CN108587149A - A kind of waste recovery conductive carbon fibre thermoplastic composite and preparation method thereof - Google Patents
A kind of waste recovery conductive carbon fibre thermoplastic composite and preparation method thereof Download PDFInfo
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- CN108587149A CN108587149A CN201810431129.6A CN201810431129A CN108587149A CN 108587149 A CN108587149 A CN 108587149A CN 201810431129 A CN201810431129 A CN 201810431129A CN 108587149 A CN108587149 A CN 108587149A
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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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
- C08K2201/001—Conductive additives
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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
- C08K2201/011—Nanostructured additives
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Abstract
The present invention relates to new-energy automobile field of material technology, more particularly to a kind of waste recovery conductive carbon fibre thermoplastic composite and preparation method thereof.It is composed of the following components by weight percentage：PA6 30‑50%；Carbon fiber 20 30%；Waste Composite Material 20 30%；Conducting particles 4 15%；Reinforcing agent 1 10%；Heat stabilizer 0.1 1%；Dispersant 1 3%, wherein conducting particles include carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1: 1；The PA6 grain sizes are no more than 25 μm.The object of the present invention is to provide a kind of waste recovery conductive carbon fibre thermoplastic composites and preparation method thereof with preferable electric conductivity.
Description
Technical field
The present invention relates to new-energy automobile field of material technology, more particularly to a kind of waste recovery conductive carbon fibre thermoplasticity
Composite material and preparation method.
Background technology
Carbon fibre composite is an important branch in composite material, since it has excellent performance, this material in recent years
The purposes and yield of material gradually expand.For a long time, carbon fibre reinforced composite is counted as a kind of material of costliness, price
About ten times of glass fibre reinforced composion are served only for the sophisticated technologies industry such as military project, aerospace.In recent years, carbon fiber is every
Year is increased with 50% or more speed, wherein there are two the development that key factor has pushed carbon fibre composite, first, to above-mentioned
Deepening continuously for material understanding, makes its performance be gradually improved, can reach the performance that many other materials hardly match, it is promoted to make
Dosage constantly rises.Second is that the continuous reduction of cost effectiveness, this be mainly attributed to Industry of Carbon Fiber can provide the fiber of high quality with
And fiber/matrix melting technology is constantly progressive.The large-scale production of carbon fiber makes its Quality advance and price fall, and adds
The progress of work technology makes the carbon fiber dimensional ratio in addition composite material constantly rise again, at present up to volume ratio 60% with
On.
Carbon fibre composite development is like a raging fire, breaks with tremendous force.Thermosetting is mostly applied in space flight and aviation and national defense industry
Property composite material, however same with thermosetting compound material is of high cost, and molding cycle is long, and greatest problem is difficult to recycle, and pollutes environment
Consequence is serious.By being dedicated to base-material research and development for many years, successively select PC, PEEK, PPS, PI, PA, PET, PP as the examination of base-material
It tests.From the experiment, it was found that PA is a kind of particularly important thermoplastic web.Though PA itself is the engineering plastics haveing excellent performance, inhale
Moist big, product size stability is poor, and intensity is also nothing like metal with hardness, in order to overcome these disadvantages, using carbon fiber
Or the fiber of other kinds is enhanced to improve its performance.It has developed rapidly in recent years with fibre reinforced PA materials, because of PA
All be the material that engineering plastics field is had excellent performance with carbon fiber, the compound synthesis of the two embodies respective advantage, intensity with just
Property it is more much higher than non-reinforced nylon, creep is small, and dimensional accuracy is good, and thermal stability significantly improves, wear-resisting, and damping and amortization is excellent, with
Fiberglass reinforced, which is compared, better performance.But it is poor to exist on electric conductivity with regard to the carbon fibre composite that PA is base-material at present
Different, conductivity is not high, and therefore, the present invention has made improvement for such case.
Invention content
In order to overcome the shortcomings of background technology, it is useless that the object of the present invention is to provide one kind with preferable electric conductivity
Material recycling conductive carbon fibre thermoplastic composite and preparation method thereof.
The technical solution adopted in the present invention is：A kind of waste recovery conductive carbon fibre thermoplastic composite, by weight
Percentage is composed of the following components：
PA6 30-50%
Carbon fiber 20-30%
Waste Composite Material 20-30%
Conducting particles 4-15%
Reinforcing agent 1-10%
Heat stabilizer 0.1-1%
Dispersant 1-3%
The conducting particles includes carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；
The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1: 1；
The PA6 grain sizes are no more than 25 μm.
Preferably, the heat stabilizer is organic tin heat stabilizer or organic compound heat stabilizer.
Preferably, the reinforcing agent is maleic anhydride grafted high density polyethylene.
Preferably, the dispersant is that barium stearate, zinc stearate or calcium stearate are one such.
Preferably, the length of carbon nanotube is 50-100nm.
Preferably, a diameter of 20-30nm of the nanometer alumina particles.
A kind of preparation method of waste recovery conductive carbon fibre thermoplastic composite, includes the following steps：
1）By carbon fiber and PA6 by the abundant drying for standby of dryer, drying time is 4-5 hours, and the material after drying is made to contain
Water is less than 0.02wt%；
2）The PA6 thermoplastic composites scrapped are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into dryer
Waste material after go-no-go is granulated by comminutor spare by drying by the waste material after drying by separating machine go-no-go；
3）It will be stirred in nanometer alumina particles under vacuum 70-100 degree Celsius ranges, be passed through the hydrogen of 30-50 pa pressure, together
When be passed through the graphite gas of 50-100 pas, by 24-48 hours, then cool down and the dilute coating nano aluminium particle of graphite oxide be made
It is spare.
4）Receiving in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3 is expected into alumina particles, carbon
Nanotube, reinforcing agent and heat stabilizer hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4, dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
The beneficial effects of the invention are as follows：The waste material recycled using automobile is added in composite material, reduces cost, and meet
Environmental requirement；Conducting particles is added in base-material, makes composite material that there is preferable conductive effect, conductive particle of the invention
Son is carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；Due to the dilute cladding alumina particles of graphite oxide so that graphite oxide
Dilute outer diameter increases, and can thus reduce the possibility of the dilute aggregation of graphite oxide, and graphite oxide is dilute is coated on a nanometer alumina particles
It is upper, therefore can prevent to receive material alumina particles oxidation again, coordinate dispersant, not only carbon fiber is made to be uniformly dispersed, while making oxidation stone
The dilute coating nano aluminium particle of ink is evenly distributed in the composite, increases its electric conductivity, and the composite material of the present invention is made to have
Preferable conductive effect.
Specific implementation mode
The present invention provides a kind of waste recovery conductive carbon fibre thermoplastic composites, by weight percentage by with the following group
It is grouped as：
PA6 30-50%
Carbon fiber 20-30%
Waste Composite Material 20-30%
Conducting particles 4-15%
Reinforcing agent 1-10%
Heat stabilizer 0.1-1%
Dispersant 1-3%
The conducting particles includes carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；
The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1: 1；
The PA6 grain sizes are no more than 25 μm.
The heat stabilizer is organic tin heat stabilizer or organic compound heat stabilizer.
The reinforcing agent is maleic anhydride grafted high density polyethylene.
The dispersant is that barium stearate, zinc stearate or calcium stearate are one such.
The length of carbon nanotube is 50-100nm.
A diameter of 20-30nm of the nanometer alumina particles.
A kind of preparation method of waste recovery conductive carbon fibre thermoplastic composite, includes the following steps：
1）By carbon fiber and PA6 by the abundant drying for standby of dryer, drying time is 4-5 hours, and the material after drying is made to contain
Water is less than 0.02wt%；
2）The PA6 thermoplastic composites scrapped are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into dryer
Waste material after go-no-go is granulated by comminutor spare by drying by the waste material after drying by separating machine go-no-go；
3）It will be stirred in nanometer alumina particles under vacuum 70-100 degree Celsius ranges, be passed through the hydrogen of 30-50 pa pressure, together
When be passed through the graphite gas of 50-100 pas, by 24-48 hours, then cool down and the dilute coating nano aluminium particle of graphite oxide be made
It is spare.
4）Receiving in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3 is expected into alumina particles, carbon
Nanotube, reinforcing agent and heat stabilizer hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4, dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
In said program, the waste material recycled using automobile is added in composite material, reduces cost, and meet environmental protection and want
It asks；Conducting particles is added in base-material, makes composite material that there is preferable conductive effect, conducting particles of the invention to be received for carbon
Mitron and the dilute coating nano aluminium particle of graphite oxide；Due to the dilute cladding alumina particles of graphite oxide so that the dilute outer diameter of graphite oxide
Increase, can thus reduce the possibility of the dilute aggregation of graphite oxide, and graphite oxide is dilute is coated on the upper of nanometer alumina particles, therefore
It can prevent to receive again and expect alumina particles oxidation, coordinate dispersant, not only carbon fiber is made to be uniformly dispersed, while the dilute cladding of graphite oxide being made to receive
Rice alumina particles are evenly distributed in the composite, increase its electric conductivity, so that the composite material of the present invention is had preferable conductive
Effect.
Below by four groups of embodiments, the invention will be further described：
Embodiment one：
1）By 30% carbon fiber and 30% PA6 by the abundant drying for standby of dryer, drying time is 4 hours, make it is dry after
Material moisture be less than 0.02wt%；
2）Scrap 30% PA6 thermoplastic composites are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by comminutor spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3）By nanometer alumina particles stir in 70 degree Celsius ranges under vacuum, be passed through the hydrogen of 30 pa pressure, lead to simultaneously
The graphite gas for entering 50 pas, by 24 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4）By 6% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 2% reinforcing agent and 1% heat stabilizer hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4,1% dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
Embodiment two：
1）By 30% carbon fiber and 40% PA6 by the abundant drying for standby of dryer, drying time is 4 hours, make it is dry after
Material moisture be less than 0.02wt%；
2）Scrap 20% PA6 thermoplastic composites are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by comminutor spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3）By nanometer alumina particles stir in 80 degree Celsius ranges under vacuum, be passed through the hydrogen of 30 pa pressure, lead to simultaneously
The graphite gas for entering 70 pas, by 30 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4）By 8% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 1% reinforcing agent hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4,1% dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
Embodiment three：
1）By 50% carbon fiber and 20% PA6 by the abundant drying for standby of dryer, drying time is 4 hours, make it is dry after
Material moisture be less than 0.02wt%；
2）Scrap 20% PA6 thermoplastic composites are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by comminutor spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3）By nanometer alumina particles stir in 90 degree Celsius ranges under vacuum, be passed through the hydrogen of 30 pa pressure, lead to simultaneously
The graphite gas for entering 90 pas, by 35 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4）By 7% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 1% reinforcing agent and 1% heat stabilizer hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4,1% dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
Example IV：
1）By 25% carbon fiber and 40% PA6 by the abundant drying for standby of dryer, drying time is 4 hours, make it is dry after
Material moisture be less than 0.02wt%；
2）Scrap 25% PA6 thermoplastic composites are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by comminutor spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3）By nanometer alumina particles stir in 100 degree Celsius ranges under vacuum, be passed through the hydrogen of 30 pa pressure, lead to simultaneously
The graphite gas for entering 90 pas, by 35 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4）By 7% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 1% reinforcing agent glue and 1% heat stabilizer hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4,1% dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
Embodiment 1~4 is formulated and material property is shown in Table 1：
| Embodiment one | Embodiment two | Embodiment three | Example IV | |
| PA6 | 30 | 40 | 50 | 40 |
| Carbon fiber | 30 | 30 | 20 | 25 |
| The composite material scrapped | 30 | 20 | 20 | 25 |
| Conducting particles | 6 | 8 | 7 | 7 |
| Reinforcing agent | 2 | 1 | 1 | 1 |
| Heat stabilizer | 1 | 0 | 1 | 1 |
| Dispersant | 1 | 1 | 1 | 1 |
| Interlaminar fracture toughness/(kj/m2) | 1.1-2.0 | 1.2-1.5 | 0.8-1.0 | 1.1-1.2 |
| Tensile strength/MPa | 3053 | 3057 | 2870 | 3032 |
| Tensile modulus of elasticity/GPa | 152 | 150 | 131 | 149 |
| Bending strength/MPa | 1580 | 1572 | 1480 | 1558 |
| The modulus of elasticity in static bending/GPa | 142 | 137 | 114 | 139 |
| Conductivity（S/cm） | 6500 | 6500 | 6500 | 6500 |
| Notch impact strength | 10.2 | 9.7 | 8.6 | 9.8 |
Claims (8)
1. a kind of waste recovery conductive carbon fibre thermoplastic composite, it is characterised in that：By weight percentage by following components
Composition：
PA6 30-50%
Carbon fiber 20-30%
Waste Composite Material 20-30%
Conducting particles 4-15%
Reinforcing agent 1-10%
Heat stabilizer 0.1-1%
Dispersant 1-3%
The conducting particles includes carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；
The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1: 1；
The PA6 grain sizes are no more than 25 μm.
2. a kind of waste recovery conductive carbon fibre thermoplastic composite according to claim 1, it is characterised in that：It is described
Heat stabilizer be organic tin heat stabilizer or organic compound heat stabilizer.
3. a kind of waste recovery conductive carbon fibre thermoplastic composite according to claim 1, it is characterised in that：It is described
Reinforcing agent be maleic anhydride grafted high density polyethylene.
4. a kind of waste recovery conductive carbon fibre thermoplastic composite according to claim 1, it is characterised in that：It is described
Dispersant be barium stearate, zinc stearate or calcium stearate it is one such.
5. a kind of waste recovery conductive carbon fibre thermoplastic composite according to claim 1, it is characterised in that：Carbon is received
The length of mitron is 50-100nm.
6. a kind of waste recovery conductive carbon fibre thermoplastic composite according to claim 1, it is characterised in that：It is described
A diameter of 20-30nm of nanometer alumina particles.
7. a kind of preparation method of waste recovery conductive carbon fibre thermoplastic composite, it is characterised in that：Include the following steps：
1）By carbon fiber and PA6 by the abundant drying for standby of dryer, drying time is 4-5 hours, and the material after drying is made to contain
Water is less than 0.02wt%；
2）The PA6 thermoplastic composites scrapped are recycled and are cleaned by cleaning machine, the waste material after cleaning is passed through into dryer
Waste material after go-no-go is granulated by comminutor spare by drying by the waste material after drying by separating machine go-no-go；
3）It will be stirred in nanometer alumina particles under vacuum 70-100 degree Celsius ranges, be passed through the hydrogen of 30-50 pa pressure, together
When be passed through the graphite gas of 50-100 pas, by 24-48 hours, then cool down and the dilute coating nano aluminium particle of graphite oxide be made
It is spare.
8.4）Receive material alumina particles, carbon in mixed PA6 in step 1, the Waste Composite Material in step 2, step 3 is received
Mitron, reinforcing agent and heat stabilizer hybrid reaction；
5）Screw extruder hopper is added in mixture after hybrid reaction in step 4, dispersion is added when stirring for high-speed stirred
Agent, and add fine mouth to be added by extruder on carbon fiber, extruding pelletization is to get to conductive carbon fibre thermoplastic composite.
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Application publication date: 20180928 |