CN110343364A - A kind of epoxy resin toughened composite material and its preparation and application - Google Patents
A kind of epoxy resin toughened composite material and its preparation and application Download PDFInfo
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- CN110343364A CN110343364A CN201910574632.1A CN201910574632A CN110343364A CN 110343364 A CN110343364 A CN 110343364A CN 201910574632 A CN201910574632 A CN 201910574632A CN 110343364 A CN110343364 A CN 110343364A
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- epoxy resin
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- curing agent
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
Abstract
The present invention relates to a kind of epoxy resin toughened composite material and its preparations and application, and in parts by weight, raw material components include: 80-100 parts of epoxy resin, and 10-20 parts of curing agent, 10-25 parts of polysulfones PSF, carbon nanotube and/or 0.01-1 parts of graphene.Epoxy resin provided by the invention, impact flexibility, bending strength and modulus, tensile strength and modulus all improve.
Description
Technical field
The invention belongs to epoxy resin composite material and its preparation and application fields, in particular to a kind of epoxy resin toughened
Composite material and its preparation and application.
Background technique
Epoxy resin is a kind of thermosetting polymer in molecule containing two or more epoxy groups, excellent because having
The characteristics such as different mechanical performance, heat resistance, chemical stability, and it is widely used in the Primary resins matrix of advanced composite material.
It is in tridimensional network since epoxy resin cure post-crosslinking density is high, thus that there are internal stress is big, matter is crisp, poor impact resistance
The disadvantages of, it is difficult to meet advanced composite material in the requirement of engineering field, is subject to certain restrictions its application.Therefore to epoxy
The toughening modifying of resin is always the heat subject studied.
Carbon nanotube is the co-axial hollow " micro-pipe " as made of the hexagonal mesh winding of similar graphite-structure, both ends
" carbon cap " participates in closing by pentagon or heptagon grid.According to the difference of the graphite flake number of plies, carbon nanotube can be divided into single-walled pipe
With two kinds of multi-walled pipes, due to the radial dimension very little of carbon nanotube, diameter is generally in a few nanometers to tens of nanometers, and carbon nanotube
Length generally at several microns to several millimeters, therefore, it is century that carbon nanotube, which is considered as a kind of typical monodimension nanometer material,
One of most promising nano material is theoretically the ideal function of composite material and reinforcing material.
Polysulfones is a kind of thermoplastic engineering plastic, and excellent in mechanical performance, rigidity is big, wear-resisting, high-intensitive, even if at high temperature
Also excellent mechanical property is kept, long-term use temperature is 160 DEG C, and short-period used temperature is 190 DEG C, and thermal stability is high, water-fast
It solves, good stability of the dimension, under molding shrinkage, nontoxic, radiation hardness, resistance to combustion has self-extinguishment.Have in entire thermoplastic
Highest creep properties.The ductile rupture intensity of product significantly increases after its modified epoxy, it is however generally that, molecular weight is got over
Greatly, proportion is bigger, and the toughness of modified oxygen resin is bigger, but the melting of system is suddenly spent and also increased with it, under processing performance
Drop.
Carbon nanotube and the own hot spot through becoming carbon nanomaterial research field of carbon nano-fiber enhancing composite material.
Compared with traditional polyacrylonitrile-based carbon fibre, carbon nanotube and carbon nano-fiber have excellent elasticity modulus, intensity, fracture
Toughness and bending property, therefore carbon nanomaterial can be used as the nanocomposite of reinforcement preparation excellent in mechanical performance, in addition
Addition can also improve the glass transition temperature of composite material, improve the heat resistance of composite material.Epoxy resin is multiple
The common thermosetting resin matrix of condensation material is handed over if formed using carbon nanotube as the curing agent of epoxy resin and epoxy resin
Networking network, can not only improve the dispersibility of carbon nanotube, but also the enhancing composite material of available function admirable.CN
109517344 A disclose a kind of high-modulus high-toughness epoxy resin, but the toughening agent content being added is larger, production cost
Higher, production process is complex, and dispersion effect of the nanoparticle in toughened system be not excellent.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of epoxy resin toughened composite material and its preparation and application,
Existing inorganic nano-particle is overcome to disperse uneven defect in resin matrix, the present invention is a kind of using epoxy resin as base-material,
Carbon nanotube or graphene, polysulfone resin and curing agent are added, is heating and curing to obtain the ring of carbon nanotube and polysulfones activeness and quietness
Epoxy resin composite material.
A kind of epoxy resin composite material of the invention, in parts by weight, raw material components include: epoxy resin 80-100
Part, 10-20 parts of curing agent, 10-25 parts of polysulfones PSF, carbon nanotube and/or 0.01-1 parts of graphene.
The epoxy resin is bisphenol A type epoxy resin；Curing agent is amine curing agent, one in acid anhydride type curing agent
Kind；Polysulfones used is hydroxy-end capped.
The amine curing agent is DETDA or GY-051, and acid anhydride type curing agent is methyl tetrahydro phthalic anhydride or methyl hexahydro
Phthalic anhydride；Epoxy resin is epoxy resin E51.
In parts by weight, raw material components are as follows: 80 parts of epoxy resin；20 parts of curing agent, 10-25 parts of polysulfones, graphene 0.25-
1 part.
In parts by weight, raw material components are as follows: 80 parts of epoxy resin；20 parts of curing agent, 10-25 parts of polysulfones, carbon nanotube
0.01-0.125 parts.
A kind of preparation method of epoxy resin composite material of the invention, comprising:
(1) epoxy resin of drying and polysulfones are mixed, oil bath pan heating stirring becomes clarifying to system from muddiness, is added
Carbon nanotube and/or graphene dispersing solution, stirring, vacuum defoamation are added curing agent, obtain curing system；
(2) curing system is poured into and is previously added in the casting grinding tool of release agent, heating in vacuum deaeration solidifies to get ring
Epoxy resin composite material.
The preferred embodiment of above-mentioned preparation method is as follows:
Oil bath pan heating stirring temperature is 120 DEG C in the step (1).
The solvent of carbon material dispersion liquid is N, N- dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydro in the step (1)
Furans.Carbon nanotube or graphene dispersing solution specifically: solvent in solvent, ultrasound point is added in carbon nanotube and/or graphene
It dissipates and uniformly (takes minute quantity dispersion liquid to carry out 50 times of dilutions, to see whether naked eyes visible particle), wherein ultrasonic time 1h, ultrasound
Between be divided into 5s.
Solidify 2-4h under the conditions of being cured as 120-140 DEG C in the step (2).
A kind of epoxy resin composite material of the method preparation of the invention.
A kind of application of epoxy resin composite material of the invention.
Beneficial effect
(1) compatibility of polysulfones and epoxy resin of the present invention is fine, can improve the brittleness of epoxy resin, while can mention
High carbon nanotube and/or graphene are in matrix dispersibility；
(2) carbon nanotube of the present invention and/or graphene can be very good to effectively improve the stretching of epoxy resin, impact, curved
Qu Xingneng improves the resistance to of material simultaneously because the addition of carbon nanotubes can be improved the glass transition temperature of composite material
It is hot；
(3) operation of the present invention is simple, and raw material sources are extensive, and required laboratory apparatus is also fairly simple, at low cost, can high-volume
Preparation；
(4) present invention is compared epoxy with the epoxy resin composite material of carbon nanotube and the epoxy resin toughened preparation of polysulfones
The toughness of resin itself improves a lot.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Raw materials are as shown in table 1.
1 raw materials of table
Tensile property test is carried out according to American Society Testing and Materials ASTM D638-10 material tensile property measuring method
Test.
Bending property test is according to American Society Testing and Materials ASTM D790-07 is non-reinforcing and reinforced plastic material
The standard test method of bending property is tested.
Fracture toughness test becomes fracture toughness according to American Society Testing and Materials' ASTM D5045-14 plastic material and answers
The standard test method for becoming energy release rate is tested.
Impact property is tested according to the impact strength test side ASTM D256-10 plastics IZOD, American Society Testing and Materials
Method is tested.
Embodiment 1
It takes 0.25g graphene (Graphene) powder, is added 300ml THF dissolution, ultrasound is to being uniformly dispersed.By drying
PSF and E51 presses 80:15, that is, epoxy resin 80g, and polysulfones 15g is added in flask, in oil bath pan heating stirring (120 DEG C of temperature), machine
Tool, which is stirred, becomes clarification system addition MWCNT dispersion liquid to system from muddiness.Continue to stir, until being uniformly dispersed.Solidify initial vacuum
DMF is removed, DETDA 20g is added, obtains curing system.Curing system is poured into and is previously added in the casting grinding tool of release agent,
Heating in vacuum deaeration, until bubble is completely out.Elevated cure, solidification temperature are 120 DEG C, and curing time is 2 hours, obtain epoxy
Resin composite materials.
Compared with pure epoxy resin, the tensile property of prepared Graphene/PSF/EP composite material, bending property,
Fracture toughness and impact strength have obtained significantly improving, and have been respectively increased 4%, 107%, 132% and 183%.It is resulting multiple
Condensation material mechanical property is as shown in table 1.
1 composite materials property of table
| Performance | Value |
| Tensile strength (MPa) | 77.63 |
| Stretch modulus (GPa) | 1.80 |
| Bending strength (MPa) | 118.77 |
| Bending modulus (GPa) | 3.87 |
| Fracture toughness (MPam1/2) | 1.87 |
| Impact strength (J/m) | 65.6 |
Embodiment 2
It takes 0.5g graphene (Graphene) powder, is added 300ml THF dissolution, ultrasound is to being uniformly dispersed.By drying
PSF and E51 presses 80:15, that is, epoxy resin 80g, and polysulfones 15g is added in flask, in oil bath pan heating stirring (120 DEG C of temperature), machine
Tool, which is stirred, becomes clarification system addition MWCNT dispersion liquid to system from muddiness.Continue to stir, until being uniformly dispersed.Solidify initial vacuum
DMF is removed, DETDA 20g is added, obtains curing system.Curing system is poured into and is previously added in the casting grinding tool of release agent,
Heating in vacuum deaeration, until bubble is completely out.Elevated cure, solidification temperature are 120 DEG C, and curing time is 2 hours, obtain epoxy
Resin composite materials.
Compared with pure epoxy resin, the tensile property of prepared Graphene/PSF/EP composite material, bending property,
Fracture toughness and impact strength have obtained significantly improving, and have been respectively increased 12.8%, 33.6%, 141.9% and 158.4%.
Resulting composite materials property is as shown in table 2.
2 composite materials property of table
| Performance | Value |
| Tensile strength (MPa) | 83.65 |
| Stretch modulus (GPa) | 2.12 |
| Bending strength (MPa) | 121.38 |
| Bending modulus (GPa) | 1.95 |
| Fracture toughness (MPam1/2) | 59.7 |
| Impact strength (J/m) | 65.6 |
Embodiment 3
0.75g graphene (Graphene) powder is taken, 300ml DMF (N, N- dimethylformamide) dissolution is added, ultrasound is extremely
It is uniformly dispersed.The PSF of drying and E51 is pressed into 80:15, that is, epoxy resin 80g, polysulfones 15g is added in flask, heats in oil bath pan
It stirs (120 DEG C of temperature), mechanical stirring to system becomes clarification system from muddiness and MWCNT dispersion liquid is added.Continue to stir, until point
It dissipates uniform.Solidify initial vacuum and remove DMF, DETDA 20g is added, obtains curing system.Curing system is poured into be previously added it is de-
In the casting grinding tool of mould agent, heating in vacuum deaeration, until bubble is completely out.Elevated cure, solidification temperature are 120 DEG C, when solidification
Between be 2 hours, obtain epoxy resin composite material.
Compared with pure epoxy resin, the tensile property of prepared Graphene/PSF/EP composite material, bending property,
Fracture toughness and impact strength have obtained significantly improving, and have been respectively increased 3.3%, 21.9%, 149.4% and 141.1%.Institute
The composite materials property obtained is as shown in table 3.
3 composite materials property of table
Embodiment 4
0.1g carbon nanotube (MWCNT) powder is taken, 300ml DMF (N, N- dimethylformamide) dissolution is added, ultrasound is extremely divided
It dissipates uniform.The PSF of drying and E51 is pressed into 80:10, that is, epoxy resin 80g again, polysulfones 10g is added in flask, heats in oil bath pan
It stirs (120 DEG C of temperature), mechanical stirring to system becomes clarification system from muddiness and MWCNT dispersion liquid is added.Continue to stir, until point
It dissipates uniform.Solidify initial vacuum and remove DMF, DETDA 20g is added, obtains curing system.Curing system is poured into be previously added it is de-
In the casting grinding tool of mould agent, heating in vacuum deaeration, until bubble is completely out.Elevated cure, solidification temperature are 120 DEG C, when solidification
Between be 2 hours, obtain epoxy resin composite material.
Embodiment 5
0.3g carbon nanotube (MWCNT) powder is taken, 300ml DMF (N, N- dimethylformamide) dissolution is added, ultrasound is extremely divided
It dissipates uniform.The PSF of drying and E51 is pressed into 80:10, that is, epoxy resin 80g again, polysulfones 10g is added in flask, heats in oil bath pan
It stirs (120 DEG C of temperature), mechanical stirring to system becomes clarification system from muddiness and MWCNT dispersion liquid is added.Continue to stir, until point
It dissipates uniform.Solidify initial vacuum and remove DMF, DETDA 20g is added, obtains curing system.Curing system is poured into be previously added it is de-
In the casting grinding tool of mould agent, heating in vacuum deaeration, until bubble is completely out.Elevated cure, solidification temperature are 120 DEG C, when solidification
Between be 2 hours, obtain epoxy resin composite material.
Embodiment 6
0.5g carbon nanotube (MWCNT) powder is taken, DMF (N, the N- dimethylformamide) dissolution of 300ml is added, ultrasound is extremely divided
It dissipates uniform.The PSF of drying and E51 is pressed into 80:25, that is, epoxy resin 80g again, polysulfones 25g is added in flask, heats in oil bath pan
It stirs (120 DEG C of temperature), mechanical stirring to system becomes clarification system from muddiness and MWCNT dispersion liquid is added.Continue to stir, until point
It dissipates uniform.Solidify initial vacuum and remove DMF, DETDA 20g is added, obtains curing system.Curing system is poured into be previously added it is de-
In the casting grinding tool of mould agent, heating in vacuum deaeration, until bubble is completely out.Elevated cure, solidification temperature are 120 DEG C, when solidification
Between be 2 hours, obtain epoxy resin composite material.
Claims (10)
1. a kind of epoxy resin composite material, in parts by weight, raw material components include: 80-100 parts of epoxy resin, curing agent 10-
20 parts, PSF10-25 parts of polysulfones, carbon nanotube or 0.01-1 parts of graphene.
2. composite material according to claim 1, which is characterized in that the epoxy resin is bisphenol A type epoxy resin；Solidification
Agent is one of amine curing agent, acid anhydride type curing agent.
3. composite material according to claim 2, which is characterized in that the amine curing agent is DETDA or GY-051, acid
Anhydride curing agent is methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride；Epoxy resin is epoxy resin E51.
4. composite material according to claim 1, which is characterized in that in parts by weight, raw material components are as follows: epoxy resin 80
Part；20 parts of curing agent, 10-25 parts of polysulfones, 0.25-1 parts of graphene.
5. composite material according to claim 1, which is characterized in that in parts by weight, raw material components are as follows: epoxy resin 80
Part；20 parts of curing agent, 10-25 parts of polysulfones, 0.01-0.125 parts of carbon nanotube.
6. a kind of preparation method of epoxy resin composite material, comprising:
(1) epoxy resin of drying and polysulfones are mixed, oil bath pan heating stirring becomes clarifying to system from muddiness, and carbon is added and receives
Mitron and/or graphene dispersing solution, stirring, vacuum defoamation are added curing agent, obtain curing system；
(2) curing system is poured into and is previously added in the casting grinding tool of release agent, heating in vacuum deaeration solidifies to get asphalt mixtures modified by epoxy resin
Resin composite material.
7. preparation method according to claim 6, which is characterized in that oil bath pan heating stirring temperature is in the step (1)
120℃。
8. preparation method according to claim 6, which is characterized in that be cured as under the conditions of 120-140 DEG C in the step (2)
Solidify 2-4h.
9. a kind of epoxy resin composite material of claim 6 the method preparation.
10. a kind of application of epoxy resin composite material described in claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760159A (en) * | 2019-11-01 | 2020-02-07 | 嘉兴烯成新材料有限公司 | Preparation method of xanthium-shaped carbon material reinforced epoxy resin mechanical property |
| CN114456410A (en) * | 2022-01-12 | 2022-05-10 | 东华大学 | High-performance epoxy resin toughening agent for winding and forming of composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084655A (en) * | 2016-11-21 | 2018-05-29 | 航天特种材料及工艺技术研究所 | A kind of low temperature resistant epoxy resin material and preparation method |
-
2019
- 2019-06-28 CN CN201910574632.1A patent/CN110343364A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084655A (en) * | 2016-11-21 | 2018-05-29 | 航天特种材料及工艺技术研究所 | A kind of low temperature resistant epoxy resin material and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| BAHAREH RAZAVI，ET AL: ""Effect of Polysulfone and Graphene Nanosheets on the Flexibility of Epoxy Coatings"", 《IRAN. J. POLYM. SCI. TECHNOL. (PERSIAN)》 * |
| NAN ZHENG，ET AL: ""Effects of carboxylated carbon nanotubes on the phase separation behaviour and fracture-mechanical properties of an epoxy/polysulfone blend"", 《COMPOSITES SCIENCE AND TECHNOLOGY》 * |
| TONG-TONG WANG，ET AL: ""Epoxy nanocomposites significantly toughened by both poly(sulfone) and graphene oxide"", 《COMPOSITES COMMUNICATIONS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760159A (en) * | 2019-11-01 | 2020-02-07 | 嘉兴烯成新材料有限公司 | Preparation method of xanthium-shaped carbon material reinforced epoxy resin mechanical property |
| CN114456410A (en) * | 2022-01-12 | 2022-05-10 | 东华大学 | High-performance epoxy resin toughening agent for winding and forming of composite material and preparation method thereof |
| CN114456410B (en) * | 2022-01-12 | 2023-09-05 | 东华大学 | High-performance epoxy resin toughening agent for winding and forming composite material and preparation method thereof |
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Application publication date: 20191018 |