CN105778464B - A kind of graphene/glass fiber reinforced polycarbonate composite and preparation method thereof - Google Patents
A kind of graphene/glass fiber reinforced polycarbonate composite and preparation method thereof Download PDFInfo
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- CN105778464B CN105778464B CN201610315601.0A CN201610315601A CN105778464B CN 105778464 B CN105778464 B CN 105778464B CN 201610315601 A CN201610315601 A CN 201610315601A CN 105778464 B CN105778464 B CN 105778464B
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A kind of graphene/glass fiber reinforced polycarbonate composite, described graphene/glass fiber reinforced polycarbonate composite, include the components of following components parts by weight：The mass parts of makrolon 60 90, the mass parts of epoxy resin 5 20, the mass parts of graphene 0.01 5, the mass parts of glass fibre 5 20, the mass parts of silane coupler 0.1 1, the mass parts of ethanol 5 10, the mass parts of antioxidant 0.05 2, the mass parts of compatible toughening agents 0.5 3.The invention also discloses the preparation method of above-mentioned graphene/glass fiber reinforced polycarbonate composite.Graphene/glass fiber reinforced polycarbonate composite prepared by the present invention, not only preparation technology is simple, and experimental result shows that heat endurance, intensity and the toughness of prepared graphene/glass fiber reinforced polycarbonate composite are obviously improved, and floating fine phenomenon has been effectively eliminated, thus the practical application of polycarbonate composite material can be expanded.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of graphene/glass fiber reinforced polycarbonate is compound
Material and preparation method thereof.
Background technology
Makrolon is the polymer of bisphenol-A, belongs to thermoplastic resin, is widely used as engineering plastic materials, is shown
Excellent impact resistance, electrical property and moldability, physical property is kept within the scope of wider temperature, and there is self-extinguishment.
There is the shortcomings that bad processing characteristics yet with makrolon, be accordingly difficult to makrolon is small and more multiple used in size
In miscellaneous electric, electronic product shell.In order to solve this problem, the industrial tree used makrolon and other species
The method of fat blending, high impact is kept while the processing characteristics of material is improved.Glass fibre reinforced composite material is with poly-
Compound is matrix, using glass as reinforcing material manufactured composite, combine the performance of polymer and glass.Research shows
Fibrous material is added in makrolon, can greatly reinforcing material intensity and shrinkage factor, and improve the heat resistance of material.
Rubber and plastic industry has carried out in the industry the research work related to makrolon/graphene nanocomposite material high performance
Make.Chinese patent 201280029564.7, the composite that the invention is characterised by provided include makrolon, graphene
The components such as piece, obtained being formed anti-flammability, rigidity, impact resistance, electric conductivity, shaping outward appearance and thermal conductivity etc. it is excellent into
Body polycarbonate compositions；Chinese patent 201410041139.0, there is provided a kind of graphene modified high-strength degree, high heat conduction are gathered
Carbonic ester master batch and preparation method thereof, not only heat conductivility is greatly improved prepared composite, while its mechanics
Performance also has certain amplitude lifting；Chinese patent 201410837169.2, it is compound to disclose a kind of graphene/makrolon heat conduction
The addition of material and preparation method thereof, wherein graphene is 5-20 mass parts；Chinese patent 201110008919.1, pass through by
Fibrous heat filling and high heat conduction filler graphene be well mixed with thermoplastic poly carbonic ether it is scattered after be granulated, form height and lead
Hot composite pellet, heat filling dosage is few, mechanical property is good.
Correlative study shows that the addition of graphene makes polycarbonate composite material possess excellent mechanics, calorifics, electricity etc.
Combination property, but in method made above, graphene incorporation matrix is directly unfavorable for graphene in polycarbonate matrix
Dispersiveness and compatibility；And composite is prepared by the methods of graphene in-situ polymerization, coupling modifier, in actual production
Technique is cumbersome, and the form and performance change of graphene are difficult to control.The graphene of structural integrity is made up of phenyl ring, chemical stability
Height, surface is inert, is acted on other media weak；And be present stronger Van der Waals force in graphene film interlayer, easily reunite, greatly limitation
It studies application；How high-efficient simple, the method for application easy to implement is used to realize that graphene is good in makrolon material
It is good scattered, it is the key for preparing high performance polycarbonate/graphene nanocomposite material.Epoxy resin is added to glass fibre
In polycarbafil material, floating fine phenomenon can be effectively eliminated, and by selecting raw material and control preparation condition, graphene
Good dispersiveness, therefore dispersiveness of the present invention first with epoxy resin to graphene can be realized in the epoxy,
Graphene dispersing solution is made, then graphene-epoxy resin is added to polycarbonate composite material, obtains a kind of novel graphite
Alkene/glass fiber reinforced polycarbonate composite.
The content of the invention
It is an object of the invention to provide a kind of graphene/glass fiber reinforced polycarbonate composite and its preparation side
Method, the material possess that graphene addition is low, good mechanical property, processing characteristics and heat endurance.Eliminating glass fibers
While tieing up the floating fine phenomenon of polycarbafil composite, graphene in the composite dispersed is realized.
To reach above-mentioned purpose, composite provided by the invention includes the component of following parts by weight：Makrolon 60-
90 mass parts, epoxy resin 5-20 mass parts, graphene 0.01-5 mass parts, glass fibre 5-20 mass parts, silane coupler
0.1-1 mass parts, ethanol 5-10 mass parts, antioxidant 0.05-2 mass parts, compatible toughening agents 0.5-3 mass parts.
The polycarbonate is inherent viscosity in 45-55ml/g aromatic copolycarbonates, suitable aromatic polycarbonate
Ester has the methods of passing through interfacial polymerization by least one divalent phenol and a kind of carbonate precursor to be made, and carbonate precursor can be carbonyl
Base halide, halocarbonate or formic acid esters, preferably bisphenol A polycarbonate, inherent viscosity 48ml/g；The epoxy resin is
Propane type epoxy resin of di phenolic group, glycidyl ester epoxy resin, glycidyl amine epoxy resin and aliphatic ring oxygen tree
At least one of fat；Described glass fibre is alkali-free short glass fiber, and length is the silane coupler described in 3-12mm
For 3- aminopropyl triethoxysilanes, vinyl three（'beta '-methoxy ethyoxyl）Silane and vinyltrimethoxy silane are at least
It is a kind of；One or several kinds of the antioxidant in pentaerythritol ester, phosphite ester, the positive octadecanol ester of propionic acid；Institute
State compatible toughening agents and be selected from silicone powder, modified ethylene bis-fatty acid amides, methyl methacrylate-styrene-butadiene copolymerization
Thing.
The graphene has following performance parameter：Piece footpath is 5-500 microns, absorptance 3%-5%, used in the present invention
Graphene is usually the graphene with single or multiple lift structure, and preferably piece footpath is 10-50 microns, and thickness is 1-5 nanometers, compares table
Area is 20m-800m2/ g single-layer graphene, single-layer graphene specific surface area is bigger, and the hot property enhancing of product becomes apparent from,
Therefore preferably.
Heretofore described graphene/glass fiber reinforced polycarbonate composite, 0.01-5 parts are added in proportion
Graphene, preferably 0.1-2 parts.When content is too low, the enhancing effect that graphene plays is limited；When it is too high, it is multiple
Realize that the dispersed of graphene can be relatively difficult in condensation material, significantly improve material processing technique requirement, therefore preferably
Above range.
The preparation method of heretofore described graphene/glass fiber reinforced polycarbonate composite, including it is following
Step：
（1）Weigh 60-90 parts drying makrolon, antioxidant 0.05-2 parts, compatible toughening agents 0.5-3 parts, mixing
Uniformly；
（2）The graphene of 0.01-5 mass parts is added in the epoxy resin of 5-20 mass parts, low speed stirs at normal temperatures
Mix assisting ultrasonic and disperse 0.5-3h, graphene dispersing solution is made；
（3）0.1-1 mass parts silane couplers are dissolved in 5-10 mass parts absolute ethyl alcohols, are configured to silane coupled
Agent-ethanol solution, using spray-on process by spray solution on 5-20 part glass fibres, be then placed in baking oven dry 50-
80min, 90-110 DEG C of drying temperature；
（4）By step（1）Middle compound is sent into double screw extruder through upstream spout；By step（2）Middle graphene point
Dispersion liquid is sent into double screw extruder melting and squeezed through fed downstream mouth；By step（3）Glass fibre after middle processing through gas outlet,
It is sent into double screw extruder.Three of the above material adds speed using variable pump control, realizes the purpose being uniformly added into；
（5）Described double screw extruder is with vacuumizing and temperature control device, composite use extruder melting extrusion
It is granulated, is 180-200 DEG C respectively from spout to extrusion die temperature, 200-230 DEG C, 220-240 DEG C, 230-250 DEG C, 240-
260 DEG C, the machine screw speed 500-800r/min of extruder, charging rotating speed 40-70r/min.Product is made in cooling, pelletizing.
The invention has the advantages that：Graphene/glass fiber reinforced polycarbonate prepared by the present invention is compound
Material, not only preparation technology is simple, and experimental result shows the impact strength, heat-resisting of prepared polycarbonate composite material
The performance such as property, tensile strength, molding shrinkage is obviously improved, thus can expand the practical application model of polycarbonate composite material
Enclose.
Brief description of the drawings：
Fig. 1 is the microscopic appearance figure of comparative example 4 in the present invention.
Fig. 2 is the microscopic appearance figure of embodiment 3 in the present invention.
Embodiment
Embodiments of the invention are given below, the present invention is specifically described by embodiment.Be necessary it is pointed out here that
, embodiment is simply to further instruction of the present invention, it is impossible to is interpreted as limitation of the scope of the invention, the technology in the field
Personnel can make some adjustment to present disclosure.
A kind of preparation process of graphene/glass fiber reinforced polycarbonate composite comprises the following steps：（1）Weigh
Dry makrolon（Bisphenol A polycarbonate, inherent viscosity 48ml/g）, antioxidant, compatible toughening agents, be well mixed；
（2）Graphene is added in glycidyl amine epoxy resin, stirring at low speed assisting ultrasonic disperses 2h at normal temperatures, and stone is made
Black alkene dispersion liquid；（3）Silane coupler is dissolved in absolute ethyl alcohol, silane coupler-ethanol solution is configured to, utilizes spraying
Spray solution on the glass fibers, is then placed in baking oven and dries 50-80min by method, 90-110 DEG C of drying temperature；（4）Will step
Suddenly（1）Middle compound is sent into double screw extruder through upstream spout.By step（2）Middle graphene dispersing solution is through fed downstream
Mouthful, it is sent into double screw extruder melting and squeezes.By step（3）Glass fibre after middle processing is sent into twin-screw extrusion through gas outlet
Machine.Three of the above material adds speed using variable pump control, realizes the purpose being uniformly added into；（5）Described twin-screw extrusion
Machine is with vacuumizing and temperature control device, and composite is using extruder melting extrusion granulation, from spout to extrusion die temperature
It is 180-200 DEG C respectively, 200-230 DEG C, 220-240 DEG C, 230-250 DEG C, 240-260 DEG C, the machine screw speed of extruder
500-800r/min, charging rotating speed 40-70r/min.Product is made in cooling, pelletizing.
The mass fraction of each component is shown in Table 1 in embodiment and comparative example：
The ratio of the composite each component of table 1.
Sampling material is molded into standard batten after being dried 4 hours in 95 DEG C, carries out performance test, and performance data is shown in Table 2：
The performance test of the composite of table 2.
In embodiments of the invention, tensile strength is tested according to national standard GB/T1040.2-2006；It is bending strength, curved
Bent modulus is tested according to national standard GB/T9341-2000；Izod notched impact strength is according to national standard GB/T1843.2-1996
Tested；Heat distortion temperature is tested according to national standard GB/T1634.2-2004；Molding shrinkage presses national standard GB/
T17037.4-2003 is tested.
It can see from table 2, the compound system formed with graphene and glass fibre, to polycarbonate composite material
The performances such as impact strength, heat resistance, tensile strength, molding shrinkage all make moderate progress.
Also, shown by microscopic appearance test, the polycarbonate composite material for the epoxy resin not added（Comparative example 4）Go out
Surface floating fiber phenomenon is showed（Referring to Fig. 1）；After epoxy resin is added, embodiment 1-4 surface does not occur the phenomenon for floating fibre
（Referring to Fig. 2）.The impact strength of products obtained therefrom is strong compared with the impact for being not added with products obtained therefrom after addition graphene-epoxy resin
Degree is high, shows that graphene-epoxy resin plays stronger compatibility in the composite, by glass fibre and makrolon material
Combine, while improving the surface floating fiber phenomenon that fibrous composite easily occurs, also improve composite wood
The intensity of material.
Claims (9)
1. a kind of graphene/glass fiber reinforced polycarbonate composite, it is characterised in that including following components：60-90 matter
Measure the makrolon of part, the epoxy resin of 5-20 mass parts, the graphene of 0.01-5 mass parts, the glass fibers of 5-20 mass parts
Dimension, the silane coupler of 0.1-1 mass parts, the absolute ethyl alcohol of 5-10 mass parts, the antioxidant of 0.05-2 mass parts, 0.5-3
The compatible toughening agents of mass parts, the graphene/glass fiber reinforced polycarbonate composite is by the side that comprises the following steps
Method is made：
（1）Makrolon, the antioxidant of 0.05-2 mass parts and the 0.5-3 mass parts that 60-90 mass parts are dried it is compatible
Toughener is well mixed；
（2）The graphene of 0.01-5 mass parts is added in the epoxy resin of 5-20 mass parts, stirring at low speed is auxiliary at normal temperatures
Ultrasonic disperse 0.5-3h is helped, graphene dispersing solution is made；
（3）0.1-1 mass parts silane couplers are dissolved in 5-10 mass parts absolute ethyl alcohols, are configured to silane coupler-second
Alcoholic solution, silane coupler-ethanol solution is sprayed on 5-20 mass parts glass fibres using spray-on process, is then placed in baking oven
Middle dry 50-80min, 90-110 DEG C of drying temperature；
（4）By step（1）Middle compound is sent into double screw extruder through upstream spout；By step（2）Middle graphene dispersing solution
Through fed downstream mouth, double screw extruder melting extrusion is sent into；By step（3）Glass fibre after middle processing is sent through gas outlet
Enter double screw extruder；Three of the above material adds speed using variable pump control, realizes the purpose being uniformly added into；
（5）Described double screw extruder with vacuumizing and temperature control device, composite using extruder melting extrusion granulation,
It is 180-200 DEG C respectively from spout to extrusion die temperature, 200-230 DEG C, 220-240 DEG C, 230-250 DEG C, 240-260
DEG C, the machine screw speed 500-800r/min of extruder, charging rotating speed 40-70r/min；Product is made in cooling, pelletizing.
2. graphene according to claim 1/glass fiber reinforced polycarbonate composite, it is characterised in that described
Makrolon be inherent viscosity in 45-55ml/g aromatic copolycarbonates, aromatic copolycarbonate by least one divalent phenol and
A kind of carbonate precursor is made up of interfacial polymerization method, and carbonate precursor is carbonylic halide, halocarbonate or first
Acid esters.
3. graphene according to claim 1/glass fiber reinforced polycarbonate composite, it is characterised in that described
Makrolon is bisphenol A polycarbonate, inherent viscosity 48ml/g.
4. graphene according to claim 1/glass fiber reinforced polycarbonate composite, it is characterised in that：It is described
Epoxy resin is propane type epoxy resin of di phenolic group, glycidyl ester epoxy resin, glycidyl amine epoxy resin and fat
At least one of ring race epoxy resin.
5. graphene/glass fiber reinforced polycarbonate composite according to claim 1,2 or 3, it is characterised in that
The graphene has following performance parameter：Piece footpath is 10-50 microns, absorptance 3%-5%；Described glass fibre is alkali-free
Short glass fiber, length 3-12mm.
6. graphene according to claim 1/glass fiber reinforced polycarbonate composite, it is characterised in that：It is described
Silane coupler be 3- aminopropyl triethoxysilanes, vinyl three（'beta '-methoxy ethyoxyl）Silane and vinyl trimethoxy
At least one of base silane.
7. graphene according to claim 1/glass fiber reinforced polycarbonate composite, it is characterised in that described
One or several kinds of the antioxidant in pentaerythritol ester, phosphite ester, the positive octadecanol ester of propionic acid.
8. graphene according to claim 1/glass fiber reinforced polycarbonate composite, it is characterised in that described
Compatible toughening agents are selected from silicone powder, modified ethylene bis-fatty acid amides, copolymer of methyl methacrylate-styrene-butadiene
In one or several kinds.
A kind of 9. preparation side of graphene/glass fiber reinforced polycarbonate composite described in claim any one of 1-8
Method, it is characterised in that comprise the following steps：
（1）Makrolon, the antioxidant of 0.05-2 mass parts and the 0.5-3 mass parts that 60-90 mass parts are dried it is compatible
Toughener is well mixed；
（2）The graphene of 0.01-5 mass parts is added in the epoxy resin of 5-20 mass parts, stirring at low speed is auxiliary at normal temperatures
Ultrasonic disperse 0.5-3h is helped, graphene dispersing solution is made；
（3）0.1-1 mass parts silane couplers are dissolved in 5-10 mass parts absolute ethyl alcohols, are configured to silane coupler-second
Alcoholic solution, silane coupler-ethanol solution is sprayed on 5-20 mass parts glass fibres using spray-on process, is then placed in baking oven
Middle dry 50-80min, 90-110 DEG C of drying temperature；
（4）By step（1）Middle compound is sent into double screw extruder through upstream spout；By step（2）Middle graphene dispersing solution
Through fed downstream mouth, double screw extruder melting extrusion is sent into；By step（3）Glass fibre after middle processing is sent through gas outlet
Enter double screw extruder；Three of the above material adds speed using variable pump control, realizes the purpose being uniformly added into；
（5）Described double screw extruder with vacuumizing and temperature control device, composite using extruder melting extrusion granulation,
It is 180-200 DEG C respectively from spout to extrusion die temperature, 200-230 DEG C, 220-240 DEG C, 230-250 DEG C, 240-260
DEG C, the machine screw speed 500-800r/min of extruder, charging rotating speed 40-70r/min；Product is made in cooling, pelletizing.
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| CN109721997A (en) * | 2018-12-28 | 2019-05-07 | 方万漂 | A kind of graphene toughening polyester material and preparation method thereof |
| CN112457548B (en) * | 2020-11-26 | 2021-08-31 | 四川六九一二科技有限公司 | Preparation method of super-wear-resistant, flame-retardant, high-strength and mould-resistant graphene composite material |
| CN113372702A (en) * | 2021-05-21 | 2021-09-10 | 大河宝利材料科技(苏州)有限公司 | Graphene composite material |
| CN113604023B (en) * | 2021-08-24 | 2023-05-02 | 中山市汇鑫打印耗材有限公司 | High-strength hard plastic scraper for printer and processing technology thereof |
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