CN101875776B - 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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CN101875776B
CN101875776B CN2010101405469A CN201010140546A CN101875776B CN 101875776 B CN101875776 B CN 101875776B CN 2010101405469 A CN2010101405469 A CN 2010101405469A CN 201010140546 A CN201010140546 A CN 201010140546A CN 101875776 B CN101875776 B CN 101875776B
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ppo
alloy material
strength
glass
mica powder
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CN101875776A (en
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徐东
贺永
周兵
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Xu Dong
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深圳市科聚新材料有限公司
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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 are excellent, 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 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, the large-scale product such as wheelhouse portions, these large-scale products not only require the strength of materials high, good heat resistance, and require the dimensional stability of material splendid.
The PPO/PA66 alloy overwhelming majority of selling on the market is the PPO/PA66 alloy of non-filling, and anti-warpage properties is good, but heat resistant type and physical strength are lower, has insufficient strength, heat-resisting inadequate defective when being used for making near the parts of engine and stress members.Mainly be to solve heat-resisting and strength problem by adopting glass fibre to strengthen the PPO/PA66 alloy at present, after glass fibre strengthens the PPO/PA66 alloy, thermotolerance and the physical strength of material significantly rise, but the dimensional stability of material but significantly descends, the serious buckling deformation of product affects 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, the high-strength PPO of low warpage/PA66 alloy material and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of high-strength PPO/PA66 alloy material is comprised 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, chopped length 3-12mm.Described glass microballon is hollow glass micropearl, and particle diameter order number is 800-5000.Described mica powder is scale structure, and particle diameter order number is 200-1000.Described oxidation inhibitor is the composite of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and three (2,4-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 weight proportion claimed in claim 1, poured whipping device into, mixed;
B: taken by weighing glass microballon, mica powder, oxidation inhibitor, other auxiliary agent by weight proportion claimed in claim 1, the plastics materials that mixes in a step is put into and is mixed in the mixing tank until evenly;
C: the raw material that mixes among the b is put into the loading hopper of twin screw extruder, and the glass fibre that takes by weighing by weight proportion claimed in 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 dimensional stability, low warpage.
3: a kind of high-strength PPO that the present invention proposes/PA66 alloy material, 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 the characteristics such as easy spraying also have low warpage simultaneously, and dimension stability is good.
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, chopped length 3-12mm; Glass microballon is hollow glass micropearl, and particle diameter order number is 800-5000; Mica powder is scale structure, and particle diameter order number is 200-1000; Oxidation inhibitor is the composite of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and three (2,4-di-t-butyl) phenyl-phosphite auxiliary anti-oxidant; Other auxiliary agent comprises lubricant, thermo-stabilizer, ultraviolet absorbers.
In the present invention, taken by weighing by weight ratio polyphenylene oxide resin, Nylon 66, compatilizer and toughner first, poured whipping device into, mixed; Taken by weighing by weight ratio again glass microballon, mica powder, oxidation inhibitor, other auxiliary agent, put into the plastics materials that mixes above and mix in the mixing tank until evenly; Then the raw material that all is mixed is put into the loading hopper of twin screw extruder, and 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, such as blue star Chemical Manufacture, trade names LXR045; Nylon 66 is selected solution solvent viscosity ratio 2.6, produces trade names 27AE1 such as Rhodia; It is 1.3 PPO-g-MAH that compatilizer is selected percentage of grafting, produces such as SABIC company, and trade names are 450C; It is 1.2 SEBS-g-MAH that toughner is selected percentage of grafting, produces such as the company of rising of section, and trade names are FX1901G; Glass fibre selects chopped length at the alkali-free chopped strand of 3-6mm, produces such as megalith company, and trade names are 560; It is 2500 purposes that glass microballon is selected particle diameter, produces such as 3M company, and trade names are KT-2500; It is 800 purposes that mica powder is selected particle diameter order number, produces such as hundred million letter mineral products companies, and trade names are YC800; Oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and three (2,4-di-t-butyl) phenyl-phosphite selects Ciba company to produce, and trade names are respectively Irganox1010, and Irganox168.Lubricant in other auxiliary agent is selected pentaerythritol stearate, produce such as Long Sha company, trade names are PETS-3, thermo-stabilizer is selected cuprous salt, produces trade names H3336 such as Brueggemann company, ultraviolet absorbers is selected the hydroxy-phenyl benzotriazole class, produce such as vapour Bagong department, trade names UV234 can select wherein one or more in an embodiment.
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 again glass microballon 5%, 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 again glass microballon 10%, 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 again glass microballon 15%, 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 again glass microballon 10%, 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 again glass microballon 10%, 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, press 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir again.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 again glass microballon 20%, 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 again mica powder 20%, 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, press 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir again.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, press 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir again.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, press 1010/1680.2/0.2%, other auxiliary agents 0.6% weigh up, and pour agitator into and stir again.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 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
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
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
Can be found out that by Comparative Examples glass fibre has obvious enhancement to the PPO/PA66 alloy, can increase substantially thermotolerance and the physical strength of material, but the angularity of material be very large, poor dimensional stability is unfavorable for moulding and the assembling of large-scale product; Compare Comparative Examples 1,2,3 can find out, 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 larger, be unfavorable for 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 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 larger, when making some stress members, do not satisfy the mechanical property requirement of product.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 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, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.

Claims (9)

1. high-strength PPO/PA66 alloy material is characterized in that, is comprised 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%;
Described glass microballon is hollow glass micropearl, and particle diameter order number is 800-5000.
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, chopped length 3-12mm.
6. high-strength PPO as claimed in claim 1/PA66 alloy material, it is characterized in that: described mica powder is scale structure, particle diameter order number is 200-1000.
7. high-strength PPO as claimed in claim 1/PA66 alloy material, it is characterized in that: described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester primary antioxidant and three (2,4-di-t-butyl) phenyl-phosphite auxiliary anti-oxidant composite.
8. 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.
9. the preparation method of high-strength PPO as claimed in claim 1/PA66 alloy material is characterized in that, may further comprise the steps:
A: taken by weighing polyphenylene oxide resin, Nylon 66, compatilizer and toughner by weight proportion claimed in claim 1, poured whipping device into, mixed;
B: taken by weighing glass microballon, mica powder, oxidation inhibitor, other auxiliary agent by weight proportion claimed in claim 1, the plastics materials that mixes in a step is put into and is mixed in the mixing tank until evenly;
C: the raw material that mixes among the b is put into the loading hopper of twin screw extruder, and the glass fibre that takes by weighing by weight proportion claimed in 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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