CN107501924A - A kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite and preparation method thereof - Google Patents
A kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite and preparation method thereof Download PDFInfo
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- CN107501924A CN107501924A CN201610425709.5A CN201610425709A CN107501924A CN 107501924 A CN107501924 A CN 107501924A CN 201610425709 A CN201610425709 A CN 201610425709A CN 107501924 A CN107501924 A CN 107501924A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2205/00—Polymer mixtures characterised by other features
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite and preparation method thereof, by PA66, PA6, continuous glass fibre, modified graphene, antioxidant, compound hydrolysis-resisting agent, the steady agent of complex light, lubricant, black masterbatch, metal oxide be blended, dipping, pelletizing are made；The modified graphene refers to that graphene carries out pre-processing formation through neopelex and silane coupler to its surface.The present invention is by adding the graphene of pre-dispersed processing and compounding multiple functions auxiliary agent, not only possess excellent rigidity and impact flexibility, there is excellent weatherability and good hydrolytic Resistance simultaneously, and Injection moulded part surface is without glass emergence on the surface, application of the fiber glass reinforced polyamide in different field can be met, the material can be by being molded straight forming, and production efficiency is high, and the product after use can recycle after crushed.
Description
Technical field
The present invention relates to technical field of polymer materials, is specifically related to a kind of graphene, continuous glass-fiber collaboration reinforced polyamide is answered
Condensation material and preparation method thereof.
Background technology
Contain highly polar amide groups in nylon66 fiber (PA66) molecular backbone, and the hydrogen bond between amide groups makes intermolecular adhesion
It is relatively strong, easily crystallize structure, so material has good mechanical property, such as intensity is high, the good, shock resistance of rigidity.
Other nylon66 fiber also has the advantages that oil resistant and chemicals, wearability, self lubricity and processing fluidity are good, especially resistance to
Hot and creep resistance is more preferably.In addition PA66 raw materials are easy to get, and cost is low, thus be widely applied to industry, clothes, decoration,
The fields such as engineering plastics.But impact properties of the PA66 under dry state and low temperature is poor, and modulus of elasticity is low, particularly hygroscopic and shadow
Ring the dimensional stability of product, it is impossible to meet the requirement of environmental stress resistance and high manufacturing accuracy.
Polyamide is greatly improved its mechanical performance, heat resistance and dimensional stability, in reality after glass fiber reinforcement is added
To mould for steel substituted metal material high-strength structure product can be met in automobile, the application of field of household appliances in the application of border.But
For most of appearance member, high mechanical strength is not only needed, while requires that product outward appearance is good, it is impossible to has obvious glass
It is fine exposed.
Two-dimentional carbon element crystal of the graphene as discovered in recent years, there is prominent and excellent heat conductivility, mechanical property and electricity
Performance, its nanostructured are also very unique；Because graphene has larger specific surface area, a small amount of addition can is to poly-
Compound substrate performance produces significant impact, but graphenic surface inert state again, with the interface compatibilities of other media compared with
Difference, and graphene has stronger Van der Waals force between layers, easily produces aggregation each other.So graphene strengthens polymer
Raising of the raising of composite property dependent on interface bond strength, the most critical factor of control interface bond strength is to graphite
Alkene is surface-treated, and increase graphenic surface effective efficiency group, different functional groups is introduced by surface treatment method, so as to
Effectively improve the interface cohesion of graphene and polymer.
In addition to covalent bond functionalization, can also by non-covalent bond connection method to graphenic surface carry out functionalization, you can with π-
The supermolecular mechanisms such as π interactions, ionic bond and hydrogen bond are modified graphenic surface, so as to improve the scattered of graphene
Property.Because graphene has height conjugated system in itself, it is easy to the conjugated structure equally with pi-pi bond or containing fragrance
Stronger π-π interactions occur for the small molecule and polymer of structure.Journal of Functional Polymers periodical " is based on π-π within 2010
Wang Ping China waits in the star-like polyacrylonitrile-graphene composite material of interaction synthesis " has synthesized the triphenylene containing 6 hydroxyls first
Derivative, star-like polyacrylonitrile polymer is then synthesized by redox initiation system, finally in the N of star-like polyacrylonitrile,
Dinethylformamide solution (DMF) obtains uniform and stable solution with hydrazine hydrate reduction graphene oxide, and places very long
Time, by being carried out to product, infrared spectrum, nuclear magnetic resoance spectrum, gel infiltration penetrated spectrum, ESEM phenetic analysis is sent out without precipitation
Existing between triphenylene structure and graphene is interacted by pi-pi bond, successfully realizes functionalization to graphene.
Although inorganic mineral raw material is added in carbon fibre reinforced polyamide material can improve the carbon fibre exposing phenomenon of product outward appearance,
It is that after adding inorganic mineral the mechanical strength of material can be caused to be decreased obviously, it is impossible to meet the design requirement of high intensity.
In addition, after fiber glass reinforced polyamide, the water absorption rate of material can be reduced to 2% or so, well below the suction of polyamide raw materials
Water rate, but still have a great impact to the performance of material, cause material tensile property to reduce by 50% or so, particularly at family
The reasons such as the light aging under the conditions of outer during use, material property conservation rate significantly limit glass increasing less than initial state 40%
Strong polyamide material uses field.Therefore for the higher structure member of mechanical property and outdoor requirement, it is necessary to develop power
Performance is higher, has the continuous glass-fiber reinforced polyamide composite of more preferable weatherability and resistant to hydrolysis.Using single nylon
Hydrolysis-resisting agent, it is impossible to ensure the material property of long-term hygrometric state.
Chinese patent CN102010590A proposes a kind of long glass fibre reinforced nylon material and preparation method thereof, and component is：Buddhist nun
Imperial 29-67wt%, long glass fibres 30-60wt%, compatilizer 2-10wt%, antioxidant 0.3-1.0wt%.Preparation method：First
Nylon, compatilizer, antioxidant are mixed；Add mixture to again in double screw extruder, processing temperature is at 235-300 DEG C；
Resin melt is squeezed into the impregnation mold being connected with double screw extruder head；Then by long glass fibres by impregnation mold,
The dipping temperature of impregnation mold is 260-320 DEG C, long glass fibres is sufficiently impregnated by melt, finally cools down, draws, pelletizing,
Obtain Long Glass Fiber Reinforced Pa pellet.The invention only proposes material of long glass fiber reinforced nylon and preparation method thereof, still
Fail to be furtherd investigate in the hydrolytic Resistance of long fiber reinforced nylon material and weather resistance.
Chinese patent CN101921474A provides a kind of enhancing high-temperature nylon and preparation method thereof.Strengthen high-temperature nylon by following heavy
The raw material of amount part ratio is made：Polyphenyl diamide 55%-80%, glass fibre 20%-45%, Brueggemann antioxidant 0.1%-1.2
%.By the way that polyphenyl diamide to be mixed to generation enhancing high-temperature nylon with glass fibre and Brueggemann antioxidant, make enhancing high temperature Buddhist nun
Dragon not only maintains the advantage of the chemical resistance that other nylon have and easy processing, and in glass fibre and Brueggemann antioxidant
In the presence of, enhancing high-temperature nylon resistance to elevated temperatures and impact strength are improved, so that enhancing high-temperature nylon can be by more
It is widely applied.The invention improves the hydrolytic resistance of material to a certain extent using Brueggemann copper salt antioxidant, but adopts
With the direct blending and modifying of double screw extruder, because the shear action of screw rod causes fibre length very little, for the property of nylon material
Energy raising is limited, and especially impact strength is than relatively low.
The content of the invention
The technical problem to be solved in the present invention is：The shortcomings that there are problems that for above prior art and, there is provided a kind of graphene,
Continuous glass-fiber collaboration reinforced polyamide composite and preparation method thereof, the material not only has good weather resistance and resistant to hydrolysis
Performance, and Injection moulded part outward appearance is good, no glass emergence on the surface.
The technical scheme is that：
A kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite, are prepared by weight by following components：PA66：
400-560 parts, PA6：100-140 parts, continuous glass fibre：300-500 parts, modified graphene：5-15 parts, antioxidant：
6-10 parts, compounding hydrolysis-resisting agent：2-6 parts, the compounding steady agent of light:3-5 parts, lubricant：4-8 parts, metal oxide：5-15
Part, black masterbatch：5-15 parts；The modified graphene refers to graphene through neopelex and silane coupler to its table
Face carries out pre-processing formation.
Further scheme, melt index of the described PA6 under 230 DEG C/2.16Kg are 20g-40g/10min；Described PA66
Melt index under 275 DEG C/0.325Kg is 20-30g/10min.
Described continuous glass fibre is selected from alkali-free glass fibre, its a diameter of 13-22 μm, line density 1200-4800g/km.
The particle diameter of the modified graphene is 24~220 microns, thickness is 2.5~50 microns, and wherein carbon content is more than 98%.
Described antioxidant is by N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and three [2.4-
Di-tert-butyl-phenyl] phosphite ester by weight be 1：2 compositions.
Described compounding hydrolysis-resisting agent is by weight being 1 by polycarbodiimide and diisobutyl phosphordithiic acid copper:1 composition.
The described steady agent of compounding light is by hindered amines light stabilizer N, the formyls of N '-two-N, N '-two (2,2,6,6- tetramethyl -4- piperidines)
- hexamethylene diamine (UV4050) and 2-hydroxy-4-n-octoxybenzophenone (UV531) are 1 by weight:1 composition.
One kind in ethylene-acrylic acid copolymer wax, calcium stearate, silicone and pentaerythrite stearate of described lubricant or
The two or more mixture of person；
Described metal oxide is one or two kinds of mixture in zinc oxide or calcium oxide, and the particle diameter of metal oxide is
4-25 microns；
Described black masterbatch is that high melanin blue phase carbon black and ethylene-vinyl acetate copolymer are formed, and wherein content of carbon black is more than 90%；
Melt index of the black masterbatch under 190 DEG C of test temperature, test load 21.6Kg is 5-10g/10min.Such as black masterbatch
T09242, T09294 etc..
Another goal of the invention of the present invention is to provide the preparation of above-mentioned graphene, continuous glass-fiber collaboration reinforced polyamide composite
Method, it comprises the following steps：
(1) pretreatment of graphene：Graphene is added in high mixer, adds the dodecane for accounting for graphene quality 1% respectively
Base benzene sulfonic acid sodium salt and 0.5% silane coupler KH-560, surface preparation is carried out to it in 50-60 DEG C of mixed at high speed 4-6 minute；
(2) by pretreated graphene and PA66, PA6, antioxidant, compounding hydrolysis-resisting agent, the steady agent of compounding light, lubricant,
Metal oxide and black masterbatch were added sequentially in high mixer in 40-60 DEG C of batch mixing 3-5 minute；
(3) mixed material being mixed evenly is added in double screw extruder, be injected into after fusion plastification in impregnating equipment；Together
When continuous glass fibre be incorporated into impregnating equipment by the access road of impregnating equipment alternately bypassed after groups of jockey pulley along rolling over
Line advance, continuous glass fibre by jockey pulley uniformly disperse dipping and with molten resin it is dispersed after pass through mouth mold of shaping, warp
Cooling, traction, pelletizing cooperate with reinforced polyamide composite into length for 6-25mm graphene, continuous glass-fiber.
The screw diameter 65mm of described double screw extruder, the draw ratio of screw rod are 40：1, the drying temperature of its hopper is 80-90
DEG C, mixed melting temperature is：140-160 DEG C of first paragraph, 230-240 DEG C of second segment, the 3rd section 250-260 DEG C, the 4th section of 260-270
DEG C, the 5th section 270-280 DEG C, melt temperature be 250-270 DEG C, head temperature be 265-275 DEG C；
The temperature of the impregnating equipment is 280-300 DEG C；The size 2.5-3.5mm of the sizing mouth mold；
Described PA66, PA6 dries 6-8h in the environment of 90-100 DEG C of temperature before combination.
In described graphene, continuous glass-fiber collaboration reinforced polyamide pellet, roving glass fiber is arranged in parallel with each other along pellet length direction,
And fibre length is identical with pellet length.
The present invention, that is, by the surface preparation to graphene, increases its boundary with polyamide as a result of above technical scheme
Face compatibility, addition compounds the steady agent of light in addition and hydrolysis-resisting agent prepares continuous glass-fiber reinforced polyamide composite, because glass exists
Dispersion mixing is carried out with molten resin in impregnating equipment, glass fibre is orientated at same direction within this material, and glass in pellet
The length of glass fiber is 6-25mm, and long fibre length can form stable three-dimensional net structure in material or product, from
And the rigidity and impact flexibility and weather-proof and hydrolytic Resistance of material is greatly improved.Add further, since being used as using PA6
Work auxiliary material, the viscosity of system is reduced, improve the processability of material, and it is fine to solve the problems, such as that article surface floats, and improves
Article surface quality.
Due to being strengthened using continuous glass-fiber, the impregnating dispersion of glass and resin is to be carried out by jockey pulley in impregnating equipment, makes to have
Effect fibre length is retained, therefore is provided simultaneously with excellent rigidity and impact flexibility, the material can by being molded straight forming,
Production efficiency is high, and the product after use can recycle after crushed.
The present invention compared with the existing technology, has the following advantages that and beneficial effect：
1st, the present invention is using modified graphene, the common reinforced polyamide material of continuous glass-fiber, by the surface preparation to graphene,
Its interface compatibility with polyamide is improved, therefore composite prepared by the present invention has higher mechanical property；
2nd, the present invention uses continuous glass fibre reinforced plastic PA66, dispersed to continuous glass fibre progress by impregnating equipment, complete
Full dipping, improves glass fibre and PA66 interface interaction, ensure that the effective length of glass fibre, glass fibre length
It is identical with gained composite pellet length in 6-25mm, so as to substantially increase the rigidity of the material and intensity with
And the shock resistance of material.
3rd, the present invention uses compound hydrolysis-resisting agent and the steady agent of complex light, makes the composite of system have excellent hydrolytic resistance and good
Weatherability.
4th, due to the use of metal oxide, the compatibility of nylon resin and glass is added, is noted using the material of the invention prepared
The product appearance surfaces of modeling are good, no glass emergence on the surface and floating fibre.
5th, the present invention is reasonable in design, simple to operate, practical, and product has the pellet (grain length of certain length：6-25mm,
Diameter：2.5-3.5mm), after drying process can direct injection molding, production efficiency is high, and after product use by crushing at
Reason can also recycle, free from environmental pollution.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Wherein, PA66 melt index is 20-30g/10min, and test condition is 275 DEG C/0.325Kg；
PA6 melt index is 20g-40g/10min, and test condition is 230 DEG C/2.16Kg；
Continuous glass fibre is alkali-free continuous glass fibre, and its fibre diameter is 17 μm, line density 1200-4800g/km；
The particle diameter of modified graphene is 24~220 microns, thickness is 2.5~50 microns, and carbon content is more than 98%；
Antioxidant is by N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine (anti-1098) and three
[2.4- di-tert-butyl-phenyls] phosphite ester (anti-168) is 1 by weight：2 compositions；
Compound hydrolysis-resisting agent is selected from the polycarbodiimide (Stabaxol P) of Rhein chemistry and diisobutyl phosphordithiic acid copper is pressed
Weight ratio is 1:1 composition；
The compounding steady agent of light is that the UV531 and UV4050 of BASF are 1 by weight:1 composition；
Lubricant includes ethylene-acrylic acid copolymer wax (AC540A), calcium stearate (CaSt), silicone (GM100) and season penta
Tetrol stearate (PETS)；
Metal oxide is zinc oxide or calcium oxide, and particle diameter is 20 microns；
The black masterbatch trade mark is the commercially available trade mark T09242, T09294.
Embodiment 1
(1) a kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite, material pelletizing length 6-25mm, particle diameter
3.5mm, it includes the component of following weight part ratio：PA6:140 parts, PA66：560 parts, continuous glass fibre：300 parts,
Graphene：5 parts, antioxidant：8 parts, compounding hydrolysis-resisting agent：4 parts, compound the steady agent of light：4 parts, lubricant：6 parts, oxygen
Change zinc：15 parts, black masterbatch：10 parts；Wherein, PA66 resins, melt index 26g/10min, test condition are 275 DEG C,
0.325Kg；PA6 resins, melt index 32g/10min, test condition are 230 DEG C, 2.16Kg；Continuous glass fibre is
Alkali-free continuous glass fibre, fibre diameter are 17 μm, line density 2400g/km；The particle diameter of modified graphene is 24~220
Micron, thickness are 2.5~50 microns；Antioxidant includes N, N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) oneself
Diamines (anti-1098) and three [2.4- di-tert-butyl-phenyls] phosphite esters (anti-168), the weight part ratio of the two are 1：2；
Compound hydrolysis-resisting agent is selected from the polycarbodiimide (Stabaxol P) and diisobutyl phosphordithiic acid copper of Rhein chemistry, the two
Weight is 1:1；The steady agent of complex light is the UV531 and UV4050 of BASF, and the weight part ratio of the two is 1:1；Lubricant includes
Ethylene-acrylic acid copolymer wax (AC540A) and calcium stearate (CaSt), the weight part ratio of the two are 1：1；Metal oxygen used
Compound is that zinc oxide particle diameter is 20 microns, and the black masterbatch trade mark is commercially available T09242；
(2) a kind of graphene, the preparation method of continuous glass-fiber collaboration reinforced polyamide composite, comprise the following steps：
A, dry and prepare：PA66/PA6 raw materials are placed in drier, drying temperature：95 DEG C, drying time：6h；
B, batch mixing prepares:By 5 parts of graphenes, 0.05 part of neopelex, 0.025 silane coupler KH-560
It is added in high mixer, 50 degree of mixture temperature, mixing time carries out pre-processing to obtain modified graphene for 6 minutes；
Then by 560 parts of PA66,140 parts of PA6,5 parts of modified graphenes, 8 parts of antioxidant, 4 parts of compounding hydrolysis-resisting agents, 4
The steady agent of part compounding light, 6 parts of lubricants, 15 parts of zinc oxide, 10 parts of black masterbatchs are added sequentially in high mixer, mixture temperature control
At 50 DEG C, mixing time stops system after 4 minutes, then mixed material is added to standby in the hopper of extruder, extruder material
The drying temperature of bucket is set as 85 DEG C；
C, the preparation of graphene, continuous glass-fiber collaboration reinforced polyamide composite：Above-mentioned material is melted by double screw extruder
Melt plasticizing to be injected into impregnating equipment, while continuous glass fibre is incorporated into impregnation mold by the access road of impregnation mold,
Alternately bypass groups of jockey pulley after advance along broken line, glass by jockey pulley uniformly disperse dipping and it is dispersed with molten resin,
By selecting the size 3.5mm of sizing mouth mold, while the engine speed for adjusting extruder exists in 16-22Hz, rate of feeding
15.0-17.0Hz, glass fiber content are controlled at 300 parts, adjust the cutter rotating velocity of pelleter, the graphene that makes to be prepared, continuous
Glass collaboration reinforced polyamide composite pelletizing length control is in 6-25mm；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature is set as：
150 DEG C of first paragraph, 240 DEG C of second segment, the 3rd section 260 DEG C, the 4th section 270 DEG C, the 5th section 280 DEG C, melt temperature 265
DEG C, 270 DEG C of head temperature；The impregnating equipment design temperature is 280 DEG C.
Embodiment 2
(1) a kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite, material pelletizing length 11-13mm, particle diameter
3.0mm, include the component of following weight part ratio：PA6:120 parts, PA66：480 parts, continuous glass fibre：400 parts, stone
Black alkene：10 parts；Antioxidant：8 parts, compounding hydrolysis-resisting agent：4 parts, compound the steady agent of light：5 parts, lubricant：8 parts, oxidation
Calcium：10 parts, black masterbatch：5 parts；Wherein, PA66 resins, melt index 26g/10min, test condition are 275 DEG C,
0.325Kg；PA6 resins, melt index 32g/10min, test condition are 230 DEG C, 2.16Kg；Continuous glass fibre is
Alkali-free continuous glass fibre, fibre diameter are 17 μm, line density 1200g/km；The particle diameter of modified graphene is 24~220
Micron, thickness are 2.5~50 microns；Antioxidant includes N, N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) oneself
Diamines (anti-1098) and three [2.4- di-tert-butyl-phenyls] phosphite esters (anti-168), the weight part ratio of the two are 1：2；
Compound hydrolysis-resisting agent is selected from the polycarbodiimide (Stabaxol P) and diisobutyl phosphordithiic acid copper of Rhein chemistry, the two
Weight is 1:1；The steady agent of complex light is the UV531 and UV4050 of BASF, and the weight part ratio of the two is 1:1；Lubricant includes
Ethene-acrylic acid copolymer wax (AC540A) and silicone (GM100), the weight part ratio of the two are 1：1；Metal oxidation used
Thing is calcium oxide, and 20 microns of particle diameter, black masterbatch is commercially available trade mark T09294；
(2) a kind of graphene, the preparation method of continuous glass-fiber collaboration reinforced polyamide composite, comprise the following steps：
A, dry and prepare：PA66/PA6 raw materials are placed in drier, drying temperature：95 DEG C, drying time：6h；
B, batch mixing prepares:By 10 parts of graphenes with account for graphene quality 1% neopelex, 0.5% it is silane coupled
Agent KH-560 is added in high mixer, 50 degree of mixture temperature, and mixing time carries out pre-processing to obtain modified graphene for 6 minutes；
480 parts of PA66,120 parts of PA6,10 parts of modified graphenes, 8 parts of antioxidant, 4 parts of compound hydrolysis-resisting agents, 5 parts are answered
The steady agent of closing light, 8 parts of lubricants, 10 parts of calcium oxide, 5 parts of black masterbatch are added sequentially in high mixer, and mixture temperature is controlled 50
DEG C, mixing time stops after 4 minutes, then mixed material is added to it is standby in the hopper of extruder, extruder hopper it is dry
Dry temperature is set as 85 DEG C；
C, the preparation of graphene, continuous glass-fiber collaboration reinforced polyamide composite：Above-mentioned material is melted by double screw extruder
Melt plasticizing to be injected into impregnating equipment, while continuous glass fibre is incorporated into impregnation mold by the access road of impregnation mold,
Alternately bypass groups of jockey pulley after advance along broken line, glass by jockey pulley uniformly disperse dipping and it is dispersed with molten resin,
By selecting the size 3.0mm of sizing mouth mold, while the engine speed for adjusting extruder exists in 16-22Hz, rate of feeding
15.0-17.0Hz, glass fiber content are controlled at 400 parts, adjust the cutter rotating velocity of pelleter, the graphene that makes to be prepared, continuous
Glass collaboration reinforced polyamide composite pelletizing length control is in 6-25mm；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature is set as：
160 DEG C of first paragraph, 240 DEG C of second segment, the 3rd section 260 DEG C, the 4th section 270 DEG C, the 5th section 280 DEG C, melt temperature 265
DEG C, 270 DEG C of head temperature；The impregnating equipment temperature is 300 DEG C.
Embodiment 3
(1) a kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite, material pelletizing length 11-13mm, particle diameter
3.5mm, include the component of following weight part ratio：PA6:100 parts, PA66：400 parts, continuous glass fibre：500 parts, stone
Black 15 parts of alkene, antioxidant：8 parts, compounding hydrolysis-resisting agent：4 parts, compound the steady agent of light：3 parts, lubricant：4 parts, zinc oxide
5 parts, black masterbatch：15 parts；Wherein, PA66 resins, melt index 24g/10min, test condition are 275 DEG C, 0.325Kg；
PA6 resins, melt index 20g/10min, test condition are 230 DEG C, 2.16Kg；Continuous glass fibre is the continuous glass of alkali-free
Glass fiber, fibre diameter are 17 μm, line density 4800g/km；The particle diameter of modified graphene is 24~220 microns, thickness is
2.5~50 microns；Antioxidant includes N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine (anti-1098)
With three [2.4- di-tert-butyl-phenyls] phosphite esters (anti-168), the weight part ratio of the two is 1：2；Compound hydrolysis-resisting agent choosing
From the polycarbodiimide (Stabaxol P) and diisobutyl phosphordithiic acid copper of Rhein chemistry, the two weight is 1:1；It is multiple
The steady agent of closing light is the UV531 and UV4050 of BASF, and the weight part ratio of the two is 1:1；Lubricant include silicone (GM100) and
Pentaerythrite stearate (PETS), the weight part ratio of the two are 1：1；Metal is oxidized to the zinc oxide for 20 microns of particle diameter,
Black masterbatch is commercially available trade mark T09294；
(2) a kind of graphene, the preparation method of continuous glass-fiber collaboration reinforced polyamide composite, comprise the following steps：
A, dry and prepare：PA66/PA6 raw materials are placed in drier, drying temperature：95 DEG C, drying time：6h；
B, batch mixing prepares:By 15 parts of graphenes and neopelex, 0.5% silane coupler of graphene quality 1%
KH-560 is added in high mixer, 50 degree of mixture temperature, and mixing time carries out pre-processing to obtain modified graphene for 6 minutes；
By 400 parts of PA66,100 parts of PA6,15 parts of modified graphene graphenes, 8 parts of antioxidant, 4 parts compounding hydrolysis-resisting agents,
The steady agent of 2 parts of compounding light, 4 parts of lubricants, 5 parts of zinc oxide, 15 parts of black masterbatch are added sequentially in high mixer, mixture temperature control
At 50 DEG C, mixing time stops after 4 minutes, then mixed material is added to standby in the hopper of extruder, extruder hopper
Drying temperature be set as 85 DEG C；
C, the preparation of graphene, continuous glass-fiber collaboration reinforced polyamide composite：Above-mentioned material is melted by double screw extruder
Melt plasticizing to be injected into impregnating equipment, while continuous glass fibre is incorporated into impregnation mold by the access road of impregnation mold,
Alternately bypass groups of jockey pulley after advance along broken line, glass by jockey pulley uniformly disperse dipping and it is dispersed with molten resin,
By selecting the size 2.5mm of sizing mouth mold, while the engine speed for adjusting extruder exists in 16-22Hz, rate of feeding
15.0-17.0Hz, glass fiber content are controlled at 500 parts, adjust the cutter rotating velocity of pelleter, the graphene that makes to be prepared, continuous
Glass collaboration reinforced polyamide composite pelletizing length control is in 6-25mm；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature is set as：
140 DEG C of first paragraph, 240 DEG C of second segment, the 3rd section 260 DEG C, the 4th section 270 DEG C, the 5th section 280 DEG C, melt temperature 265
DEG C, 270 DEG C of head temperature；The impregnating equipment temperature is 290 DEG C.
Comparative example 1
In order to use continuous glass fibre with PA66/PA6 resins in twin-screw extrusion compared with prior art, in this comparative example
The direct melting mixing of machine is disperseed, i.e., continuous glass fibre is directly added in double screw extruder from fiber entry in step (2), is led to
Adjustment screw speed and feeding rotating speed are crossed, control content of glass fiber pulls out material strip at 300 parts from double screw extruder, expected
Bar crosses water cooling, the water on blower fan drying material strip surface, then carries out pelletizing；Other components, formula rate and preparation method and reality
It is identical to apply example 1, its performance test results is shown in Table 4.
Comparative example 2
In order to which compared with technical scheme, hydrolysis-resisting agent is selected from the polycarbodiimide of Rhein chemistry in this comparative example
(Stabaxol P), addition are 4 parts, and other components and formula rate, preparation method are identical with embodiment 1, its
The performance test results are shown in Table 4.
Comparative example 3
In order to which compared with technical scheme, hydrolysis-resisting agent is selected from diisobutyl phosphordithiic acid in this comparative example, adds
Enter amount for 4 parts, other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 4.
Comparative example 4
In order to compared with technical scheme, the steady agent of light is the UV531 of BASF in this comparative example, addition 4
Part, other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 3.
Comparative example 5
In order to compared with technical scheme, the steady agent of light is the UV4050 of BASF in this comparative example, addition 4
Part, other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 3.
Comparative example 6
In order to which compared with technical scheme, the steady agent of complex light is the UV531 and UV4050 of BASF in this comparative example,
Addition is 2 parts, and other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table
3。
Comparative example 7
In order to which compared with technical scheme, hydrolysis-resisting agent is selected from common copper salt kind antioxidant Rhein in this comparative example
Polycarbodiimide (Stabaxol P) and diisobutyl phosphordithiic acid copper, the two weight are 1:1, addition 1
Part, other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 4.
Comparative example 8
In order to which compared with technical scheme, the addition of metal oxide zinc is 4 parts in this comparative example, its
His component and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 9
In order to which compared with technical scheme, the addition of metal oxide calcium is 4 parts in this comparative example, its
His component and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 10
In order to which compared with technical scheme, the addition of metal oxide zinc is 16 parts in this comparative example,
Other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 11
In order to which compared with technical scheme, the addition of metal oxide calcium is 16 parts in this comparative example,
Other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 12
In order to which compared with technical scheme, the addition of the graphene of surface preparation is 0 in this comparative example, its
His component and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 6；
Comparative example 13
In order to which compared with technical scheme, the addition of the graphene of surface preparation is 16 in this comparative example,
Other components and formula rate, preparation method are identical with embodiment 1, and its performance test results is shown in Table 6；
Injection and batten test：
Reinforced polyamide composite is cooperateed with to dry the various embodiments described above graphene preparation-obtained with comparative example, continuous glass-fiber
It is molded after drying 6-8h under 80-100 DEG C of environment in case, injection batten is ASTM battens, and injection temperature is as follows：
Blanking section：260℃；Second segment：280℃；3rd section：290℃；Nozzle：270℃；
Finally injection batten is put in drier and carries out status adjustment：Adjust temperature：23 DEG C, regulating time：16h；Batten
It can test and be carried out according to following standard scale 1, test result is shown in Table 2.
The Mechanics Performance Testing standard of table 1
| Test event | Measuring unit | Testing standard | Remarks |
| Tensile strength | MPa | ASTM D638 | |
| Bending strength | MPa | ASTM D790 | |
| Bending modulus | MPa | ASTM D790 | |
| Izod notched impact strength | KJ/m2 | ASTM D256 | 23℃ |
| Ash content | % | ASTM D2584 | |
| Density | g/cm3 | ASTM D792 | |
| Heat distortion temperature | ℃ | ASTM D648 | 1.82MPa |
Weather-proof test：
Testing standard：SAE J1960-2004. are irradiated with acceleration of the control water cooling xenon arc lamp to automotive exterior materials；Using injection sample
Performance comparison before and after bar test aging 1000h, test result are shown in Table 3；
Hydrolysis is tested：
95 DEG C of heating water bath 100h of distilled water, are placed in 100 DEG C of oven drying 6h, after status adjustment 16h, test before and after water-bath
Batten performance, test result is shown in Table 4；
Test data contrasts in 2 each embodiment of table
Each embodiment xenon lamp aging 1000h test datas contrast of table 3
Each embodiment heating water bath 100h test datas contrast of table 4
Each embodiment product outward appearance of table 5 and Mechanics Performance Testing contrast
From the point of view of data in table 2, embodiment 1 is compared with comparative example 12,13, the graphene addition after surface treatment
After amount is reduced, after material mechanical performance declines rapidly, but the addition of graphene is more than 15 parts, the mechanical property increase of material
Unobvious, therefore the addition for considering graphene is proper in 5-15 parts.
Data in table 2 are found out, in embodiment 1,2,3, with the increase of continuous glass fibre content, the power of material
Learn intensity and gradually increased trend is presented.Compared with comparative example 1 is made into the test result of material with embodiment 1, it can see
Go out, the embodiment of the present invention 1 makes gained composite pellet length and glass using roving glass fiber dipping reinforced polyamide composite
Fibre length is identical in 6-25mm, because the material property that the more common twin-screw of fibre length is granulated will be higher by a lot, so
It is particularly evident especially in terms of notch impact strength in mechanical property.
Xenon lamp aging data can be seen that comparative example 1 and comparative example 4,5,6 from table 3, reduce the content of the steady agent of light
Afterwards or the steady agent system of single light is used, do not reach the material property of the present invention.
Test data contrasts after hot bath heating from table 4, can from the test data of embodiment 1 and comparative example 2,3,7
Go out, reduce the addition of hydrolysis-resisting agent or using after single water resistant enzymatic hydrolysis system, the obvious step-down of material property, illustrate in the present invention
Compound hydrolysis-resisting agent there is obvious action in terms of the resistant to hydrolysis of polyamide.
From table 5 in terms of the different adding proportions of metal oxide, after the adding proportion of zinc oxide or calcium oxide is less than 5 parts, meeting
Obvious there is the problem of floating fine, after the adding proportion of zinc oxide or calcium oxide is more than 15 parts, although be not in floating fine,
But the mechanical properties decrease of material is obvious, therefore integrated from floating fine and stabilizing material mechanical property is improved, metal oxide
Adding proportion should be optimum addition in 5-15 parts.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using the present invention.It is familiar with
The personnel of art technology obviously can easily make various modifications to these embodiments, and should General Principle described herein
Use in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, this area skill
Art personnel do not depart from improvement that scope made and modification all should be in the protection models of the present invention according to the announcement of the present invention
Within enclosing.
Claims (10)
1. a kind of graphene, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：It is prepared by weight by following components：PA66：400-560 parts, PA6：100-140 parts, continuous glass fibre：300-500 parts, modified graphene：5-15 parts, antioxidant：6-10 parts, compounding hydrolysis-resisting agent：2-6 parts, the compounding steady agent of light:3-5 parts, lubricant：4-8 parts, metal oxide：5-15 parts, black masterbatch：5-15 parts；The modified graphene refers to that graphene carries out pre-processing formation through neopelex and silane coupler to its surface.
2. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：Melt index of the described PA6 under 230 DEG C/2.16Kg is 20g-40g/10min；Melt index of the described PA66 under 275 DEG C/0.325Kg is 20-30g/10min.
3. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：Described continuous glass fibre is selected from alkali-free glass fibre, its a diameter of 13-22 μm, line density 1200-4800g/km.
4. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：The particle diameter of the modified graphene is 24 ~ 220 microns, thickness is 2.5 ~ 50 microns, and wherein carbon content is more than 98%.
5. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：Described antioxidant is that N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and three ［ 2.4- di-tert-butyl-phenyls ］ phosphite esters are 1 by weight by N：2 compositions.
6. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：Described compounding hydrolysis-resisting agent is by weight being 1 by polycarbodiimide and diisobutyl phosphordithiic acid copper:1 composition.
7. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：The described steady agent of compounding light is by hindered amines light stabilizer N, the formyls of N '-two-N, N '-two（2,2,6,6- tetramethyl -4- piperidines）- hexamethylene diamine and 2-hydroxy-4-n-octoxybenzophenone are 1 by weight:1 composition.
8. a kind of graphene according to claim 1, continuous glass-fiber cooperate with reinforced polyamide composite, it is characterised in that：One or more kinds of mixtures of the described lubricant in ethylene-acrylic acid copolymer wax, calcium stearate, silicone and pentaerythrite stearate；
Described metal oxide is one or two kinds of mixture in zinc oxide or calcium oxide, and the particle diameter of metal oxide is 4-25 microns；
Described black masterbatch is that high melanin blue phase carbon black and ethylene-vinyl acetate copolymer are formed, and wherein content of carbon black is more than 90%；Melt index of the black masterbatch under 190 DEG C of test temperature, test load 21.6Kg is 5-10g/10min.
9. graphene, the preparation method of continuous glass-fiber collaboration reinforced polyamide composite as described in claim any one of 1-8, it is characterised in that：Comprise the following steps：
（1）The pretreatment of graphene：Graphene is added in high mixer, adds the neopelex for accounting for graphene quality 1% respectively and 0.5% silane coupler KH-560, surface preparation is carried out to it in 50-60 DEG C of mixed at high speed 4-6 minute；
（2）Pretreated graphene and PA66, PA6, antioxidant, compounding hydrolysis-resisting agent, compounding light steady agent, lubricant, metal oxide and black masterbatch were added sequentially in high mixer in 40-60 DEG C of batch mixing 3-5 minute；
（3）The mixed material being mixed evenly is added in double screw extruder, is injected into after fusion plastification in impregnating equipment；Continuous glass fibre is incorporated into impregnating equipment by the access road of impregnating equipment simultaneously after alternately bypassing groups of jockey pulley and advanced along broken line, continuous glass fibre uniformly disperseed by jockey pulley dipping and with molten resin it is dispersed after by mouth mold of shaping, through cooling down, drawing, pelletizing cooperate with reinforced polyamide composite into graphene that length is 6-25mm, continuous glass-fiber.
10. a kind of graphene according to claim 9, continuous glass-fiber cooperate with the preparation method of reinforced polyamide composite, it is characterised in that：The screw diameter 65mm of described double screw extruder, the draw ratio of screw rod are 40：1, the drying temperature of its hopper is 80-90 DEG C, and mixed melting temperature is：140-160 DEG C of first paragraph, 230-240 DEG C of second segment, the 3rd section 250-260 DEG C, the 4th section 260-270 DEG C, the 5th section 270-280 DEG C, melt temperature be 250-270 DEG C, head temperature be 265-275 DEG C；
The temperature of the impregnating equipment is 280-300 DEG C；The size 2.5-3.5mm of the sizing mouth mold；
Described PA66, PA6 dries 6-8h in the environment of 90-100 DEG C of temperature before combination.
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| CN110218443A (en) * | 2019-06-25 | 2019-09-10 | 青岛万林橡塑科技有限公司 | A kind of preparation method of high glaze high-content long glass fiber reinforced PA composite material |
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| CN115260757A (en) * | 2022-08-15 | 2022-11-01 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant glass fiber reinforced PPA material and preparation method thereof |
| CN115260757B (en) * | 2022-08-15 | 2023-04-21 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant glass fiber reinforced PPA material and preparation method thereof |
| CN115558289A (en) * | 2022-10-12 | 2023-01-03 | 安徽省华晟塑胶股份有限公司 | Polyamide material for automobile shock-absorbing spring pad and preparation method thereof |
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Application publication date: 20171222 |