change under sunlight or luminescent lamp, the color jaundice, and reason is the chain combination division that ultraviolet ray can make aromatic oxide; The fatal shortcoming of another one is poor fluidity, the forming process difficulty, and because PPO molecular chain rigidity is larger, melt viscosity is high, and this has affected applying of PPO.
Polyamide (PA) is a kind of engineering plastics of excellent property, and it makes it have that solvent resistance is good, the advantages such as mechanical strength is high, easy processing because degree of crystallinity is higher.But it exists, and shock strength is low, thermotolerance is relatively poor, because of the shortcomings such as product size poor stability that high-hydroscopicity causes, its application is restricted.
Halogen-free flameproof PPO/PA alloy had both kept the advantages such as the good heat resistance, dimensional stabilizing of PPO, had circulated again wear resistance and the organic solvent resistance of PA.In some special electronic apparatuss and main equipment, need to have the section bars such as gear, bar of property (as little in insulativity, erosion resistance, density etc.), and in industry, shape commonly used can't meet the demands.
Summary of the invention
The present invention is exactly problems such as, poor solvent resistance low for the notched Izod impact strength that solves the PPO that above-mentioned prior art exists, price are higher and a kind of halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy is provided.
Another object of the present invention is to provide the preparation method of above-mentioned halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy.
A further object of the present invention is to provide the purposes of above-mentioned halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy.
Purpose of the present invention is achieved through the following technical solutions:
A kind of halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy, made by the component that comprises following weight part:
Polyphenylene oxide 20-80 part,
Nylon 6 10-40 parts,
Compatilizer 5-35 part,
Fire retardant 5-20 part,
Toughner 5-15 part,
Oxidation inhibitor 0.2-0.5 part,
Lubricant 0.2-0.7 part,
Auxiliary agent 3-35.5 part.
Preferably, described compatilizer is selected from one or more in polyphenylene oxide grafted maleic anhydride, styrene-maleic anhydride copolymer, POE grafted maleic anhydride.
Preferably, described fire retardant is phosphate compounds.
Preferably, described phosphate compounds is selected from one or more in the two phenyl phosphate ester (RDP) of Resorcinol, triphenyl (TPP), diphenyl phosphoester (BDP), trimethyl phosphate (TMP), triethyl phosphate (TEP), Tributyl phosphate ester (TBP), tricyclohexyl phosphate, tritolyl phosphate (TCF).
Preferably, described toughner is selected from one or more in the segmented copolymer (SBS), (hydrogenated styrene/Butadiene/Styrene) segmented copolymer (SEBS), maleic anhydride graft styrene-ethylene-butadiene-styrene block copoly merization elastomerics (SEBS-g-MAH) of vinylbenzene and divinyl.
Preferably, described oxidation inhibitor be selected from antioxidant 1010 (four [
-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), antioxidant 1076 (
The positive octadecanol ester of-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid), one or more in irgasfos 168 (three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester); Described lubricant is selected from one or more in calcium stearate, silicone, paraffin, low-molecular-weight polypropylene, polyethylene wax, Zinic stearas.
Preferably, the molecular weight of described low-molecular-weight polypropylene is 3000-8000.
Preferably, described auxiliary agent is selected from one or more in filler, coupling agent.
Preferably, described filler is selected from one or more in glass fibre, calcium carbonate, Calucium Silicate powder, talcum powder, titanium dioxide; Described glass fibre is selected from long glass fibres or short glass fiber; Described coupling agent is
-aminopropyl triethoxysilane (silane resin acceptor kh-550).
A kind of preparation method of halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy comprises the following steps:
Take by weight 20-80 part polyphenylene oxide, 10-40 part nylon 6,5-35 part compatilizer, 5-20 part fire retardant, 5-15 part toughner, 0.2-0.5 part oxidation inhibitor, 0.2-0.7 part lubricant and 3-35.5 part auxiliary agent, with above-mentioned raw materials through high mixer high speed mixing, then mixture is poured in screw extrusion press, can be obtained product through the pelletizing of screw extrusion press tie rod;
Wherein, described high mixer rotating speed is 800-1000rpm, and mixing temperature is 40-80 ℃, and mixing time is 3-10min; Described screw extrusion press is single screw extrusion machine or twin screw extruder, and extrusion temperature is 240-290 ℃.
Halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy of the present invention, its performance meets the performance requriements of extrusion profile material, therefore, technical scheme of the present invention comprises that also halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy of the present invention is as the application of extrusion profile material (as bar, sheet material etc.).
Compared with prior art, the present invention has following beneficial effect:
The present invention is PA6 and PPO blending and modifying, and adds other auxiliary agents, and the halogen-free flameproof PPO/PA6 blend alloy that obtains can replace steel plate or special engineering plastics.At first, PA6 adds the processing characteristics that can improve PPO, the PPO/PA6 blend alloy is for shape, cost is lower, save energy, realized moulding the purpose of Dai Gang, and polyblend has fabulous erosion resistance and insulativity, simultaneously by adding the filler bulk strength of strongthener greatly, can improve the notched Izod impact strength of material by adding toughner, by adding halogen-free flame retardants, give polyblend good flame retardant resistance, halogen-free flame retardants is also more friendly to environment, can not cause secondary pollution.Secondly, halogen-free flameproof PPO/PA6 blend alloy extruding-out process is simple, saves tooling cost, reduces energy waste.
At last, halogen-free flameproof PPO/PA6 blend alloy of the present invention can extend to extrusion profile, have good erosion resistance, insulativity, good intensity, toughness and wear resistance, and light weight, can be used as the component in the special main equipments such as electronic apparatus, of many uses, and greatly reduce costs.The section bar that utilizes halogen-free flameproof PPO/PA6 blend alloy to make has enough intensity and rigidity, and possesses simultaneously the advantage of PPO thermotolerance and good stability of the dimension and PA6 organic solvent resistance and wear resistance, be easy to machine-shaping, can in very large range replace stainless steel and PEEK(polyether-ether-ketone) etc. section bar use, greatly reduce cost.
Embodiment
Describe the present invention in detail below in conjunction with each embodiment.
Embodiment 1
(1) take each component raw material by following weight part:
30 parts of polyphenylene oxide,
6 30 parts of nylon,
30 parts of compatilizer PPO-g-MAH,
5 parts of fire retardant RDP,
10 parts of toughner SEBS,
0.2 part of antioxidant 1010,
0.1 part of irgasfos 168,
0.2 part of calcium stearate
3 parts, calcium carbonate;
(2) with above-mentioned raw materials through high mixer high speed mixing, its high mixer speed is 800rmp, mixing temperature is 40 ℃, mixes 10min; Then mixture can be obtained product through the pelletizing of twin screw extruder tie rod, control the temperature in each district at 260-290 ℃.
Embodiment 2
(1) take each component raw material by following weight part:
32 parts of polyphenylene oxide,
6 38 parts of nylon,
5 parts of compatilizer POE-g-MAH,
20 parts of fire retardant TPP
10 parts of toughner SBS,
0.1 part of antioxidant 1010,
0.1 part of irgasfos 168,
0.2 part of silicone,
5 parts of Calucium Silicate powder;
(2) with above-mentioned raw materials through high mixer high speed mixing, controlling high mixer speed is 900rmp, mixing temperature is 80 ℃, mixes 3min, then mixture can be obtained product through the pelletizing of twin screw extruder tie rod, the temperature in each district is controlled at 240-265 ℃.
Embodiment 3
(1) take each component raw material by following weight part:
68 parts of polyphenylene oxide,
6 12 parts of nylon,
10 parts of compatilizer SMAH,
8 parts of fire retardant TCF,
10 parts of toughner SEBS-g-MAH,
0.2 part of antioxidant 1010,
0.2 part of irgasfos 168,
0.2 part, paraffin,
7 parts of talcum powder;
(2) with above-mentioned raw materials through high mixer high speed mixing, its high mixer speed is 1000rmp, mixing temperature is 60 ℃, mixes 6min; Mixture can be obtained product through the pelletizing of twin screw extruder tie rod, and the temperature in each district is controlled at 250-280 ℃.
Embodiment 4
(1) take each component raw material by following weight part:
80 parts of polyphenylene oxide,
6 10 parts of nylon,
5 parts of compatilizer SMAH,
5 parts of fire retardant BDP,
15 parts of toughner SBS,
0.3 part of antioxidant 1010,
0.2 part of irgasfos 168,
0.2 part of low-molecular-weight polypropylene,
5 parts of titanium dioxides;
(2) with above-mentioned raw materials through high mixer high speed mixing, its high mixer speed is 950rmp, mixing temperature is 60 ℃, mixes 5min; Mixture can be obtained product through the pelletizing of twin screw extruder tie rod, and the temperature in each district is controlled at 260-280 ℃.
Embodiment 5
(1) take each component raw material by following weight part:
20 parts of polyphenylene oxide,
6 25 parts of nylon,
20 parts of compatilizer PPO-g-MAH,
15 parts of fire retardant TMP,
5 parts of toughner SEBS,
0.2 part of antioxidant 1010,
0.1 part of irgasfos 168,
0.3 part of polyethylene wax,
25 parts of short glass fibers (diameter 18 μ m),
0.5 part of coupling agent KH-550;
(2) with above-mentioned raw materials through high mixer high speed mixing, controlling high mixer speed is 850rmp, mixing temperature is 55 ℃, mixes 7min; Mixture can be obtained product through the pelletizing of twin screw extruder tie rod, and the temperature in each district is controlled at 265-285 ℃.
Embodiment 6
(1) take each component raw material by following weight part:
35 parts of polyphenylene oxide,
6 12 parts of nylon,
10 parts of compatilizer POE-g-MAH,
8 parts of fire retardant TEP,
5 parts of toughner SEBS-g-MAH,
0.1 part of antioxidant 1010,
0.1 part of irgasfos 168,
0.5 part of Zinic stearas,
35 parts of long glass fibress,
0.5 part of coupling agent KH-550;
(2) with above-mentioned raw materials through high mixer high speed mixing, its high mixer speed is 920rmp, mixing temperature is 48 ℃, mixes 8min; Mixture can be obtained product through the pelletizing of single screw extrusion machine tie rod, and the temperature in each district is controlled at 250-270 ℃.
Embodiment 7
(1) take each component raw material by following weight part:
35 parts of polyphenylene oxide,
6 20 parts of nylon,
35 parts of compatilizer PPO-g-MAH,
6 parts of fire retardant TBP,
10 parts of toughner SEBS,
0.2 part of antioxidant 1010,
0.1 part of irgasfos 168,
0.7 part of Zinic stearas,
15 parts of titanium dioxides;
(2) with above-mentioned raw materials through high mixer high speed mixing, its high mixer speed is 980rmp, mixing temperature is 50 ℃, mixes 4min; Mixture can be obtained product through the pelletizing of twin screw extruder tie rod, and the temperature in each district is controlled at 245-275 ℃.
Embodiment 8
(1) take each component raw material by following weight part:
35 parts of polyphenylene oxide,
6 40 parts of nylon,
5 parts of compatilizer SMAH,
10 parts of fire retardant tricyclohexyl phosphates,
15 parts of toughner SEBS,
0.2 part of antioxidant 1076,
0.2 part of polyethylene wax,
20 parts of long glass fibress,
0.5 part of coupling agent KH-550;
(2) with above-mentioned raw materials through high mixer high speed mixing, its high mixer speed is 880rmp, mixing temperature is 70 ℃, mixes 9min; Mixture can be obtained product through the pelletizing of twin screw extruder tie rod, and the temperature in each district is controlled at 250-280 ℃.
The product that embodiment 1 is prepared carries out performance test, and test result sees Table 1.
Table 1
Halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy of the present invention, intensity or toughness all are enough to satisfy the service requirements of extrusion profile, polyblend has good erosion resistance and insulativity simultaneously, cost is much lower than shape, its density is also much lower, can reduce costs greatly, save energy realizes to mould the purpose of Dai Gang.At last, in pay attention to day by day fire-retardant today, carry out flame-retardant modifiedly with phosphoric acid ester fire retardant polyphenylene ether/nylon 6 mixing alloy, given the better insulativity of material and flame retardant effect, make material to use under more occasions.Halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy of the present invention, its performance meets the performance requriements of extrusion profile material, can be used as the extrusion profile material and makes the section bars such as bar, sheet material.
Above disclosed be only several specific embodiments of the application, but the application is not limited thereto, the changes that any person skilled in the art can think of all should drop in the application's protection domain.
Claims (10)
1. a halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy, is characterized in that, made by the component that comprises following weight part:
Polyphenylene oxide 20-80 part,
Nylon 6 10-40 parts,
Compatilizer 5-35 part,
Fire retardant 5-20 part,
Toughner 5-15 part,
Oxidation inhibitor 0.2-0.5 part,
Lubricant 0.2-0.7 part,
Auxiliary agent 3-35.5 part.
2. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 1, is characterized in that, described compatilizer is selected from one or more in polyphenylene oxide grafted maleic anhydride, styrene-maleic anhydride copolymer, POE grafted maleic anhydride.
3. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 1, is characterized in that, described fire retardant is phosphate compounds.
4. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 3, it is characterized in that, described phosphate compounds is selected from one or more in the two phenyl phosphate ester of Resorcinol, triphenyl, diphenyl phosphoester, trimethyl phosphate, triethyl phosphate, Tributyl phosphate ester, tricyclohexyl phosphate, tritolyl phosphate.
5. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 1, it is characterized in that, described toughner is selected from one or more in the segmented copolymer, (hydrogenated styrene/Butadiene/Styrene) segmented copolymer, maleic anhydride graft styrene-ethylene-butadiene-styrene block copoly merization elastomerics of vinylbenzene and divinyl.
6. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 1, is characterized in that, described oxidation inhibitor is selected from one or more in antioxidant 1010, antioxidant 1076, irgasfos 168; Described lubricant is selected from one or more in calcium stearate, silicone, paraffin, low-molecular-weight polypropylene, polyethylene wax, Zinic stearas.
7. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 1, is characterized in that, described auxiliary agent is selected from one or more in filler, coupling agent.
8. halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as claimed in claim 7, is characterized in that, described filler is selected from one or more in glass fibre, calcium carbonate, Calucium Silicate powder, talcum powder, titanium dioxide; Described glass fibre is selected from long glass fibres or short glass fiber; Described coupling agent is
-aminopropyl triethoxysilane.
9. the preparation method as the described halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy of any one in claim 1 to 8, is characterized in that, comprises the following steps:
Take by weight 20-80 part polyphenylene oxide, 10-40 part nylon 6,5-35 part compatilizer, 5-20 part fire retardant, 5-15 part toughner, 0.2-0.5 part oxidation inhibitor, 0.2-0.7 part lubricant and 3-35.5 part auxiliary agent, with above-mentioned raw materials through high mixer high speed mixing, then mixture is poured in screw extrusion press, can be obtained product through the pelletizing of screw extrusion press tie rod;
Wherein, described high mixer rotating speed is 800-1000rpm, and mixing temperature is 40-80 ℃, and mixing time is 3-10min; Described screw extrusion press is single screw extrusion machine or twin screw extruder, and extrusion temperature is 240-290 ℃.
10. a halogen-free fire-retardant polyphenyl ether/nylon 6 mixing alloy as described in any one in claim 1 to 8 is as the application of extrusion profile material.
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