CN105820496A - Graphene/ glass fiber reinforced ABS composite and preparation method thereof - Google Patents
Graphene/ glass fiber reinforced ABS composite and preparation method thereof Download PDFInfo
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—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
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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
- 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
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Abstract
The invention discloses a graphene/ glass fiber reinforced ABS composite. The graphene/ glass fiber reinforced ABS composite comprises, by weight, 60-90 parts of ABS, 5-20 parts of epoxy resin, 0.01-5 parts of graphene, 1-6 parts of glass fibers, 0.01-0.1 part of a silane coupling agent, 1-2 parts of ethanol, 0.05-2 parts of antioxidant and 0.5-3 parts of compatible flexibilizer. The invention further discloses a preparation method of the graphene/ glass fiber reinforced ABS composite. The graphene/ glass fiber reinforced ABS composite prepared through the preparation method is simple in preparation process, and in addition, the experimental results show that heat stability, strength and toughness of the prepared graphene/ glass fiber reinforced ABS composite are obviously improved; the fiber floatation phenomenon is effectively eliminated, and therefore practical application of the ABS composite can be expanded.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of Graphene/glass fiber reinforced ABS composite material and
Its preparation method.
Background technology
ABS(acrylonitrile butadiene styrene terpolymer) it is a kind of novel universal developed the forties in 20th century
Thermoplastic engineering plastic, be a kind of styrene with polybutadiene chain as skeleton and acrylonitrile graft copolymer and styrene,
The multiphase polymer that acrylonitrile is copolymer blended.ABS has a good combination property: resistance to chemical attack, processing fluidity
And higher case hardness, thermostability, toughness, impact property and rigidity, have been widely used in the various machines of making at present
Tool, the parts of instrument and equipment and electrical equipment, the shell of instrument.But, molding shrinkage bigger for ABS, relatively low thermal deformation temperature
Degree and relatively low bending strength, processing and rear assembling to goods bring certain difficulty.Glass fibre reinforced composite material be with
Polymer is matrix, the composite made with glass as reinforcing material, combines the performance of polymer and glass.Research table
Bright in ABS, add fibrous material, can the greatly intensity of reinforcing material and shrinkage factor, and improve the thermostability of material.
Rubber and plastic industry has carried out the research work relevant to ABS/ graphene nanocomposite material high performance the most.In
State's number of patent application 201510446241.3, open a kind of Graphene-ABS composite flame-proof plastics and preparation method thereof, are improving
Other performances of ABS are not affected while fire resistance.Chinese Patent Application No. 201510589095. X, it is provided that a kind of LED
With filling-modified PA6/ABS composite heat-conducting plastics of nano-silicon nitride-Graphene and preparation method thereof, this heat-conducting plastic is by PA6
Being used in mixed way with ABS, composite shows excellence in terms of plasticity, durability, electric insulating quality；Chinese patent
201410456105.8, it is specifically related to a kind of method that body in-situ polymerization prepares Graphene/ABS composite material.This method is by rubber
Peptization solution in a solvent, adds styrene, acrylonitrile monomer, Graphene, carries out polymerisation in bulk, it is thus achieved that Graphene/ABS is combined
Material；Chinese patent 201410456117. 0, it is provided that a kind of method of in-situ modified ABS resin.The method is at emulsion graft polymerization
Graphene is introduced during SAN blending method, by changing addition and the addition manner of Graphene, can be at bigger model
Enclose heat conduction, conduction and the mechanical property of interior regulation composite thus obtain the composite of excellent performance.
It is comprehensive that correlational study shows that the addition of Graphene makes ABS composite material possess excellent mechanics, calorifics, electricity etc.
Can, but in method made above, directly Graphene is mixed matrix and is unfavorable for Graphene dispersibility in ABS matrix and phase
Capacitive；And prepare composite by methods such as Graphene in-situ polymerization, coupling modifier, in actual production, technique is loaded down with trivial details, stone
Form and the performance change of ink alkene are difficult to control.The Graphene of structural integrity is made up of phenyl ring, and chemical stability is high, and surface is lazy
Property, weak with other medium effect；And graphene film interlayer exists stronger Van der Waals force, easily reunite, greatly limit its research application；
How to use high-efficient simple, the method for application easy to implement to realize Graphene fine dispersion in ABS material, be to prepare high property
The key of energy ABS/ graphene nanocomposite material.Epoxy resin is added in glass fiber reinforced ABS material, it is possible to effectively
The floating fine phenomenon of elimination, and by selecting raw material and controlling preparation condition, Graphene is capable of good in the epoxy
Dispersibility.Therefore the present invention is first with the epoxy resin dispersibility to Graphene, prepares graphene dispersing solution, then by graphite
Alkene-epoxy resin adds ABS composite material to, obtains a kind of novel graphite alkene/glass fiber reinforced ABS composite material.
Summary of the invention
It is an object of the invention to provide a kind of Graphene/glass fiber reinforced ABS composite material and preparation method thereof, should
It is low that material has possessed Graphene addition, good mechanical property, processing characteristics and heat stability.Eliminating glass fiber reinforcement
While the floating fine phenomenon of ABS composite material, it is achieved that Graphene in the composite dispersed.
For reaching above-mentioned purpose, the composite that the present invention provides includes the component of following parts by weight: 60-90 mass parts
The epoxy resin of ABS, 5-20 mass parts, the Graphene of 0.01-5 mass parts, the glass fibre of 1-6 mass parts, 0.01-0.1
The silane coupler of mass parts, the ethanol of 1-2 mass parts, the antioxidant of 0.05-2 mass parts, the compatible increasing of 0.5-3 mass parts
Tough dose.
Described ABS is acrylonitrile, butadiene and cinnamic copolymer, and wherein the percentage composition of butadiene unit is 10-
40 wt%；Described epoxy resin is propane type epoxy resin of di phenolic group, glycidyl ester epoxy resin, (+)-2,3-Epoxy-1-propanol amine ring
At least one in epoxy resins and cycloaliphatic epoxy resin；Described glass fibre is alkali-free short glass fiber, a length of 3-
Silane coupler described in 12mm is 3-aminopropyl triethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane and ethylene
At least one of base trimethoxy silane；Described antioxidant is selected from pentaerythritol ester, phosphite ester, propanoic acid positive octadecanol ester
In one or several；Described compatible toughening agents is selected from silicone powder, modified ethylene bis-fatty acid amides, methyl methacrylate
Ester-SB.
Described Graphene has following performance parameter: sheet footpath is 5-500 micron, and absorptance is 3%-5%, used by the present invention
It is 10-50 micron that Graphene usually has the Graphene of single or multiple lift structure, preferably sheet footpath, and thickness is 1-5 nanometer, compares table
Area is 20m-800m2The single-layer graphene of/g, single-layer graphene specific surface area is bigger, and the hot property enhancing of goods becomes apparent from,
The most preferred.
Heretofore described Graphene/glass fiber reinforced ABS composite material, adds the graphite of 0.01-5 part in proportion
Alkene, preferably 0.1-2 part.When content is the lowest, the reinforced effects that Graphene plays is limited；When it is too high, composite
The middle dispersed meeting realizing Graphene is relatively difficult, significantly improves material processing technique requirement, the most preferred above-mentioned model
Enclose.
The preparation method of heretofore described Graphene/glass fiber reinforced ABS composite material, comprises the following steps:
(1) ABS that 60-90 part is dried, antioxidant 0.05-2 part, compatible toughening agents 0.5-3 part, mix homogeneously are weighed；
(2) being joined by the Graphene of 0.01-5 mass parts in the epoxy resin of 5-20 mass parts, stirring at low speed is auxiliary at normal temperatures
Help ultrasonic disperse 0.5-3h, prepare graphene dispersing solution；
(3) 0.01-0.1 mass parts silane coupler is dissolved in 1-2 mass parts dehydrated alcohol, be configured to silane coupler-
Ethanol solution, utilizes nebulization by spray solution on 1-6 part glass fibre, is then placed in baking oven being dried 50-80min, dry
Dry temperature 90-110 DEG C；
(4) by compound in step (1) through upstream spout, double screw extruder is sent into；By graphene dispersing solution in step (2)
Through fed downstream mouth, send into double screw extruder melted crowded；Glass fibre after processing in step (3), through gas outlet, is sent into
Double screw extruder.Three of the above material utilizes variable pump to control to add speed, it is achieved the purpose being uniformly added into；
(5) double screw extruder described in is with evacuation and attemperating unit, and composite uses extruder to melt extrude pelletize,
It is 190-210 DEG C from spout respectively to extrusion die temperature, 210-240 DEG C, 230-250 DEG C, 240-260 DEG C, 250-270
DEG C, the machine screw speed 400-1000r/min of extruder, feed rotating speed 30-60r/min.Cooling, pelletizing prepares product.
The method have the advantages that the Graphene/glass fiber reinforced ABS composite material prepared by the present invention,
Not only preparation technology is simple, and experimental result show prepared by the impact strength of ABS composite material, thermostability, stretching strong
The performances such as degree, molding shrinkage are obviously improved, thus can expand the practical ranges of ABS composite material.
Accompanying drawing illustrates:
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.
Detailed description of the invention
Embodiments of the invention are given below, by embodiment, the present invention are specifically described.Be necessary it is pointed out here that
, embodiment is to further instruction of the present invention, it is impossible to be interpreted as limitation of the scope of the invention, the technology in this field
Present disclosure can be made some and be adjusted by personnel.
The preparation process of a kind of Graphene/glass fiber reinforced ABS composite material comprises the following steps: (1) weighs dry
ABS, antioxidant, compatible toughening agents, mix homogeneously；(2) Graphene is joined in glycidyl amine epoxy resin,
Under room temperature, stirring at low speed assisting ultrasonic dispersion 2h, prepares graphene dispersing solution；(3) silane coupler is dissolved in dehydrated alcohol
In, it is configured to silane coupler-ethanol solution, utilizes nebulization by spray solution on the glass fibers, be then placed in baking oven
It is dried 50-80min, baking temperature 90-110 DEG C；(4) by compound in step (1) through upstream spout, twin-screw extrusion is sent into
Machine.By graphene dispersing solution in step (2) through fed downstream mouth, send into double screw extruder melted crowded.Step (3) will be processed
After glass fibre through gas outlet, send into double screw extruder.Three of the above material utilizes variable pump to control to add speed, it is achieved
The purpose being uniformly added into；(5) double screw extruder described in is with evacuation and attemperating unit, and composite uses extruder to melt
Melt extruding pelletization, be 190-210 DEG C from spout respectively to extrusion die temperature, 210-240 DEG C, 230-250 DEG C, 240-260
DEG C, 250-270 DEG C, the machine screw speed 400-1000r/min of extruder, feed rotating speed 30-60r/min.Cooling, pelletizing prepares
Product.
In embodiment and comparative example, the mass fraction of each component is shown in Table 1:
The ratio of each component of table 1. composite
Sampling material is dried after 4 hours in 90 DEG C and is molded into standard batten, carries out performance test, and performance data is shown in Table 2:
The performance test of table 2. composite
In embodiments of the invention, hot strength is tested according to GB GB/T1040.2-2006；Bending strength, bending die
Amount is tested according to GB GB/T9341-2000；Izod notched impact strength is carried out according to GB GB/T1843.2-1996
Test；Heat distortion temperature is tested according to GB GB/T1634.2-2004；Molding shrinkage presses GB GB/T17037.4-
2003 test.
It will be seen that the compound system formed with Graphene and glass fibre, the impact to ABS composite material from table 2
The performances such as intensity, thermostability, hot strength, molding shrinkage all make moderate progress.
Further, microscopic appearance test showing, the ABS composite material (comparative example 4) of the epoxy resin not added occurs in that
Surface floating fiber phenomenon (sees Fig. 1)；After adding epoxy resin, the surface of embodiment 1-4 does not all occur that floating fine phenomenon (sees
Fig. 2).After adding Graphene-epoxy resin, the impact strength of products obtained therefrom is the most relatively not added with the impact strength height of products obtained therefrom,
Show that Graphene-epoxy resin plays the stronger compatibility in the composite, glass fibre is organically combined with ABS material
Together, while improving the surface floating fiber phenomenon that fibrous composite easily occurs, the intensity of composite is also improved.
Claims (10)
1. Graphene/glass fiber reinforced ABS composite material, it is characterised in that include following components: 60-90 mass parts
The epoxy resin of ABS, 5-20 mass parts, the Graphene of 0.01-5 mass parts, the glass fibre of 1-6 mass parts, 0.01-0.1
The silane coupler of mass parts, the dehydrated alcohol of 1-2 mass parts, the antioxidant of 0.05-2 mass parts, the phase of 0.5-3 mass parts
Hold toughener.
Graphene/glass fiber reinforced ABS composite material the most according to claim 1, it is characterised in that described ABS is
Being acrylonitrile, butadiene and cinnamic copolymer, wherein the percentage composition of butadiene unit is 10-40 wt%.
Graphene/glass fiber reinforced ABS composite material the most according to claim 1, it is characterised in that described asphalt mixtures modified by epoxy resin
Fat is propane type epoxy resin of di phenolic group, glycidyl ester epoxy resin, glycidyl amine epoxy resin and alicyclic ring
At least one in epoxy resins.
4. according to the Graphene/glass fiber reinforced ABS composite material described in claim 1,2 or 3, it is characterised in that described
Graphene has following performance parameter: sheet footpath is 5-500 microns, and absorptance is 3%-5%.
Graphene/glass fiber reinforced ABS composite material the most according to claim 4, it is characterised in that described Graphene
Being 10-50 micron for sheet footpath, thickness is 1-5nm, and specific surface area is 20m-800m2The single-layer graphene of/g.
Graphene/glass fiber reinforced ABS composite material the most according to claim 1, it is characterised in that: described glass
Fiber is alkali-free short glass fiber, a length of 3-12mm.
Graphene/glass fiber reinforced ABS composite material the most according to claim 1, it is characterised in that: described silane
Coupling agent is 3-aminopropyl triethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane and vinyltrimethoxy silane
At least one.
Graphene/glass fiber reinforced ABS composite material the most according to claim 1, it is characterised in that described antioxidation
Agent is selected from one or several in pentaerythritol ester, phosphite ester, propanoic acid positive octadecanol ester.
Graphene/glass fiber reinforced ABS composite material the most according to claim 1, it is characterised in that described compatible increasing
Tough dose of in silicone powder, modified ethylene bis-fatty acid amides, copolymer of methyl methacrylate-styrene-butadiene
Plant or several.
10. the preparation method of a kind of Graphene/glass fiber reinforced ABS composite material described in any one of claim 1-9, its
It is characterised by, comprises the following steps:
(1) antioxidant of ABS, 0.05-2 mass parts that 60-90 mass parts is dried and the compatible toughening agents of 0.5-3 mass parts
Mix homogeneously；
(2) being joined by the Graphene of 0.01-5 mass parts in the epoxy resin of 5-20 mass parts, stirring at low speed is auxiliary at normal temperatures
Help ultrasonic disperse 0.5-3h, prepare graphene dispersing solution；
(3) 0.01-0.1 mass parts silane coupler is dissolved in 1-2 mass parts dehydrated alcohol, be configured to silane coupler-
Ethanol solution, utilizes nebulization to be sprayed on 1-6 mass parts glass fibre by silane coupler-ethanol solution, is then placed in drying
Case is dried 50-80min, baking temperature 90-110 DEG C；
(4) by compound in step (1) through upstream spout, double screw extruder is sent into；By graphene dispersing solution in step (2)
Through fed downstream mouth, send into double screw extruder melted crowded；Glass fibre after processing in step (3), through gas outlet, is sent into
Double screw extruder；Three of the above material utilizes variable pump to control to add speed, it is achieved the purpose being uniformly added into；
(5) double screw extruder described in is with evacuation and attemperating unit, and composite uses extruder to melt extrude pelletize,
It is 190-210 DEG C from spout respectively to extrusion die temperature, 210-240 DEG C, 230-250 DEG C, 240-260 DEG C, 250-270
DEG C, the machine screw speed 400-1000r/min of extruder, feed rotating speed 30-60r/min；Cooling, pelletizing prepares product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851982A (en) * | 2019-01-23 | 2019-06-07 | 芜湖博元材料科技有限公司 | Anti-aging high fire-retardance ABS material for car interior trim parts and preparation method thereof |
| CN111019256A (en) * | 2019-12-10 | 2020-04-17 | 江门市江海区新雄利塑料科技有限公司 | Modified engineering plastic and preparation method thereof |
| CN113416352A (en) * | 2021-07-07 | 2021-09-21 | 合肥市丽红塑胶材料有限公司 | Modified plastic composite material and preparation method thereof |
| CN115449180A (en) * | 2022-09-30 | 2022-12-09 | 中国重汽集团济南动力有限公司 | Fiber-reinforced ABS material for additive manufacturing and preparation method thereof |
| CN118459925A (en) * | 2024-04-25 | 2024-08-09 | 广东君邦新材料科技有限公司 | Preparation method of functionalized graphene modified ABS composite material |
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| CN109851982A (en) * | 2019-01-23 | 2019-06-07 | 芜湖博元材料科技有限公司 | Anti-aging high fire-retardance ABS material for car interior trim parts and preparation method thereof |
| CN111019256A (en) * | 2019-12-10 | 2020-04-17 | 江门市江海区新雄利塑料科技有限公司 | Modified engineering plastic and preparation method thereof |
| CN113416352A (en) * | 2021-07-07 | 2021-09-21 | 合肥市丽红塑胶材料有限公司 | Modified plastic composite material and preparation method thereof |
| CN115449180A (en) * | 2022-09-30 | 2022-12-09 | 中国重汽集团济南动力有限公司 | Fiber-reinforced ABS material for additive manufacturing and preparation method thereof |
| CN118459925A (en) * | 2024-04-25 | 2024-08-09 | 广东君邦新材料科技有限公司 | Preparation method of functionalized graphene modified ABS composite material |
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| CN105820496B (en) | 2018-04-03 |
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