CN104448806A - Low-warping-rate halogen-free flame retardant carbon fiber-reinforced nylon alloy material and preparation method - Google Patents

Low-warping-rate halogen-free flame retardant carbon fiber-reinforced nylon alloy material and preparation method Download PDF

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Publication number
CN104448806A
CN104448806A CN201410827638.2A CN201410827638A CN104448806A CN 104448806 A CN104448806 A CN 104448806A CN 201410827638 A CN201410827638 A CN 201410827638A CN 104448806 A CN104448806 A CN 104448806A
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carbon fiber
halogen
reinforced nylon
fiber reinforced
low warpage
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郝建鑫
郝源增
邓爵安
任萍
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GUANGZHOU SUPER-DRAGON ENGINEERING PLASTIC Co Ltd
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GUANGZHOU SUPER-DRAGON ENGINEERING PLASTIC Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92561Time, e.g. start, termination, duration or interruption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention belongs to the technical field of a carbon fiber-reinforced nylon material, discloses a low-warping-rate halogen-free flame retardant carbon fiber-reinforced nylon alloy material and a preparation method as well as application thereof to the fields such as electronic and electric appliances, transportation and electric tools, and is particularly applicable to some thin-walled electronic devices and electric tools with higher material mechanical performance requirement. The material comprises the following components in percentage by mass: 32.5-57.7 percent of nylon, 5-15 percent of acrylonitrile-butadiene-styrene (ABS) plastic, 5-25 percent of carbon fiber, 5-25 percent of glass fiber, 5-12 percent of halogen-free flame retardant, 1-5 percent of flame retardant synergist, 0-5 percent of compatibilizer and 0.1-0.3 percent of other assistants. PA/ABS (Polyamide) is used as an alloy substrate, and the glass fiber and the carbon fiber are compounded and enhanced to obtain superior mechanical performance, reduce density, improve fluidity, reduce internal stress and reduce the warping rate of a thin-wall product.

Description

The halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate and preparation method
Technical field
The invention belongs to carbon fiber reinforced nylon field of material technology, in particular to a kind of halogen-free flameproof carbon fiber reinforced nylon alloy material and preparation method thereof of low warpage rate and the application in the fields such as electronic apparatus, aerospace, communications and transportation, power tool, be specially adapted to some thin-walleds and to the higher electron device of material mechanical performance requirement and power tool.
Background technology
Tynex is commonly called as nylon (Nylon), density 1.15g/cm 3, be on molecular backbone chain containing recurring amide radical group-[NHCO]-thermoplastic resin general name, carrying out classifying according to polymer backbone conformation mainly comprises amorphous nylon and aromatic nylon two class.Because it has wear-resisting, oil resistant, self-lubricating, many premium propertiess such as shock-resistant, nylon material is widely used in the industries such as machinery, automobile, instrument.High polar amide groups in fatty polyamide molecular structure and long flexible aliphatic segment make this kind of material have the shortcomings such as water-absorbent is high, contractibility is large simultaneously, especially glass or carbon fiber reinforced nylon material easily produce shrink of product and warpage when doing thin-gage goods, have a strong impact on the practical application of this kind of material.In addition, the application of nylon material in fields such as electronic apparatuss needs material to use under long term high temperature environment usually, and often can touch electrical spark.How improving use temperature and the halogen-free flameproof performance of nylon material, is a kind of important research topic in polyamide material modification field equally.
Carbon fiber is the tencel material of a kind of carbon content more than 95%, it is with organic fibre, as acrylics filament (PAN), pitch and viscose fiber etc. do raw material, the micro crystal graphite filamentary material obtained after high-temperature calcination greying in rare gas element.Because carbon fiber has in physicals, proportion is little, intensity is large, modulus is high, linear expansivity is little, electroconductibility is strong, thermal conductivity high, in the enhancing that this kind of material has been widely used in thermoplasticity and thermosetting resin and functional modification.Carbon fiber is utilized to carry out its physical and mechanical property of thermoplastics of modification and thermotolerance has great raising, as PA66 material add the carbon fiber of 20% after material tensile strength improve nearly 3 times, modulus in flexure improves nearly 4 times, and heat-drawn wire is increased to 250 DEG C.By the optimization to surface treatment of carbon fibers mode and complex machining process, improving the use properties of carbon fiber modifying nylon material, will be an important research direction of following Reinforced Nylon development.
Nylon alloy technology is based on nylon resin, and the polymer multicomponent system of other polymer materials of blending, this modification technology can significantly improve the use properties of nylon material.Nylon alloy technology is the important channel of nylon high performance, multifunction, and has the advantage that the process-cycle is short, equipment is simple, cost is low.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is the halogen-free flameproof carbon fiber reinforced nylon alloy material providing a kind of low warpage rate, and this material has the features such as high strength, high heat resisting temperature, high flame retardant grade, high workability, low density, low warpage rate.The present invention, by utilizing the mobility adding raising resin base material on the one hand of the second resin base material, reduces the internal stress of moulded products; Reduce the overall degree of crystallinity of resin base material in addition on the one hand, reduce molding shrinkage and the warpage rate of moulded products, exploitation obtains the carbon fiber reinforced nylon matrix material with low warpage rate, this matrix material is applicable to prepare the higher thin-gage goods of lightweight requirements by injection moulding, can be applicable to the field such as electronic apparatus and power tool.
Another object of the present invention is the preparation method of the halogen-free flameproof carbon fiber reinforced nylon alloy material providing a kind of above-mentioned low warpage rate.
Still a further object of the present invention is the application of halogen-free flameproof carbon fiber reinforced nylon alloy material in the fields such as electronic apparatus, aerospace, communications and transportation, power tool providing above-mentioned low warpage rate, be particularly useful for making some thin-walleds and to the higher electron device of material mechanical performance requirement and power tool, as notebook computer, phone housing, electrical condenser etc., the thin-gage goods utilizing alloy material of the present invention to prepare has the features such as intensity is high, flame retardant properties good, warpage rate is low.
Object of the present invention is realized by following proposal:
A halogen-free flameproof carbon fiber reinforced nylon alloy material for low warpage rate, comprises the component of following mass percent:
Nylon selected by the present invention is preferably the low sticky nylon that viscosity is 2.0 ~ 2.8Pa.S, as low sticky nylon 6 (PA6), nylon66 fiber (PA66), nylon 46 (PA46), Nylon 1012 (PA1012) etc., be wherein more preferably low sticky nylon 6 (PA6).
In order to realize the present invention better further, in alloy material of the present invention, the content of described nylon is more preferably 40 ~ 50wt%.
Acrylonitrile-butadiene-styrene (ABS) plastics (ABS) selected by the present invention are preferably the ABS of mass polymer method synthesis, and the specific product trade mark comprises: Shanghai Gaoqiao petrochemical industry ABS8391, DOW Chemical ABS 3504 etc.
In order to realize the present invention better further, in alloy material of the present invention, the content of described acrylonitrile-butadiene-styrene (ABS) plastics (ABS) is more preferably 8 ~ 10wt%.
The alloy material of the nylon (PA) selected by the present invention and acrylonitrile-butadiene-styrene (ABS) plastics (ABS), the consumption of acrylonitrile-butadiene-styrene (ABS) plastics (ABS) is 10 ~ 40wt% of nylon (PA) quality, is preferably 20 ~ 30wt%.
Carbon fiber selected by the present invention is preferably the carbon fiber of polyacrylonitrile base material, filament diameter 4 ~ 8 μm, synnema linear density 200 ~ 800tex, and the carbon fiber that the present invention uses has the feature of high strength.
In order to realize the present invention better further, in alloy material of the present invention, the content of described carbon fiber is more preferably 10wt%.
It is 3 ~ 10 μm that glass fibre selected by the present invention is preferably filament diameter, and filament length is the alkali-free short glass fiber of 300 ~ 500mm.
In order to realize the present invention better further, in alloy material of the present invention, the content of described glass fibre is more preferably 15wt%.
In order to realize the present invention better further, the reinforcement selected by the present invention is the compound system of carbon fiber and glass fibre, and in alloy material of the present invention, wherein the total content of glass fibre and carbon fiber is preferably 25wt%.
In order to realize the present invention better further, the composite strengthening system of the glass fibre selected by the present invention and carbon fiber, wherein the mass ratio of glass fibre and carbon fiber is preferably 3:2.
Halogen-free flame retardants selected by the present invention is preferably the expansion type flame retardant of triazines, specifically comprises the acid of cyanogen urea and derivative, melamine phosphate, guanidinesalt and Dyhard RU 100 salt etc., is preferably melamine phosphate.
Fire retarding synergist selected by the present invention is preferably antimonous oxide (Sb 2o 3).
The present invention selects halogen-free flame retardants and fire retarding synergist composition flame-retardant system, thus realizes excellent flame retardant effect, and in order to realize the present invention better further, the mass ratio of halogen-free flame retardants used and fire retarding synergist is 5:1 ~ 2:1, is more preferably 3:1.
Compatilizer selected by the present invention is preferably maleic anhydride class grafts, comprise acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH), polypropylene grafted maleic anhydride (PP-g-MAH), Research of Grafting Malaic Anhydride Onto Polyethylene (PE-g-MAH) and styrene-acrylonitrile-copolymer-maleic anhydride (SAM) etc., be wherein more preferably acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH).
The addition of the compatilizer selected by the present invention is optimized according to the difference of acrylonitrile-butadiene-styrene (ABS) plastics (ABS) content, is more preferably compatilizer acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) adding 4wt%.
Other auxiliary agents selected by the present invention refer to the auxiliary agent such as processing stabilizers and oxidation inhibitor being suitable for arbitrarily nylon and ABS system in this area, can be phosphinate compounds, as: 3,9-bis-(2,4-dicumyl phenoxy group)-2,4,8,10-tetra-oxa--3,9-bis-phospha spiral shell [5.5] undecane (S9228), three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (168) etc., wherein be preferably three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (168).
Present invention also offers a kind of preparation method of halogen-free flameproof carbon fiber reinforced nylon alloy material of above-mentioned low warpage rate, specifically comprise the following steps:
Nylon (PA) 32.5 ~ 57.7wt%, acrylonitrile-butadiene-styrene (ABS) plastics (ABS) 5 ~ 15wt%, halogen-free flame retardants 5 ~ 12wt%, fire retarding synergist 1 ~ 5wt%, compatilizer 0 ~ 5wt% and other auxiliary agents 0.1 ~ 0.3wt% mixing is added by twin-screw extrusion owner spout, carbon fiber (CF) 5 ~ 25wt% is added by the exclusion mouth of twin screw extruder, glass fibre (GF) 5 ~ 25wt% is added by the side spout of twin screw extruder, melt blending, cooling granulation, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate.
Mixing of the present invention preferably mixes in homogenizer, and mixing temperature is not higher than 80 DEG C, and stirring velocity is 300r/min, and mixing time is 10 ~ 30min.
The condition optimization of melt blending of the present invention be the temperature of each heating zone between 230 ~ 260 DEG C, the screw speed of main frame is 350 ~ 430r/min, and the rotating speed of hopper feed screw rod is 24 ~ 35r/min.
The halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate of the present invention has the features such as intensity is high, flame retardant properties good, warpage rate is low, its physical and mechanical property, processing characteristics and appearance performance are all good, relative common carbon fibers Reinforced Nylon material has higher resistance to warping, can be applicable in the fields such as electronic apparatus, aerospace, communications and transportation, power tool, be particularly useful for making some thin-walleds and to the higher electron device of material mechanical performance requirement and power tool, as notebook computer, phone housing, electrical condenser etc.
Mechanism of the present invention is:
The present invention selects nylon (PA) and acrylonitrile-butadiene-styrene (ABS) plastics (ABS) as polymeric substrate, acrylonitrile-butadiene-styrene (ABS) plastics (ABS) are utilized to be amorphous material, have that molding shrinkage is low, good fluidity, shock strength high, nylon (PA) and acrylonitrile-butadiene-styrene (ABS) plastics (ABS) make by the mode of melt blending the mobility that alloy material can improve material, reduce the molecular chain orientation in moulding process, reduce the internal stress of material, reduce the warpage rate of thin-gage goods.Carbon fiber and glass fibre compound system are as composite enhancing system, utilize carbon fiber to have higher intensity, density is less and less than glass fibre on the impact of forming materials shrinking percentage, and glass fibre has low cost, high tensile, affects the features such as little to resistivity of material, select glass fibre and the composite enhancing of carbon fiber, and when preferably both composite total mass hundred parts of content are 25%, the mechanical property of material can reach best; The alloy material prepared has excellent physical and mechanical property, and has lower molding shrinkage and warpage rate, obviously reduces the density of material, can be applied to the thin wall parts that preparation is high to product lightweight requirements.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention utilizes PA/ABS as alloy substrate, has good mechanical property, improves the mobility of material, reduces the molecular chain orientation in moulding process, reduces the internal stress of material, reduces the warpage rate of thin-gage goods.
(2) the present invention utilizes glass fibre and the composite enhancing of carbon fiber, while reaching best mechanical property, reduces density of material, reduces the warpage rate of goods.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 41.8wt%, ABS8391A 13wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 2: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 49.8wt%, ABS8391A 5wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 3: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 45.8wt%, ABS8391A 9wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 4: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 45.8wt%, ABS8391A 9wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 5: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 45.8wt%, ABS8391A 9wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 5wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 20wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 6: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 49.8wt%, ABS8391A 10wt% (Shanghai Gaoqiao petrochemical industry), halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 5wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS 3014B) 20wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 7: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 44.8wt%, ABS8391A 9wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 5wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 8: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 40.8wt%, ABS8391A 9wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 25wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 5wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Embodiment 9: the preparation of the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate
By PA6M2400 (Yueyang petrochemical industry) 52.8wt%, ABS8391A 11wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 5wt% (melamine phosphate), fire retarding synergist Sb 2o 32wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Comparative example 1
By PA6M2400 (Yueyang petrochemical industry) 45.8wt%, ABS8391A 9wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, short glass fiber (ECS 3014B) 25wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain nylon alloy material, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Comparative example 2
By PA6M2400 (Yueyang petrochemical industry) 61.8wt%, ABS8391A 18wt% (Shanghai Gaoqiao petrochemical industry), acrylonitrile-butadiene-styrene (ABS) plastics grafted maleic anhydride (ABS-g-MAH) 4wt%, halogen-free flame retardants 12wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain nylon alloy material, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Comparative example 3
By PA6M2400 (Yueyang petrochemical industry) 59.8wt%, halogen-free flame retardants 11wt% (melamine phosphate), fire retarding synergist Sb 2o 34wt%, oxidation inhibitor 0.2wt% (phosphiinic acid ester irgasfos 168) join in homogenizer and are uniformly mixed, mixing temperature not higher than 80 DEG C, mixing time 15min, the material stirred being joined length-to-diameter ratio L/D is 40:1, screw diameter is in the hopper of the parallel double-screw extruder of 30mm, the each section temperature of setting forcing machine from hopper to die head is respectively in (nine district) totally: 180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C, the screw speed of main frame is 350r/min, the rotating speed of hopper feed screw rod is 28r/min, carbon fiber T700SC-12K (east is beautiful) 10wt% is added by the exclusion mouth of twin screw extruder, short glass fiber (ECS 3014B) 15wt% is added by the side spout of twin screw extruder, material is extruded through melt blending, cool through tank, enter dicing machine after air-dry and carry out pelletizing, obtain nylon alloy material, be injection molded into after test bars according to GB, the standard testing performances such as ISO or UL94.
Measurement of Material Mechanical Performance is according to GB standard, and the molding shrinkage of material adopts a dimension electronics height gauge test according to ISO294-4 standard, and the flame retardant properties test foundation UL94 standard results of material is in table 1.
The performance index of table 1 nylon alloy material
Embodiment Density MI Tensile strength Elongation Notch shock Flexural strength Modulus in flexure HDT Molding shrinkage
1 1.304 18 141 10 7.82 232 10845 185 0.6
2 1.329 12 145 11 7.53 243 11034 255 0.5
3 1.343 14 153 12 8.15 258 12907 243 0.6
4 1.335 25 150 9 7.98 251 12854 247 0.5
5 1.415 12 141 11 7.76 253 11086 252 0.4
6 1.322 13 165 8 5.72 242 11323 258 0.4
7 1.341 11 158 12 7.54 242 9807 251 0.4
8 1.302 13 163 9 7.32 256 10563 258 0.4
9 1.341 16 168 12 9.32 246 10438 252 0.5
Comparative example 1 1.365 15 138 10 6.84 263 13037 257 0.6
Comparative example 2 1.145 28 78 101 2.13 87 2805 83 1.6
Comparative example 3 1.353 9 154 11 6.51 260 13705 248 0.9
From table 1, the carbon fibre reinforced composite that the present invention obtains after adopting acrylonitrile-butadiene-styrene (ABS) plastics (ABS) and nylon (PA) compound has excellent mechanical property and processing characteristics; Density and the physical mechanics intensity of material significantly can be reduced after replacing glass fibre with part carbon fiber; Material after alloying has the directed warpage rate obviously reduced than simple carbon fiber or glass fibre molding shrinkage and goods.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a halogen-free flameproof carbon fiber reinforced nylon alloy material for low warpage rate, is characterized in that the component comprising following mass percent:
2. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: the low sticky nylon of described nylon to be viscosity be 2.0 ~ 2.8Pa.S.
3. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: the consumption of acrylonitrile-butadiene-styrene (ABS) plastics used is 10 ~ 40wt% of nylon quality.
4. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: the mass ratio of glass fibre used and carbon fiber is 3:2.
5. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: the mass ratio of halogen-free flame retardants used and fire retarding synergist is 5:1 ~ 2:1.
6. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: described carbon fiber is the carbon fiber of polyacrylonitrile base material, filament diameter 4 ~ 8 μm, synnema linear density 200 ~ 800tex; Described glass fibre is filament diameter is 3 ~ 10 μm, and filament length is the alkali-free short glass fiber of 300 ~ 500mm.
7. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: the content of described nylon is 40 ~ 50wt%; The content of described acrylonitrile-butadiene-styrene (ABS) plastics is 8 ~ 10wt%; The content of described carbon fiber is 10wt%; The content of described glass fibre is 15wt%.
8. the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate according to claim 1, is characterized in that: described halogen-free flame retardants is the expansion type flame retardant of triazines; Described fire retarding synergist is antimonous oxide; Described compatilizer is maleic anhydride class grafts; Other described auxiliary agents comprise at least one in processing stabilizers and oxidation inhibitor.
9. a preparation method for the halogen-free flameproof carbon fiber reinforced nylon alloy material of the low warpage rate according to any one of claim 1 ~ 8, is characterized in that specifically comprising the following steps:
Nylon 32.5 ~ 57.7wt%, acrylonitrile-butadiene-styrene (ABS) plastics 5 ~ 15wt%, halogen-free flame retardants 5 ~ 12wt%, fire retarding synergist 1 ~ 5wt%, compatilizer 0 ~ 5wt% and other auxiliary agents 0.1 ~ 0.3wt% mixing are added by twin-screw extrusion owner spout, carbon fiber 5 ~ 25wt% is added by the exclusion mouth of twin screw extruder, glass fibre 5 ~ 25wt% is added by the side spout of twin screw extruder, melt blending, cooling granulation, obtains the halogen-free flameproof carbon fiber reinforced nylon alloy material of low warpage rate.
10. the application of halogen-free flameproof carbon fiber reinforced nylon alloy material in electronic apparatus, aerospace, communications and transportation, field of power tools of the low warpage rate according to any one of claim 1 ~ 8.
CN201410827638.2A 2014-12-25 2014-12-25 Low-warping-rate halogen-free flame retardant carbon fiber-reinforced nylon alloy material and preparation method Pending CN104448806A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105670275A (en) * 2016-04-12 2016-06-15 苏州甫众塑胶有限公司 Mobile phone shell plastic material and preparation method thereof
CN107298849A (en) * 2016-12-26 2017-10-27 上海普利特化工新材料有限公司 A kind of flame-retardant conductive PA and ABS alloy material and preparation method thereof
CN109627751A (en) * 2018-11-30 2019-04-16 上海日之升科技有限公司 Fire-retardant continuous long glass fiber reinforced PA6 material of one kind and preparation method thereof
CN110511559A (en) * 2019-09-06 2019-11-29 深圳市银宝山新科技股份有限公司 Mixed fiber plastic cement and preparation method thereof is kneaded injection-moulding device

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CN102276977A (en) * 2011-06-10 2011-12-14 东莞劲胜精密组件股份有限公司 High-performance anti-warping nylon material and preparation method thereof
CN104072933A (en) * 2014-06-13 2014-10-01 安徽皖东化工有限公司 Heat-resistant flame-retardant ABS (Acrylonitrile-Butadiene-Styrene) resin

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Publication number Priority date Publication date Assignee Title
CN102276977A (en) * 2011-06-10 2011-12-14 东莞劲胜精密组件股份有限公司 High-performance anti-warping nylon material and preparation method thereof
CN104072933A (en) * 2014-06-13 2014-10-01 安徽皖东化工有限公司 Heat-resistant flame-retardant ABS (Acrylonitrile-Butadiene-Styrene) resin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105670275A (en) * 2016-04-12 2016-06-15 苏州甫众塑胶有限公司 Mobile phone shell plastic material and preparation method thereof
CN107298849A (en) * 2016-12-26 2017-10-27 上海普利特化工新材料有限公司 A kind of flame-retardant conductive PA and ABS alloy material and preparation method thereof
CN109627751A (en) * 2018-11-30 2019-04-16 上海日之升科技有限公司 Fire-retardant continuous long glass fiber reinforced PA6 material of one kind and preparation method thereof
CN110511559A (en) * 2019-09-06 2019-11-29 深圳市银宝山新科技股份有限公司 Mixed fiber plastic cement and preparation method thereof is kneaded injection-moulding device

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