CN101875776A - High-strength PPO/PA66 alloy material and preparation method thereof - Google Patents

High-strength PPO/PA66 alloy material and preparation method thereof Download PDF

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CN101875776A
CN101875776A CN2010101405469A CN201010140546A CN101875776A CN 101875776 A CN101875776 A CN 101875776A CN 2010101405469 A CN2010101405469 A CN 2010101405469A CN 201010140546 A CN201010140546 A CN 201010140546A CN 101875776 A CN101875776 A CN 101875776A
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ppo
alloy material
strength
glass
mica powder
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CN101875776B (en
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徐东
贺永
周兵
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Xu Dong
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Polymer Science Shenzhen New Materials Co Ltd
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    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • 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
    • B29C48/92—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
    • B29C2948/92514—Pressure
    • 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
    • B29C2948/92561—Time, e.g. start, termination, duration or interruption
    • 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
    • B29C2948/92895—Barrel or housing
    • 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
    • B29C2948/92904—Die; Nozzle zone

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high-strength PPO/PA66 alloy material and a preparation method thereof. The high-strength PPO/PA66 alloy material is prepared from the following components in percentage by weight: 20-40% of polyphenyl ether resin, 20-40% of nylon 66 resin, 5-10% of compatilizer, 5-10% of toughener, 5-15% of glass fiber, 5-15% of glass microballoon, 5-15% of mica powder, 0.2-0.4% of antioxidant and 0.5-1% of other assistants. By compounding the glass fiber, the glass microballoon and the mica powder to enhance PPO/PA66 alloy, the prepared alloy material not only has excellent combination properties including high strength, good heat resistance and easy spraying, but also has excellent dimensional stability and low warpage rate. Therefore, the invention is suitable for molding large structural parts and heated components.

Description

A kind of high-strength PPO/PA66 alloy material and preparation method thereof
[technical field]
The present invention relates to technical field of polymer materials, relate in particular to a kind of high-strength PPO/PA66 alloy material and preparation method thereof.
[background technology]
PPO (polyphenylene oxide) resin and PA66 (nylon 66) resin all is one of widely used engineering plastics, and PPO belongs to the amorphism material, and is high heat-resisting, dimensional stabilizing, electric insulating quality and creep resistance excellence, but its processing fluidity is poor, organic solvent-resistant and glass consistency are not poor, PA66 belongs to crystalline material, good fluidity, organic solvent-resistant, good with the glass consistency, but its easy suction, poor dimensional stability, thermotolerance is relatively poor.
Along with developing rapidly of automotive industry, become the trend and the direction of automotive material development to mould Dai Gang, the PPO/PA66 alloy is with its excellent thermotolerance, good processibility, but sprayability etc., the door-plate that is widely used in automobile, guard shield, spoiler, large-scale product such as wheelhouse portions, these large-scale products not only require strength of materials height, good heat resistance, and require the dimensional stability of material splendid.
The PPO/PA66 alloy overwhelming majority of Chu Shouing is the PPO/PA66 alloy of non-filling on the market, and anti-warpage properties is good, but heat resistant type and physical strength are lower, has insufficient strength, heat-resisting not enough defective when being used for making near the parts of engine and stress members.Mainly be to solve heat-resisting and strength problem at present by adopting glass fibre to strengthen the PPO/PA66 alloy, after glass fibre strengthens the PPO/PA66 alloy, the thermotolerance and the physical strength of material significantly rise, but the dimensional stability of material but descends significantly, the serious buckling deformation of product influences product outward appearance and assembling after the moulding.
[summary of the invention]
The technical problem to be solved in the present invention provides a kind of high heat resistance, good dimensional stability, high-strength PPO/PA66 alloy material of low warpage and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, a kind of high-strength PPO/PA66 alloy material is made up of following component by weight percentage:
Polyphenylene oxide resin 20-40%;
Nylon 66 20-40%;
Compatilizer 5-10%;
Toughner 5-10%;
Glass fibre 5-15%;
Glass microballon 5-15%;
Mica powder 5-15%;
Oxidation inhibitor 0.2-0.4%;
Other auxiliary agent 0.5-1%.
Above-described high-strength PPO/PA66 alloy material, described polyphenylene oxide resin, its limiting viscosity is 0.35-0.5dl/g; Described Nylon 66, its solution solvent viscosity ratio are 2.4-3.0.Described compatilizer is PPO-g-MAH, and percentage of grafting is 1.0-1.7%.Described toughner is SEBS-g-MAH, and percentage of grafting is 0.8-1.5%.Described glass fibre is the alkali-free chopped strand, the short length 3-12mm that cuts.Described glass microballon is a hollow glass micropearl, and particle diameter order number is 800-5000.Described mica powder is a scale structure, and particle diameter order number is 200-1000.Described oxidation inhibitor is the composite of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and three (2, the 4-di-t-butyl) phenyl-phosphite auxiliary anti-oxidant.Described other auxiliary agent comprises lubricant, thermo-stabilizer, one or more in the ultraviolet absorbers.
A kind of above-mentioned high-strength PPO/PA66 alloy material, preparation method's technical scheme be may further comprise the steps:
A: taken by weighing polyphenylene oxide resin, Nylon 66, compatilizer and toughner by the described weight proportion of claim 1, poured whipping device into, mixed;
B: taken by weighing glass microballon, mica powder, oxidation inhibitor, other auxiliary agent by the described weight proportion of claim 1, the plastics materials that mixes in a step is put in the mixing tank and to be mixed up to evenly;
C: mixed raw materials among the b is put into the loading hopper of twin screw extruder, and the glass fibre that takes by weighing by the described weight proportion of claim 1 joins in the forcing machine by the side feeding, through melt extruding granulation; Complete processing is as follows: twin screw extruder one district temperature 220-240 ℃, two district temperature 230-250 ℃, three district temperature 260-270 ℃, four district temperature 250-270 ℃, head 260-270 ℃, the residence time 2～3min, pressure are 12-18MPa.
The present invention has following beneficial effect:
1: the starting material of use all are the environmentally-friendly sanitary levels, and the material of preparation contacts with human body can not cause any harmful material.
2: guaranteeing that material has high strength, high heat-resisting, when easily spraying, also have excellent size stability, low warpage.
3: a kind of high-strength PPO/PA66 alloy material that the present invention proposes, and preparation technology is simple.
[embodiment]
By glass fibre compound glass microballon, mica powder strengthens the PPO/PA66 alloy, and the alloy that makes has the intensity height, good heat resistance, and characteristics such as easy spraying also have low warpage, the scantling good stability simultaneously.
A kind of high-strength PPO provided by the invention/PA66 alloy material,, its composition is (%) by weight ratio: polyphenylene oxide 20-40%; Nylon 6620-40%; Compatilizer 5-10%; Toughner 5-10%; Glass fibre 5-15%; Glass microballon 5-15%; Mica powder 5-15%; Oxidation inhibitor 0.2-0.4%; Other auxiliary agent 0.5-1%.
Wherein, polyphenylene oxide resin, its limiting viscosity is 0.35-0.5dl/g; Nylon 66, its solution solvent viscosity ratio are 2.4-3.0; Compatilizer is PPO-g-MAH, and percentage of grafting is 1.0-1.7%; Toughner is SEBS-g-MAH, and percentage of grafting is 0.8-1.5%; Glass fibre is the alkali-free chopped strand, the short length 3-12mm that cuts; Glass microballon is a hollow glass micropearl, and particle diameter order number is 800-5000; Mica powder is a scale structure, and particle diameter order number is 200-1000; Oxidation inhibitor is the composite of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and three (2, the 4-di-t-butyl) phenyl-phosphite auxiliary anti-oxidant; Other auxiliary agent comprises lubricant, thermo-stabilizer, ultraviolet absorbers.
In the present invention, taken by weighing polyphenylene oxide resin, Nylon 66, compatilizer and toughner by weight ratio earlier, poured whipping device into, mixed; Taken by weighing glass microballon, mica powder, oxidation inhibitor, other auxiliary agent more by weight ratio, put in the mixing tank with the plastics materials that mixes above and mix up to evenly; Then all mixed raw materials are put into the loading hopper of twin screw extruder, glass fibre joins in the forcing machine by the side feeding, through melt extruding granulation; Complete processing is as follows: twin screw extruder one district temperature 220-240 ℃, two district temperature 230-250 ℃, three district temperature 260-270 ℃, four district temperature 250-270 ℃, head 260-270 ℃, the residence time 2～3min, pressure are 12-18MPa.
For ease of the present invention is further understood, now describe the present invention in conjunction with specific embodiments:
In the composite-material formula of the following example, it is 0.45dl/g that polyphenylene oxide resin is selected limiting viscosity for use, as blue star Chemical Manufacture, trade names LXR045; Nylon 66 is selected solution solvent viscosity ratio 2.6 for use, produces trade names 27AE1 as Rhodia; It is 1.3 PPO-g-MAH that compatilizer is selected percentage of grafting for use, produces as SABIC company, and trade names are 450C; It is 1.2 SEBS-g-MAH that toughner is selected percentage of grafting for use, produces as the company of rising of section, and trade names are FX1901G; Glass fibre is selected the short alkali-free chopped strand of length at 3-6mm of cutting for use, produces as megalith company, and trade names are 560; It is 2500 purposes that glass microballon is selected particle diameter for use, produces as 3M company, and trade names are KT-2500; It is 800 purposes that mica powder is selected particle diameter order number for use, produces as hundred million letter mineral products companies, and trade names are YC800; Oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and three (2, the 4-di-t-butyl) phenyl-phosphite selects for use Ciba company to produce, and trade names are respectively Irganox1010, and Irganox168.Lubricant in other auxiliary agent is selected pentaerythritol stearate for use, produce as Long Sha company, trade names are PETS-3, thermo-stabilizer is selected cuprous salt for use, produces trade names H3336 as Brueggemann company, ultraviolet absorbers is selected the hydroxy-phenyl benzotriazole class for use, produce as vapour Bagong department, trade names UV234 can select wherein one or more in an embodiment for use.
Embodiment 1:
With PPO by weight percentage be 27% (following all be weight percentage), PA6630%, PPO-g-MAH 6%, and SEBS-g-MAH 6%, weighs up and pours agitator into, stir, press glass microballon 5% again, mica powder 15%, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Embodiment 2:
PPO is 27% by weight (below be weight ratio), PA6630%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stir, press glass microballon 10% again, mica powder 10%, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Embodiment 3:
PPO is 27% by weight (below be weight ratio), PA6630%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stir, press glass microballon 15% again, mica powder 5%, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Embodiment 4:
PPO is 20% by weight (below be weight ratio), PA6637%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stir, press glass microballon 10% again, mica powder 10%, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Embodiment 5:
PPO is 37% by weight (below be weight ratio), PA6620%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stir, press glass microballon 10% again, mica powder 10%, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Comparative Examples 1:
PPO is 27% by weight (below be weight ratio), PA6630%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stirs, and presses 1010/1680.2/0.2% again, and other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 30% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Comparative Examples 2:
PPO is 27% by weight (below be weight ratio), PA6630%, PPO-g-MAH6%, SEBS-g-MAH 6%, weigh up and pour agitator into, stir, press glass microballon 20% again, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa
Comparative Examples 3:
PPO is 27% by weight (below be weight ratio), PA6630%, PPO-g-MAH6%, SEBS-g-MAH 6%, weigh up and pour agitator into, stir, press mica powder 20% again, 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 10% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa
Comparative Examples 4:
PPO is 20% by weight (below be weight ratio), PA6637%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stirs, and presses 1010/1680.2/0.2% again, and other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 30% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3mi n.Pressure is 14MPa.
Comparative Examples 5:
PPO is 37% by weight (below be weight ratio), PA6620%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stirs, and presses 1010/1680.2/0.2% again, and other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder, glass fibre 30% joins in the forcing machine by the side feeding, and through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Comparative Examples 6:
PPO is 43% by weight (below be weight ratio), PA6644%, PPO-g-MAH6%, SEBS-g-MAH 6%, weighs up to pour agitator into, stirs, and presses 1010/1680.2/0.2% again, and other auxiliary agents 0.6% weigh up, and pour agitator into and stir.The material that mixes is joined in the hopper of twin screw extruder through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: district's temperature: 230 ℃; Two districts: 250 ℃; Three districts: 270 ℃; Four districts: 260 ℃; Head: 260 ℃; The residence time 2～3min.Pressure is 14MPa.
Performance test:
Tensile strength is tested by GB/T 1040 standards, and specimen types is an II type sample, batten size (mm): 115 (length) * (6 ± 0.04) (middle parallel portion width) * 2 (thickness), and draw speed is 200mm/min;
Flexural strength and modulus in flexure are tested by GB 9341/T standard.Specimen types is specimen size (mm): (80 ± 0.4) * (10 ± 0.1) * (4 ± 0.02), rate of bending are 20mm/min;
The angularity test is tested according to the angularity judgement criteria on the plane, and specimen types is specimen size (mm): (1000 ± 2) * (1000 ± 2) * (2 ± 0.02), test condition are that the 5KG clamping plate are tested after pressing 24h after the moulding.
Thermal distortion test is tested according to ASTM D648 standard, and specimen types is specimen size (mm): (128 ± 0.2) * (13 ± 0.04) * (6.4 ± 0.02). and test pressure is 1.82MPa, and unit is ℃.
Embodiment and Comparative Examples prescription and material property see the following form:
Form Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
??PPO(％) ??27 ??27 ??27 ??20 ??37
??PA66(％) ??30 ??30 ??30 ??37 ??20
Compatilizer (%) ??6 ??6 ??6 ??6 ??6
Toughner (%) ??6 ??6 ??6 ??6 ??6
Glass fibre (%) ??10 ??10 ??10 ??10 ??10
Glass microballon (%) ??5 ??10 ??15 ??10 ??10
Mica powder (%) ??15 ??10 ??5 ??10 ??10
??1010(％) ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
Form Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
??168(％) ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
Other auxiliary agent (%) ??0.6 ??0.6 ??0.6 ??0.6 ??0.6
Tensile strength (MPa) ??108 ??102 ??100 ??106 ??101
Flexural strength (MPa) ??155 ??146 ??140 ??152 ??145
Modulus in flexure (MPa) ??6400 ??6150 ??5400 ??6240 ??6120
Angularity (mm) ??0.38 ??0.31 ??0.26 ??0.32 ??0.30
Thermal distortion (℃) ??222 ??216 ??212 ??218 ??215
Form Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6
??PPO(％) ??27 ??27 ??27 ??20 ??37 ??43
??PA66(％) ??30 ??30 ??30 ??37 ??20 ??44
Compatilizer (%) ??6 ??6 ??6 ??6 ??6 ??6
Toughner (%) ??6 ??6 ??6 ??6 ??6 ??6
Glass fibre (%) ??30 ??10 ??10 ??30 ??30 ??/
Glass microballon (%) ??/ ??20 ??/ ??/ ??/ ??/
Mica powder (%) ??/ ??/ ??20 ??/ ??/ ??/
??1010(％) ??0.2 ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
??168(％) ??0.2 ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
Form Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6
Other auxiliary agent (%) ??0.6 ??0.6 ??0.6 ??0.6 ??0.6 ??0.2
Tensile strength (MPa) ??135 ??82 ??108 ??138 ??132 ??64
Flexural strength (MPa) ??172 ??132 ??152 ??175 ??168 ??95
Modulus in flexure (MPa) ??7500 ??4600 ??5860 ??7650 ??7340 ??2450
Angularity (mm) ??1.8 ??0.22 ??0.62 ??2.0 ??1.6 ??0.28
Thermal distortion (℃) ??232 ??198 ??224 ??235 ??230 ??125
By Comparative Examples as can be seen, glass fibre has tangible enhancement to the PPO/PA66 alloy, can increase substantially the thermotolerance and the physical strength of material, but the angularity of material is very big, and poor dimensional stability is unfavorable for the moulding and the assembling of large-scale product; Compare Comparative Examples 1,2,3 as can be seen, adopt glass fibre combined mica powder to strengthen the PPO/PA66 alloy in the Comparative Examples 3, the purer glass of the thermotolerance of material and intensity strengthens to some extent and descends, angularity also decrease (0.62), but still bigger, be unfavorable for the moulding and the assembling of large-scale product, adopt glass fibre compound glass microballon to strengthen the PPO/PA66 alloy in the Comparative Examples 2, the material warp degree is very little, be beneficial to the moulding and the assembling of product, but the strength of materials and heat-resisting purer glass strengthen decline obviously, the material mechanical performance loss is bigger, when making some stress members, do not satisfy the mechanical performance of products requirement.Embodiment 1,2, and 3,4,5 adopt glass fibre compound glass microballon, and the mica powder ternary strengthens the PPO/PA66 alloy, with Comparative Examples 1,2,3 compare, the excellent combination property of material, and physical strength and the heat-resisting ratio 1 that compares descend to some extent, but intensity is still up to more than the 100MPa, thermal distortion can be satisfied the requirement of stress members and heat-resisting product more than 210 ℃, and the material warp degree is very little simultaneously, angularity near Comparative Examples 2, about 0.3, be fit to the moulding and the assembling of large-scale product, the angularity 0.62 that compares ratio 3 has reduced half, and the angularity of Comparative Examples 1 is especially up to 1.8, poor dimensional stability.
In sum, glass fibre compound glass microballon, the mica powder ternary strengthens PPO/PA66 alloy, excellent combination property, be fit to make intensity, heat-resisting having relatively high expectations, large-scale product and heating part that dimensional stability requires, product angularity after the moulding is low, and outward appearance is good, is beneficial to assembling and post-treatment.
More than a kind of high-strength PPO provided by the present invention/PA66 alloy material and preparation method thereof is described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.

Claims (10)

1. high-strength PPO/PA66 alloy material,, it is characterized in that, form by following component by weight percentage:
Polyphenylene oxide resin 20-40%;
Nylon 66 20-40%;
Compatilizer 5-10%;
Toughner 5-10%;
Glass fibre 5-15%;
Glass microballon 5-15%;
Mica powder 5-15%;
Oxidation inhibitor 0.2-0.4%;
Other auxiliary agent 0.5-1%.
2. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described polyphenylene oxide resin, its limiting viscosity are 0.35-0.5dl/g; Described Nylon 66, its solution solvent viscosity ratio are 2.4-3.0.
3. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described compatilizer is PPO-g-MAH, percentage of grafting is 1.0-1.7%.
4. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described toughner is SEBS-g-MAH, percentage of grafting is 0.8-1.5%.
5. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described glass fibre is the alkali-free chopped strand, the short length 3-12mm that cuts.
6. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described glass microballon is a hollow glass micropearl, particle diameter order number is 800-5000.
7. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described mica powder is a scale structure, particle diameter order number is 200-1000.
8. high-strength PPO as claimed in claim 1/PA66 alloy material, it is characterized in that: described oxidation inhibitor is the composite of four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and three (2, the 4-di-t-butyl) phenyl-phosphite auxiliary anti-oxidant.
9. high-strength PPO as claimed in claim 1/PA66 alloy material,, it is characterized in that: described other auxiliary agent comprises lubricant, thermo-stabilizer, one or more in the ultraviolet absorbers.
10. high-strength PPO as claimed in claim 1/PA66 alloy material, the preparation method, it is characterized in that, may further comprise the steps:
A: taken by weighing polyphenylene oxide resin, Nylon 66, compatilizer and toughner by the described weight proportion of claim 1, poured whipping device into, mixed;
B: taken by weighing glass microballon, mica powder, oxidation inhibitor, other auxiliary agent by the described weight proportion of claim 1, the plastics materials that mixes in a step is put in the mixing tank and to be mixed up to evenly;
C: mixed raw materials among the b is put into the loading hopper of twin screw extruder, and the glass fibre that takes by weighing by the described weight proportion of claim 1 joins in the forcing machine by the side feeding, through melt extruding granulation; Complete processing is as follows: twin screw extruder one district temperature 220-240 ℃, two district temperature 230-250 ℃, three district temperature 260-270 ℃, four district temperature 250-270 ℃, head 260-270 ℃, the residence time 2～3min, pressure are 12-18MPa.
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CN102040830A (en) * 2010-12-20 2011-05-04 金发科技股份有限公司 Polyamide composition and preparation method thereof
CN102417720A (en) * 2011-11-24 2012-04-18 上海日之升新技术发展有限公司 High-performance glass fiber reinforcement polyphenyl ether/polyamide alloy and production method thereof
CN102417717A (en) * 2011-11-24 2012-04-18 上海日之升新技术发展有限公司 Compatilizer and preparation method thereof, alloy comprising same and production method thereof
CN102585478A (en) * 2011-01-14 2012-07-18 合肥杰事杰新材料股份有限公司 Toughened polyphenyl ether and nylon alloy and preparation method for toughened polyphenyl ether and nylon alloy
CN102863776A (en) * 2012-09-05 2013-01-09 忻峰 Polyphenylene oxide/polyamide 66 (PPO/PA66) synthetic plastic
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CN102964828A (en) * 2012-11-22 2013-03-13 象山华鹰塑料工程有限公司 PA66 plastic for automobile parts
CN103087500A (en) * 2012-10-22 2013-05-08 虞海香 PA66 (polyamide 66) plastic
CN103160108A (en) * 2011-12-09 2013-06-19 上海杰事杰新材料(集团)股份有限公司 Halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as well as preparation and application for same
CN103351620A (en) * 2013-06-25 2013-10-16 中山赛特工程塑料有限公司 High-strength and high-fluidity glass fiber reinforced PPO/PA alloy material and preparation method thereof
CN103804883A (en) * 2012-11-15 2014-05-21 常熟市沈氏塑业有限公司 Preparation method of phosphate flame retardant modified polyphenylether material
CN103804884A (en) * 2012-11-15 2014-05-21 常熟市沈氏塑业有限公司 Phosphate flame retardant modified polyphenylether material
CN106084770A (en) * 2016-04-05 2016-11-09 南京聚隆科技股份有限公司 A kind of heat-proof aging, low temperature high impact polyphenylene ether/nylon composite materials and preparation method thereof
CN108034242A (en) * 2017-12-27 2018-05-15 南京鸿瑞塑料制品有限公司 A kind of fiberglass reinforced high wear-resistant PA 66/PPO composite material and preparation method thereof
CN108485252A (en) * 2018-04-27 2018-09-04 黑龙江鑫达企业集团有限公司 A kind of reinforced nylon 6 material of resistance to warping deformation and preparation method thereof
CN108587109A (en) * 2018-03-12 2018-09-28 广东顺威赛特工程塑料开发有限公司 A kind of high heat-resistant high-strength PPE alloy materials and preparation method thereof
CN111117221A (en) * 2019-12-10 2020-05-08 珠海格力绿色再生资源有限公司 Low-water-absorption composite material and preparation method thereof
CN112898677A (en) * 2021-01-20 2021-06-04 长虹美菱股份有限公司 High-rigidity PP and manufacturing method thereof
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CN102585478A (en) * 2011-01-14 2012-07-18 合肥杰事杰新材料股份有限公司 Toughened polyphenyl ether and nylon alloy and preparation method for toughened polyphenyl ether and nylon alloy
CN102417720A (en) * 2011-11-24 2012-04-18 上海日之升新技术发展有限公司 High-performance glass fiber reinforcement polyphenyl ether/polyamide alloy and production method thereof
CN102417717A (en) * 2011-11-24 2012-04-18 上海日之升新技术发展有限公司 Compatilizer and preparation method thereof, alloy comprising same and production method thereof
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CN103160108A (en) * 2011-12-09 2013-06-19 上海杰事杰新材料(集团)股份有限公司 Halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as well as preparation and application for same
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CN102863777A (en) * 2012-09-05 2013-01-09 忻峰 Plastic and preparation method thereof
CN102898824A (en) * 2012-10-08 2013-01-30 惠州市华聚塑化科技有限公司 Moisture-proof leadless soldering nylon 46 composite material and preparation method thereof
CN103087500A (en) * 2012-10-22 2013-05-08 虞海香 PA66 (polyamide 66) plastic
CN103804883A (en) * 2012-11-15 2014-05-21 常熟市沈氏塑业有限公司 Preparation method of phosphate flame retardant modified polyphenylether material
CN103804884A (en) * 2012-11-15 2014-05-21 常熟市沈氏塑业有限公司 Phosphate flame retardant modified polyphenylether material
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CN102952398A (en) * 2012-11-19 2013-03-06 宁波瑞祥电器有限公司 Material for manufacturing power socket
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CN103351620A (en) * 2013-06-25 2013-10-16 中山赛特工程塑料有限公司 High-strength and high-fluidity glass fiber reinforced PPO/PA alloy material and preparation method thereof
CN106084770A (en) * 2016-04-05 2016-11-09 南京聚隆科技股份有限公司 A kind of heat-proof aging, low temperature high impact polyphenylene ether/nylon composite materials and preparation method thereof
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CN108034242A (en) * 2017-12-27 2018-05-15 南京鸿瑞塑料制品有限公司 A kind of fiberglass reinforced high wear-resistant PA 66/PPO composite material and preparation method thereof
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CN111117221A (en) * 2019-12-10 2020-05-08 珠海格力绿色再生资源有限公司 Low-water-absorption composite material and preparation method thereof
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