CN103992630A - Polyphenylether resin alloy material for automobile wheel hub housings and preparation method thereof - Google Patents
Polyphenylether resin alloy material for automobile wheel hub housings and preparation method thereof Download PDFInfo
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- CN103992630A CN103992630A CN201410219832.2A CN201410219832A CN103992630A CN 103992630 A CN103992630 A CN 103992630A CN 201410219832 A CN201410219832 A CN 201410219832A CN 103992630 A CN103992630 A CN 103992630A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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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
- B29C48/03—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
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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
- B29C48/36—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
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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
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92657—Volume or quantity
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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Abstract
The invention discloses a polyphenylether resin alloy material for automobile wheel hub housings and a preparation method thereof. The polyphenylether resin alloy material for automobile wheel hub housings comprises the following components in parts by weight: 10-70 parts of polyphenylether resin, 20-60 parts of nylon resin, 1-8 parts of elastomer, 8-22 parts of glass fiber, 1-8 parts of polyolefin, 5-30 parts of graft body, 1-5 parts of functional master batch, 1-3 parts of black master batch, 0.2-0.5 part of main antioxidant and 0.1-0.5 part of auxiliary antioxidant. The polyphenylether resin alloy material for automobile wheel hub housings has the advantages of high brittleness resistance, favorable flowability, high solvent resistance and favorable adhesiveness to on-line spray paint on the premise of effectively maintaining excellent properties of the polyphenylether resin.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of polyphenylene oxide resin alloy material for processing automobile wheel hub outer cover and preparation method thereof.
Background technology
Polyphenylene oxide resin has the performance of a lot of excellences, and such as mechanical property, resistance toheat, dimensional stability, from flame retardant properties etc., its alloy is widely used in the fields such as electronic apparatus, automobile component, communication photovoltaic.In recent years, polyphenylene oxide alloy material is more and more for auto-parts field, but due to the defect in its fragility and mobility, particularly on-line spray aspect, the not solvent of resistance to organic chemistry, easily produces the reason such as stress cracking or spraying poor adhesive force, and the utilization of polyphenylene oxide alloy material on a lot of automobile component is limited by very large, particularly relate to larger Injection moulded part, as automotive hub outer cover part.These drawbacks limit its application in automotive field.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of polyphenylene oxide resin alloy material for processing automobile wheel hub outer cover and preparation method thereof, to solve the anti-fragility of existing polyphenylene oxide resin, mobility and the poor defect of the solvent of resistance to organic chemistry.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
For a polyphenylene oxide resin alloy material for automotive hub outer cover, comprise the component of following weight part:
And a kind of preparation method of the polyphenylene oxide resin alloy material for automotive hub outer cover, comprises the following steps:
Take respectively each component according to above-mentioned polyphenylene oxide resin alloy material;
The described polyphenylene oxide resin taking and grafting body are carried out to mixing treatment, obtain the first mixture;
The described elastomerics, polyolefine, functional agglomerate, black masterbatch, primary antioxidant and the auxiliary anti-oxidant that take are carried out to mixing treatment, obtain the second mixture;
Described the first mixture, the second mixture and nylon resin are added from main spout respectively, described glass fibre is added and carries out mixed melting and extrude from side spout.
Compared with prior art, the above-mentioned polyphenylene oxide resin alloy material for automotive hub outer cover passes through at polyphenylene oxide resin, in the matrix resins such as nylon resin, add grafting body, functional agglomerate and other components, it is acted synergistically, give polyphenylene oxide resin alloy material of the present invention in the mechanical property that can effectively keep polyphenyl ether resin material, on the basis of the excellent properties such as resistance toheat, polyphenylene ether resin fragility, mobility, the tack of solvent resistance and on-line spray paint is improved, can well meet the injection moulding of automotive hub outer cover, following process is processed and service requirements.
The above-mentioned polyphenylene oxide resin alloy material preparation method for automotive hub outer cover only need carry out each component to melt extrude after mixing treatment, its preparation method can make each component be uniformly dispersed and act synergistically, in realizing the above-mentioned excellent properties of polyphenylene oxide resin alloy material of the present invention, make its stable performance.In addition, its preparation method technique is simple, and condition is easily controlled, with low cost, and feature low for equipment requirements, is suitable for suitability for industrialized production.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of anti-fragility strong, the good polyphenylene oxide resin alloy material for automotive hub outer cover of tack of good fluidity, solvent resistance and on-line spray paint.This polyphenylene oxide resin alloy material that is used for automotive hub outer cover comprises following components by weight percent:
Particularly, above-mentioned polyphenylene oxide resin and nylon resin are matrix composition, in a preferred embodiment, this polyphenylene oxide resin is the polymkeric substance, 2 of 2,6-xylenol, 6-xylenol and 2, the multipolymer of 3,6-pseudocuminol, its limiting viscosity is 0.2-0.6dl/g.
In specific embodiment, the content of this polyphenylene oxide resin can be the weight parts such as 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts.
Above-mentioned nylon resin is selected the mixture of a kind of in nylon 6 or nylon 66 or two kinds, and in further preferred embodiment, it is 2.43 ± 0.03 nylon 6 that this nylon 6 is selected relative viscosity, and it is 2.67 ± 0.03 nylon 66 that nylon 66 is selected relative viscosity.
In specific embodiment, the content of this nylon resin can be the weight parts such as 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts.
Above-mentioned elastomerics is preferably at least one in polyhutadiene, chloroprene rubber, polyisoprene rubber, using trans-polyisoprene, styrene-butadiene rubber(SBR), HSBR, hydrogenation nitrile rubber, ethylene-propylene rubber(EPR), ethylene copolymer.
In specific embodiment, this elastomeric content can be the weight parts such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts.
Above-mentioned glass fibre improves the rigidity intensity of above-mentioned polyphenylene oxide resin alloy material, and accordingly, in a preferred embodiment, this glass fibre is selected alkali-free glass fiber.
In specific embodiment, the content of this glass fibre can be 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts,, the weight parts such as 20 parts, 21 parts, 22 parts.
Said polyolefins can improve mobility, the surface luster of above-mentioned polyphenylene oxide resin alloy material and reduce costs.Accordingly, in a preferred embodiment, at least one in polyethylene, polypropylene, poly 1-butene, poly(4-methyl-1-pentene), ethylene-propylene copolymer, ethylene-butene copolymer.
In specific embodiment, this polyolefinic content can be the weight parts such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts.
Above-mentioned grafting body can make the conjugation between consistency between each resin and resin and glass fibre improve.Therefore, in a preferred embodiment, this grafting body is taking at least one in polyphenylene oxide resin, nylon resin, ethylene-butene copolymer as base material, taking at least one in MALEIC ANHYDRIDE, benzoyl oxide, Tetra hydro Phthalic anhydride, diacetyl oxide, propionic anhydride, citric acid as grafts.This base material and grafts can form this grafting body according to known grafting method.This grafting body can obtain base material and grafts by melt extruding granulation, in a preferred embodiment, the weight ratio of base material and grafts is (6～9): (4～1).In another preferred embodiment, the condition that base material and grafts melt extrude processing is: temperature is 200～300 DEG C, and vacuum tightness is 0.5～0.8MPa, and screw speed is 260～300RPM.This melt extrudes processing and can adopt twin screw extruder to realize.
In specific embodiment, the content of this grafting body can be the weight parts such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts.
Above-mentioned functions master batch on-line spray strong adhesion, suppresses small organic molecule and separates out the appearance that causes surface irregularity or pit.Accordingly, in a preferred embodiment, taking described functional agglomerate gross weight as 100%, described functional agglomerate comprises the composition of following percentage composition:
Wherein, resin binder is selected at least one in polyphenylene oxide resin, nylon resin, ethylene-butene copolymer.Chirality organic inorganic hybridization mesoporous material is preferably taking C-Si key as main chain, has chiral structure, has meso-hole structure material.Lubricant is preferably at least one in paraffin class, lipid acid and ester class thereof, fatty acid amide, silicoorganic compound.Epoxy resin is preferably at least one in bisphenol A type epoxy resin, phenol aldehyde type epoxy resin.Inorganic filler is at least one in mesoporous silicon oxide, mesoporous TiO 2, nano imvite, superfine talcum powder.This preferred each component on-line spray sticking power is stronger, more effectively suppresses small organic molecule and separates out the appearance that causes surface irregularity or pit.
In specific embodiment, the content of this functional agglomerate can be the weight parts such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts.
In the various embodiments described above, functional agglomerate can be prepared as follows acquisition:
Will component as each in above-mentioned functional agglomerate as 60-90% resin binder, 3-15% chirality organic inorganic hybridization mesoporous material, 3-10% lubricant, 1-12% epoxy resin, 3-8% inorganic filler carry out mixing treatment, then melt extrude processing.Wherein, the condition that melt extrudes processing is: temperature is 200～280 DEG C, and vacuum tightness is 0.5～0.8MPa, and screw speed is 260～300RPM.This melt extrudes processing and can adopt twin screw extruder to realize.
Above-mentioned black masterbatch can improve the spray colouration of above-mentioned polyphenylene oxide resin alloy material, anti-ultraviolet function, the aging speed of reduction material itself.The black masterbatch functional agglomerate that it can directly select Cabot high performance material (Tianjin) company limited to produce.In specific embodiment, the content of this black masterbatch can be the weight parts such as 1 part, 2 parts, 3 parts.
Above-mentioned primary antioxidant and auxiliary antioxidant are given the above-mentioned polyphenylene oxide resin alloy material antioxygenation for automotive hub outer cover, delaying retrogradation.This primary antioxidant and auxiliary antioxidant are mainly that material acts synergistically and realizes the thermo oxidative aging of this polyphenylene oxide resin alloy material in extruding pelletization and injection molding process.Therefore, in a preferred embodiment, this primary antioxidant is 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) mixture of a kind of in propionic acid stearyl alcohol ester or two kinds, auxiliary antioxidant is the mixture of a kind of in two (2,4-di-t-butyl) pentaerythritol diphosphites, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters or two kinds.In specific embodiment, the content of this primary antioxidant can be the weight part such as 0.2 part, 0.3 part, 0.4 part, 0.5 part; The content of this auxiliary antioxidant can be the weight part such as 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part.
From the above mentioned, the above-mentioned polyphenylene oxide resin alloy material for automotive hub outer cover interacts by each component, giving polyphenylene oxide resin alloy material of the present invention can effectively keep on the basis of the excellent properties such as mechanical property, resistance toheat of polyphenyl ether resin material, the tack of polyphenylene ether resin fragility, mobility, solvent resistance and on-line spray paint is improved, and injection moulding, the following process that can well meet automotive hub outer cover are processed and service requirements.Meanwhile, this polyphenylene oxide resin alloy material oxidation-resistance that is used for automotive hub outer cover is strong, the automotive hub outer cover long service life of preparing with it.
Correspondingly, the embodiment of the present invention also provides the preparation method of the above-mentioned polyphenylene oxide resin alloy material for automotive hub outer cover.The method comprises the steps:
S01. take respectively each component according to the above-mentioned polyphenylene oxide resin alloy material for automotive hub outer cover;
S02. the described polyphenylene oxide resin taking and grafting body are carried out to mixing treatment, obtain the first mixture;
S03. the described elastomerics, polyolefine, functional agglomerate, black masterbatch, primary antioxidant and the auxiliary anti-oxidant that take are carried out to mixing treatment, obtain the second mixture;
S04. described the first mixture, the second mixture and nylon resin are added from main spout respectively, described glass fibre is added and carries out mixed melting and extrude from side spout.
Particularly, the polyphenylene oxide resin alloy material for automotive hub outer cover in above-mentioned steps S01 with and each component preferred content and kind as described above, in order to save length, do not repeat them here.
Mixing treatment in above-mentioned steps S02, S03 can be carried out according to conventional mixing method, as stirred etc., as long as each component is mixed.
In above-mentioned steps S04, the first mixture, the second mixture, nylon resin can be respectively from weightless major ingredient mouth add, glass fibre adds from side spout.Melt extrude and can adopt screw machine to melt extrude, as dual-screw-stem machine.After each material is admitted in screw machine, each material by plasticizing, melting, during this period, is had an effect between each component under the effect of high pressure and high temperature.In a preferred embodiment, these processing condition that melt extrude are: temperature is 250～300 DEG C, and vacuum tightness is 0.5～0.8MPa, and screw speed is 260～300RPM
Certainly,, after melt extruding, can also comprise tie rod, cooling, pelletizing and particle is dried etc. to treatment step.
The above-mentioned polyphenylene oxide resin alloy material preparation method for automotive hub outer cover can make each component be uniformly dispersed and act synergistically, and in realizing the above-mentioned excellent properties of polyphenylene oxide resin alloy material of the present invention, makes its stable performance.In addition, its preparation method technique is simple, and condition is easily controlled, with low cost, and feature low for equipment requirements, is suitable for suitability for industrialized production.
Be now example for polyphenylene oxide resin alloy material component concentration and the preparation method of automotive hub outer cover, the present invention is further elaborated.
Wherein, in following each embodiment, polyphenylene oxide resin is selected the product of engineering plastics company limited of Mitsubishi, nylon resin is selected Jiangsu Rui Meifu Industrial Co., Ltd., the product of China Ping Meishen horse group, elastomerics is selected the product of the Ba Ling of asset management company limited petrochemical industry branch office of SINOPEC, glass fibre is selected the product of Chongqing Polycomp International Co., Ltd, polyolefine is selected the product of Shanghai Petrochemial Co Ltd, China Petrochemical Corp, grafting body, functional agglomerate is according to method preparation above, black masterbatch is selected the product of Cabot high performance material (Tianjin) company limited, oxidation inhibitor, auxiliary antioxidant is selected the product of Shanghai Jinhaiyabao Precision Chemical Co., Ltd..
Embodiment 1
Be used for polyphenylene oxide resin alloy material of processing automobile wheel hub outer cover and preparation method thereof.Wherein, for the polyphenylene oxide resin weight ratio ingredient that alloy material comprises of processing automobile wheel hub outer cover described in below table 1.Wherein, the base material of grafting body is polyphenylene oxide resin, and grafts is citric acid; The weight of base material and grafts is 6:4, the component that functional agglomerate comprises has (weight ratio): polyphenylene oxide resin base-material 81%, C-Si key is main chain, have meso-hole structure material chirality organic inorganic hybridization mesoporous material 10%, lubricant 4%, epoxy resin 2%, inorganic filler 3%.
Its preparation method: 15 parts of polyphenylene oxide resins (PPO) and 20 parts of grafting bodies add from the first weight-loss type feeder mouth, 31.7 parts of nylon resins add from the second weightless feeder mouth, 8 parts of elastomericss, 1 part of polyolefine, 3 parts of functional agglomerates, 1 part of black masterbatch, 0.2 part of primary antioxidant and 0.1 part of auxiliary anti-oxidant add from the 3rd weightless feeder mouth after too high mixing, 20 parts of glass fibre add from side direction spout, then through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 110 DEG C of dry 2h of gas blower drying oven, and then test bars or goods are prepared in injection moulding.
Embodiment 2
Be used for polyphenylene oxide resin alloy material of processing automobile wheel hub outer cover and preparation method thereof.Wherein, for the polyphenylene oxide resin weight ratio ingredient that alloy material comprises of processing automobile wheel hub outer cover described in below table 1.Wherein, the base material of grafting body is polyphenylene oxide resin, and grafts is citric acid, and the weight ratio of base material and grafts is 6:4; The component that functional agglomerate comprises has (weight ratio): polyphenylene oxide resin base-material 81%, C-Si key is main chain, have meso-hole structure material chirality organic inorganic hybridization mesoporous material 10%, lubricant 4%, epoxy resin 2%, inorganic filler 3%.
Its preparation method: 20 parts of polyphenylene oxide resins (PPO) and 15 parts of grafting bodies add from the first weight-loss type feeder mouth, 31.7 parts of nylon resins add from the second weightless feeder mouth, 8 parts of elastomericss, 1 part of polyolefine, 3 parts of functional agglomerates, 1 part of black masterbatch, 0.2 part of primary antioxidant and 0.1 part of auxiliary anti-oxidant add from the 3rd weightless feeder mouth after too high mixing, 20 parts of glass fibre add from side direction spout, then through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 110 DEG C of dry 2h of gas blower drying oven, and then test bars or goods are prepared in injection moulding.
Embodiment 3
Be used for polyphenylene oxide resin alloy material of processing automobile wheel hub outer cover and preparation method thereof.Wherein, for the polyphenylene oxide resin weight ratio ingredient that alloy material comprises of processing automobile wheel hub outer cover described in below table 1.Wherein, the base material of grafting body is polyphenylene oxide resin, and grafts is citric acid, and the weight of base material and grafts is 6:4; The component that functional agglomerate comprises has (weight ratio): polyphenylene oxide resin base-material 81%, C-Si key is main chain, have meso-hole structure material chirality organic inorganic hybridization mesoporous material 10%, lubricant 4%, epoxy resin 2%, inorganic filler 3%.
Its preparation method: 25 parts of polyphenylene oxide resins (PPO) and 10 parts of grafting bodies add from the first weight-loss type feeder mouth, 31.7 parts of nylon resins add from the second weightless feeder mouth, 8 parts of elastomericss, 1 part of polyolefine, 3 parts of functional agglomerates, 1 part of black masterbatch, 0.2 part of primary antioxidant and 0.1 part of auxiliary anti-oxidant add from the 3rd weightless feeder mouth after too high mixing, 20 parts of glass fibre add from side direction spout, then through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 110 DEG C of dry 2h of gas blower drying oven, and then test bars or goods are prepared in injection moulding.
Embodiment 4
Be used for polyphenylene oxide resin alloy material of processing automobile wheel hub outer cover and preparation method thereof.Wherein, for the polyphenylene oxide resin weight ratio ingredient that alloy material comprises of processing automobile wheel hub outer cover described in below table 1.Wherein, the base material of grafting body is polyphenylene oxide resin, and grafts is citric acid, and the weight of base material and grafts is 6:4; The component that functional agglomerate comprises has (weight ratio): polyphenylene oxide resin base-material 81%, C-Si key is main chain, have meso-hole structure material chirality organic inorganic hybridization mesoporous material 10%, lubricant 4%, epoxy resin 2%, inorganic filler 3%.
Its preparation method: 30 parts of polyphenylene oxide resins (PPO) and 5 parts of grafting bodies add from the first weight-loss type feeder mouth, 31.7 parts of nylon resins add from the second weightless feeder mouth, 8 parts of elastomericss, 1 part of polyolefine, 3 parts of functional agglomerates, 1 part of black masterbatch, 0.2 part of primary antioxidant and 0.1 part of auxiliary anti-oxidant add from the 3rd weightless feeder mouth after too high mixing, 20 parts of glass fibre add from side direction spout, then through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 110 DEG C of dry 2h of gas blower drying oven, and then test bars or goods are prepared in injection moulding.
Comparative example 1
A kind of polyphenylene oxide resin alloy material and preparation method thereof.Wherein, polyphenylene oxide resin weight ratio ingredient that alloy material comprises is described in below table 1.
Its preparation method: 35 parts of polyphenylene oxide resins (PPO) are added from the first weight-loss type feeder mouth, 34.7 parts of nylon resins add from the second weightless feeder mouth, 8 parts of elastomericss, 1 part of polyolefine, 1 part of black masterbatch, 0.2 part of primary antioxidant and 0.1 part of auxiliary anti-oxidant add from the 3rd weightless feeder mouth after too high mixing, 20 parts of glass fibre add from side direction spout, then through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 110 DEG C of dry 2h of gas blower drying oven, and then test bars or goods are prepared in injection moulding.
Performance test:
The prepared polyphenylene oxide resin alloy material of polyphenylene oxide resin alloy material for processing automobile wheel hub outer cover prepared by above-described embodiment 1 to embodiment 4 and comparison example 1 carries out respectively the performance test as table 2.Correlated performance testing method is as follows:
(1) tensile strength: described tensile strength is pressed ASTM D-638 test.
(2) flexural strength: described flexural strength is pressed ASTM D-790 test.
(3) modulus in flexure: described flexural strength is pressed ASTM D-790 test.
(4) Izod notch shock: described Izod notch shock is pressed ASTM D-256 test.
(5) heat-drawn wire: described heat-drawn wire is hit by ASTM D-648 and tested.
(6) mobility: certain thickness spiral of Archimedes cavity plate is carried out to the injection moulding test of produced polyphenylene oxide resin alloy material.Injection moulding wall thickness is 2mm, and width is 5mm, and injection temperature is 270～300 DEG C, and injection pressure is 90～110MPa, and be 10s cooling time, and dwell pressure is 60～90MPa, and the dwell time is 5～10s.
(7) organic solvent immersion test: the goods of injection formed are immersed in toluene and xylene solution, splashes into a small amount of methyl red solution, seals and soaks 24 hours, takes out goods and observes, and repeats 3 times, and whether observe goods has cracking phenomena.
(8) hundred lattice experiments: the goods of injection formed, after on-line spray, are dried, after 24 hours, take out goods, be cooled to room temperature, allow the rear sub-box that marks 5mm × 5mm with guarded blade utility knife on product surface, with adhesive tape sticking on surface, after cementing, tear rapidly adhesive tape off, see that whether paint after spraying is by adhesive tape stick-down, if there is no stick-down, be considered as hundred lattice stand the tests, vice versa.
After tested, above-described embodiment 1 to embodiment 4 and comparison example 1 material correlated performance are in table 2.
The raw material weight umber proportioning of table 1: embodiment 1～4, comparative example 1
Table 2:
As shown in Table 2, compare with the comparative example 1 that does not contain grafting body and functional agglomerate, the anti-fragility of polyphenylene oxide resin alloy material for automotive hub outer cover of embodiment 1 to 4 preparation is strong, when good fluidity, solvent resistance, and other mechanical property excellences.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. for a polyphenylene oxide resin alloy material for automotive hub outer cover, comprise the component of following weight part:
2. polyphenylene oxide resin alloy material according to claim 1, is characterized in that: taking described functional agglomerate gross weight as 100%, described functional agglomerate comprises following formula composition:
Described resin matrix is at least one in polyphenylene oxide resin, nylon resin, ethylene-butene copolymer.
3. polyphenylene oxide resin alloy material according to claim 2, is characterized in that: described chirality organic inorganic hybridization mesoporous material is taking C-Si key as main chain, has chiral structure, has meso-hole structure material; And/or
Described lubricant is at least one in paraffin class, lipid acid and ester class thereof, fatty acid amide, silicoorganic compound; And/or
Described epoxy resin is at least one in bisphenol A type epoxy resin, phenol aldehyde type epoxy resin; And/or
Described inorganic filler is at least one in mesoporous silicon oxide, mesoporous TiO 2, nano imvite, superfine talcum powder.
4. according to the polyphenylene oxide resin alloy material described in claim 2 or 3, it is characterized in that: described functional agglomerate is to be prepared as follows acquisition:
Described resin binder, chirality organic inorganic hybridization mesoporous material, lubricant, epoxy resin, inorganic filler are carried out after mixing treatment, under 200～280 DEG C of conditions, melt extrude, wherein, melt extruding screw speed in process is 260～300RPM, and vacuum tightness is 0.5～0.8MPa.
5. polyphenylene oxide resin alloy material according to claim 1, it is characterized in that: described grafting body is taking at least one in polyphenylene oxide resin, nylon resin, ethylene-butene copolymer as base material, taking at least one in MALEIC ANHYDRIDE, benzoyl oxide, Tetra hydro Phthalic anhydride, diacetyl oxide, propionic anhydride, itaconic anhydride, citric acid as grafts.
6. polyphenylene oxide resin alloy material according to claim 1, is characterized in that: described polyphenylene oxide resin is the polymkeric substance, 2 of 2,6-xylenol, the multipolymer of 6-xylenol and 2,3,6-TMP, and its limiting viscosity is 0.2-0.6dl/g.
7. polyphenylene oxide resin alloy material according to claim 1, is characterized in that: described nylon resin is the mixture of a kind of in nylon 6 or nylon 66 or two kinds.
8. polyphenylene oxide resin alloy material according to claim 1, is characterized in that: described elastomerics is at least one in polyhutadiene, chloroprene rubber, polyisoprene rubber, using trans-polyisoprene, styrene-butadiene rubber(SBR), HSBR, hydrogenation nitrile rubber, ethylene-propylene rubber(EPR), ethylene copolymer.
9. polyphenylene oxide resin alloy material according to claim 1, is characterized in that: described polyolefine is at least one in polyethylene, polypropylene, poly 1-butene, poly(4-methyl-1-pentene), ethylene-propylene copolymer, ethylene-butene copolymer.
10. for a preparation method for the polyphenylene oxide resin alloy material of automotive hub outer cover, comprise the following steps:
Take respectively each component according to the polyphenylene oxide resin alloy material described in claim 1～9 any one;
The described polyphenylene oxide resin taking and grafting body are carried out to mixing treatment, obtain the first mixture;
The described elastomerics, polyolefine, functional agglomerate, black masterbatch, primary antioxidant and the auxiliary anti-oxidant that take are carried out to mixing treatment, obtain the second mixture;
Described the first mixture, the second mixture and nylon resin are added from main spout respectively, described glass fibre is added and carries out mixed melting and extrude from side spout.
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