CN106867244A - A kind of heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite material and preparation method - Google Patents

Abstract

The invention discloses a kind of nylon composite materials, it is made up of the component of following weight portion：100 parts, carbon fiber 5-95 parts, fire retardant 5-55 parts, auxiliary flame retardant 1-19 parts, expanded graphite 1-19 parts, heat filling 5-35 parts, antioxidant 0.1-3.5 parts, lubricant 0.1-3.5 parts of high-temperature nylon resin.The invention also discloses the preparation method of the nylon composite materials.The present invention utilizes parallel dual-screw extruding machine, makes the lamella of insertion expanded graphite under high-temperature nylon resin, expanded graphite that the dispersion of nanoscale lamella is formed in high-temperature nylon resin under the collective effect of Strong shear and high temperature；The lamellar structure of expanded graphite and the fiber acicular texture of heat filling are mutually cooperatively configured the network of interconnection, the network is interconnected with the carbon fiber through composite, preferably conductive, thermal conducting path is formed, preferable conductive, heat-conducting effect is played.

Description

A kind of heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite material and preparation method

Technical field

The present invention relates to technical field of polymer materials, more particularly to a kind of heat conduction antistatic environmental protection flame retardant high temperature resistant nylon is combinedMaterial and preparation method.

Background technology

Nylon resin is excellent performance, widely used industrial chemicals, due to nontoxic, light weight, wear-resisting, corrosion-resistant and machineThe characteristic such as tool performance is good, therefore, it is widely used in the industrial circles such as machinery, automobile, chemical industry, instrument.Nylon resin hasSheet resistance very high, in use because friction is easy in surface stored charge, causes static discharge, produce electric spark andCause fire.People generally improve the electrical property and heat conductivility of polymer by adding the method for conductive filler, but,Assigning the preferable electric conductivity of nylon resin and heat conductivility needs to fill substantial amounts of conductive filler, can cause the shaping of compositeThe significantly decline of processing characteristics and mechanical property.In recent years, the antistatic and Heat Conduction Problems of nylon resin how to be solved in high scoreSub- field of compound material causes highest attention.With the development of industrial technology, to the resistance to elevated temperatures requirement more and more higher of material；In order to meet needs, material needs not only light but also heatproof, possesses the performance such as high intensity, dimensionally stable, fire-retardant.High temperature resistant nylon intoIt is one of comparatively ideal material.The development of high temperature resistant nylon makes it possible the miniaturization of products, lightweight and powerful.It is resistance toHigh-temperature nylon can bring heat resistance higher for some parts, or simply instead of metal material to produce these parts.

Carbon fiber has the advantages that high specific strength, high ratio modulus, high temperature resistant, conductive heat transfer and thermal coefficient of expansion are small.Therefore,Conductive, heat conduction and enhanced effect can be simultaneously played by addition carbon fiber in high-temperature nylon resin.But, using carbonWhen fiber is as conductive filler, need to such as make polymer that there is preferable electric conductivity must make to be connected with each other between carbon fiber, formation is ledElectric pathway.So, the addition of carbon fiber is larger, can increase substantially cost.

The content of the invention

There is a problem of that antistatic property, electric conductivity and resistance to elevated temperatures are poor for existing nylon resin, the purpose of the present invention isA kind of heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite material is provided.

It is a further object to provide a kind of preparation side of the heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite materialMethod.

To achieve the above object, the present invention uses following technical scheme：

A kind of heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite material, is made up of the component of following weight portion：High-temperature nylon tree100 parts of fat, carbon fiber 5-95 parts, fire retardant 5-55 parts, auxiliary flame retardant 1-19 parts, expanded graphite 1-19 parts, heat conduction fills out5-35 parts, antioxidant 0.1-3.5 parts, lubricant 0.1-3.5 parts of material.

The heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite material is made up of the component of following weight portion：High-temperature nylon resin100 parts, carbon fiber 50-90 parts, fire retardant 15-45 parts, auxiliary flame retardant 5-15 parts, expanded graphite 5-15 parts, heat conduction fills out10-30 parts, antioxidant 0.3-1.3 parts, lubricant 0.3-0.7 parts of material.

The high-temperature nylon resin is in PA6T, PA9T, PA10T, PA12T, PA13T, PA46, PA4T, PPAIt is at least one；It is preferred that at least one in PA6T, PA10T, PA46.

The fire retardant is at least one in brominated Polystyrene, diethyl hypo-aluminum orthophosphate, Melamine Polyphosphate.

The auxiliary flame retardant is at least one in Firebrake ZB, antimony oxide, sodium antimonate.

The heat filling is the heat filling by pre-processing；Further, the heat filling by pretreatment is by pre-The alumina whisker for the treatment of, potassium titanate crystal whisker, calcium carbonate crystal whisker, aluminium borate whisker, ZnOw, magnesium sulfate crystal whisker, seaAt least one in afrodite whisker, xonotlite fiber；Preferably through calcium carbonate crystal whisker, ZnOw, the oxidation of pretreatmentAt least one in al whisker.

The processing method of the heat filling by pretreatment is comprised the following steps：Heat filling is mixed with water, SnCl is added₄,Regulation pH value is alkalescence, is reacted under heating condition, filtering after reaction completely, dry, calcining, then will calcineHeat filling is sufficiently cool, adds coupling agent to be sufficiently mixed, and obtains the heat filling by pretreatment.

The heat filling, water and SnCl₄Mass ratio be 10:30:2.

The regulation pH value is 9.

The pH adjusting agent that the regulation pH value is used is for concentration for the potassium hydroxide or concentration of 0.05mol/L are 0.05mol/LAmmoniacal liquor.

The temperature of the heating is 60~80 DEG C, and the time of reaction is 30~60min.

The temperature of the calcining is 600~700 DEG C, and the time of calcining is 2~5h.

The coupling agent is KH550 coupling agents.

It is 0.1~1%, preferably 0.5% that the addition of the coupling agent accounts for thermal conductivity filler quality percentage.

The antioxidant is at least one in phenols or phosphite ester kind antioxidant.

The antioxidant be antioxidant 1098 (N, N'- double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine) orAt least one in antioxidant S-9228 (double (2,4 one di-t-butyl) season tetrol diphosphites).

The lubricant is at least one in fatty acid salt, fatty acyl amide or lignite wax.

The lubricant is pentaerythritol stearate.

A kind of preparation method of the heat conduction antistatic environmental protection flame retardant high temperature resistant nylon composite material, comprises the following steps：By drying100 parts of high-temperature nylon resins, 5-55 parts of fire retardant, 1-19 parts of auxiliary flame retardant, 1-19 parts of expanded graphite, 5-35 parts of processThe heat filling of pretreatment, 0.1-3.5 parts of antioxidant and 0.1-3.5 parts of lubricant are sufficiently mixed, and after mixing completely, are counted by precisionThe feed device of amount, by material feeding parallel dual-screw extruding machine, 5-95 parts of carbon fiber passes through the side feeding feeding of delicate meteringDevice enters double screw extruder, is sufficiently fused under mixed material and fine shearing, mixing and the conveying in twin-screw of carbon, finallyThe nylon composite materials are obtained by after extrusion, tie rod, cooling, being made pellet.

The double screw extruder temperature setting is 270-340 DEG C, preferably 295-325 DEG C.

There is advantages below and beneficial effect due to using above-mentioned technical proposal, the present invention：

The present invention utilizes parallel dual-screw extruding machine, makes to insert swollen under high-temperature nylon resin under the collective effect of Strong shear and high temperatureThe lamella of swollen graphite, expanded graphite forms the dispersion of nanoscale lamella in high-temperature nylon resin；The lamellar structure of expanded graphite and leadThe fiber acicular texture of hot filler is mutually cooperatively configured the network of interconnection, the network with through compositeCarbon fiber is interconnected, and forms preferably conductive, thermal conducting path, preferable conductive, heat-conducting effect is played, while reducing carbonThe consumption of fiber, and through carbon fiber filling enhancing after, the heat distortion temperature of composite is greatly promoted, while fire retardant and auxiliaryThe auxiliary flame retardant flame retardant effect good for composite is provided.

Specific embodiment

With reference to embodiment, the present invention is further detailed explanation.

In the case of being clear to the purpose of the present invention by following examples, being explained, the component of the composition is with weightAmount part is released bright for the universal standard.In the case of without special instruction, for simplicity, " part " described in the embodiment of the present inventionThere is identical meaning with weight portion.

In the citing that 1-8 by the following examples is further clear to the present invention, heat filling in the embodiment of the present inventionProcessing method is：

Heat filling is mixed with water, SnCl is added₄, regulation pH value is 9, and 45min is reacted at 70 DEG C；Dried after filtering,Then calcine 3.5 hours at 650 DEG C, then by the good heat filling of above-mentioned calcining it is sufficiently cool after, mixed at high speed, addition is accounted for and ledHot packing quality percentage is that 0.5% KH550 coupling agents are sufficiently mixed, and obtains final product the heat filling by pretreatment.Wherein heat filling, water and SnCl₄Quality proportioning be 10:30:2, described pH adjusting agent is the potassium hydroxide of 0.05mol/LOr the ammoniacal liquor of 0.05mol/L.

In the citing that 1-8 by the following examples is further clear to the present invention, heat conduction antistatic ring in the embodiment of the present inventionThe preparation method of environment friendly flame-retardant high temperature resistant nylon composite material is：

By dry high-temperature nylon resin, fire retardant, auxiliary flame retardant, expanded graphite, the heat filling, anti-by pre-processingOxygen agent and lubricant proportionally accurate weighing, are subsequently adding in homogenizer and are sufficiently mixed uniform, after mixing completely, pass throughThe feed device of delicate metering, by material feeding parallel dual-screw extruding machine, carbon fiber passes through the side feeding feeding of delicate meteringDevice enters parallel dual-screw extruding machine, is sufficiently fused under material and fine shearing, mixing and the conveying in screw rod of carbon, most passes through afterwardsAfter crossing extrusion, tie rod, cooling, pellet is made, wherein double screw extruder temperature setting is 270-340 DEG C, preferably 295-325 DEG C.

The formula of embodiment 1-8 as shown in table 1, is parts by weight.

Table 1

Calcium carbonate crystal whisker used, alumina whisker and ZnOw are treated whisker in table 1.

The performance test results of embodiment 1-8 products obtained therefroms are as shown in table 2.

Table 2

From Table 2, it can be seen that comparative example is compared with embodiment, the heat filling and expanded graphite of embodiment are substituted for comparative exampleThe carbon fiber of moderate, remaining component is identical, and by test, test result shows that the resistivity of embodiment product is obviousDecline, thermal conductivity factor substantially rises, illustrate that the lamellar structure and the fiber acicular texture of heat filling of Graphene really can be mutualIt is cooperatively configured the network of interconnection so that product has preferably conductive, heat conductivility, while the fire resistance of productStabilization is kept, FV-0 is reached, changes additional proportion of species, heat filling and expanded graphite of high-temperature nylon resin etc., productProperties change therewith, but can prepare with the preferably conductive, flame retardant products of heat conductivility.

The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.It is familiar withThe personnel of art technology obviously can easily make various modifications to these embodiments, and should General Principle described hereinUse in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, this area skillArt personnel announcement of the invention, does not depart from improvement that scope made and modification all should be in protection model of the inventionWithin enclosing.

Claims (10)

1. a kind of nylon composite materials, it is characterised in that：It is made up of the component of following weight portion：100 parts of high-temperature nylon resin,Carbon fiber 5-95 parts, fire retardant 5-55 parts, auxiliary flame retardant 1-19 parts, expanded graphite 1-19 parts, heat filling 5-35 parts,Antioxidant 0.1-3.5 parts, lubricant 0.1-3.5 parts.

2. nylon composite materials according to claim 1, it is characterised in that：The nylon composite materials are by following weight portionComponent be made：100 parts of high-temperature nylon resin, carbon fiber 50-90 parts, fire retardant 15-45 parts, auxiliary flame retardant 5-15 parts,Expanded graphite 5-15 parts, heat filling 10-30 parts, antioxidant 0.3-1.3 parts, lubricant 0.3-0.7 parts.

3. nylon composite materials according to claim 1 and 2, it is characterised in that：The high-temperature nylon resin be PA6T,At least one in PA9T, PA10T, PA12T, PA13T, PA46, PA4T, PPA；It is preferred that PA6T, PA10T,At least one in PA46.

4. nylon composite materials according to claim 1 and 2, it is characterised in that：The fire retardant be brominated Polystyrene,At least one in diethyl hypo-aluminum orthophosphate, Melamine Polyphosphate；

Preferably, the auxiliary flame retardant is at least one in Firebrake ZB, antimony oxide, sodium antimonate.

5. nylon composite materials according to claim 1 and 2, it is characterised in that：The heat filling is by pretreatmentHeat filling；Further, it is described by pretreatment heat filling be through pretreatment alumina whisker, potassium titanate crystal whisker,In calcium carbonate crystal whisker, aluminium borate whisker, ZnOw, magnesium sulfate crystal whisker, sepiolite whisker, xonotlite fiber at leastIt is a kind of；Preferably through at least one in calcium carbonate crystal whisker, ZnOw, the alumina whisker of pretreatment；

Preferably, the processing method of the heat filling by pretreatment is comprised the following steps：Heat filling is mixed with water,Add SnCl₄, regulation pH value is alkaline, is reacted under heating condition, filtering, dry, calcining after reaction completely, thenThe heat filling that will have been calcined is sufficiently cool, adds coupling agent to be sufficiently mixed, and obtains the heat filling by pretreatment.

6. nylon composite materials according to claim 5, it is characterised in that：The heat filling, water and SnCl₄MatterAmount is than being 10:30:2；

Preferably, the regulation pH value is 9；

Preferably, the pH adjusting agent that the regulation pH value is used is for concentration for the potassium hydroxide or concentration of 0.05mol/L areThe ammoniacal liquor of 0.05mol/L；

Preferably, the temperature of the heating is 60~80 DEG C, and the time of reaction is 30~60min；

Preferably, the temperature of the calcining is 600~700 DEG C, and the time of calcining is 2~5h；

Preferably, the coupling agent is KH550 coupling agents；

Preferably, it is 0.1~1%, preferably 0.5% that the addition of the coupling agent accounts for thermal conductivity filler quality percentage.

7. nylon composite materials according to claim 1 and 2, it is characterised in that：The antioxidant is phenols or phosphorous acidAt least one in esters antioxidant；

Preferably, the lubricant is at least one in fatty acid salt, fatty acyl amide or lignite wax.

8. nylon composite materials according to claim 7, it is characterised in that：The antioxidant is antioxidant 1098 or anti-At least one in oxygen agent S-9228；

Preferably, the lubricant is pentaerythritol stearate.

9. the preparation method of any described nylon composite materials of a kind of claim 1 to 8, it is characterised in that：Including following stepSuddenly：By dry 100 parts of high-temperature nylon resins, 5-55 parts of fire retardant, 1-19 parts of auxiliary flame retardant, 1-19 parts of expanded graphite,5-35 parts is sufficiently mixed by heat filling, 0.1-3.5 parts of antioxidant and the 0.1-3.5 parts of lubricant for pre-processing, after mixing completely,By the feed device of delicate metering, by material feeding double screw extruder, 5-95 parts of carbon fiber is fed by the side of delicate meteringFeed device enters parallel dual-screw extruding machine, under mixed material and fine shearing, mixing and the conveying in twin-screw of carbon sufficientlyFusion, after eventually passing extrusion, tie rod, cooling, is made pellet and obtains the nylon composite materials.

10. the preparation method of nylon composite materials according to claim 9, it is characterised in that：The double screw extruderTemperature setting is 270-340 DEG C, preferably 295-325 DEG C.