CN107955134A - A kind of application of graphene in epoxy resin composite material - Google Patents
A kind of application of graphene in epoxy resin composite material Download PDFInfo
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- CN107955134A CN107955134A CN201711253684.6A CN201711253684A CN107955134A CN 107955134 A CN107955134 A CN 107955134A CN 201711253684 A CN201711253684 A CN 201711253684A CN 107955134 A CN107955134 A CN 107955134A
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- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
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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
- C08K3/04—Carbon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of application of graphene in epoxy resin composite material, cured by pentaerythrite four mercaptopropionic acid ester epoxy prepolymer (PPTM) curing agent of preparation, adjust graphene dosage, hardener dose, curing agent species etc. optimizes combination, prepare the epoxy resin composite polymer material for including graphene, the high molecular material is fast with curing rate, graphene disperses more uniform in the substrate, graphene and epoxy resin compatibility are good, resulting materials mechanical property is good, it is of low cost, preparation method is simple, the features such as environmental pollution is small.
Description
Technical field
The invention belongs to polymer material science field, more particularly, to a kind of graphene in epoxy resin composite material
Application.
Background technology
Epoxy resin is mainly used in coating, civil engineering, material engineering, electronic and electrical industry and a small amount of adhesive.But
In 2010, the application field of epoxy resin changed there occurs obvious, it is greatly increased in the application of adhesive field, and
It is more and more extensive.Meanwhile epoxy resin has a wide range of applications in fields such as electronics, electric appliance, aerospace, coating.Wherein, change
Property coating is most widely used, and modified coating shows more excellent performance, is favored be subject to people.
The development space of epoxy resin is huge, and market is also continuously increased the demand of epoxy resin, to its performance requirement
Gradually stepping up, high tensile, rapid curing, high temperature resistant, high pressure resistant, low stain etc. are all that the development in epoxy resin future becomes
Gesture.
On the other hand preliminary exploration has been carried out early in preparations of the people just to graphene composite material of 20th century, but ought
When it is limited due to research means at that time and scientific and technological level, the research for application and development to these composite materials does not obtain enough
Attention and popularization.Until graphene was successfully prepared in 2004 in laboratory, just it is widely used, in 2006
Ruoff et al. has acquired the graphene for possessing relatively good dispersiveness and stability, and on this basis synthesize with than
The graphene polymer composite of preferable electric conductivity, since then, the research and application of graphene composite material just start
Obtain due importance and cause more and more concerns.
Due to low cost, and itself there are many excellent performances, graphene is wide in the field such as electronic device and communication
It is general to be employed.Graphene composite material has high intensity, excellent electric conductivity and good heat transfer property.Therefore, graphene is multiple
The preparation and application of condensation material receive the extensive concern of researcher.But graphene is due to autoreactivity poor activity, with high score
Son compatibility it is poor, therefore, it is difficult to high molecular material direct combination.So how to be prepared by simple effective method
Graphene composite polymer material, and make its performance obtain preferably improving the great difficult problem for being badly in need of solution into people.
With the development of science and technology, people are more and more extensive to the demand of fast epoxy resin curing system, it is in vapour
Very important effect is played in the industries such as car maintenance, mechanical processing, ship's space paint, the time can be greatlyd save, improved
Construction speed is so as to reach the purpose of rapid construction, bonding, repairing.With epoxy resin (128) for binding agent, bond strength height,
The features such as shrinkage is good, shrinking percentage is low, particle diameter is big, good weatherability, is used in combination with synthesized solidified dose, can overcome graphene with
The problem of high molecular material poor compatibility, it is dispersed in wherein, and then obtain the graphene/epoxy with excellent properties
Resin compounded high molecular material.
The content of the invention
It is an object of the invention to provide a kind of application of graphene in epoxy resin composite material, solves existing skill
Graphene reactivity is low in art, and high molecular material poor compatibility, and then bad dispersibility, it is difficult to directly multiple with high molecular material
The technical problem of conjunction.Gained composite polymer material, which has, prepares simple, easy to use, the power such as tensile strength, elongation at break
Excellent performance is learned, solidified forming time is short, lower-price characteristic.
The present invention adopt the following technical scheme that for：
A kind of application of graphene in epoxy resin composite material, the epoxy resin composite material are by component A and B
Component composite curing obtains, and the component A includes graphene, epoxy resin (128), and the B component includes curing agent, catalysis
Agent, the curing agent are four mercaptopropionic acid ester epoxy prepolymer (PPTM) of pentaerythrite, and the dosage of the graphene is ring
The 5-15% of oxygen tree fat (128) quality.
The quality of curing agent (PPTM) and epoxy resin (128) in the graphene-epoxy resin composite polymer material
Than for 1：1-1:3.
The catalyst is (three-(dimethylamino methyl) phenol) or benzyl dimethylamine, and dosage is epoxy resin (128) matter
The 1%-5% of amount.
The hardening time is 99-261 seconds.
The tensile strength of the material is 6.75-28.29N/mm.
Application process of a kind of graphene in epoxy resin composite material, it is characterised in that the application process is included such as
Lower step：
(1) by 3- mercaptopropionic acids, pentaerythrite, catalyst p-methyl benzenesulfonic acid, is put into three-necked flask progress after toluene mixing
Reflux water-dividing liquid into reaction bulb is changed into limpid from muddiness, after reaction filters solution through funnel, by the thing after filtering
Body, to neutrality, is then evaporated under reduced pressure with neutralizing treatment, obtains colourless oil liquid, colourless oil liquid is through acetic acid and petroleum ether
(1:1) washing, purifying is carried out, then adds 20% epoxy resin, condensing reflux stirs evenly at 100 DEG C, overnight, rotation
It is dry, up to four mercaptopropionic acid ester epoxy prepolymer curing agent (PPTM) of pentaerythrite,
(2) above-mentioned four mercaptopropionic acid ester epoxy prepolymer curing agent (PPTM) of pentaerythrite is mixed with catalyst
It is even, component A is obtained,
(3) graphene is added in beaker with epoxy resin (128) and is mixed evenly, obtain component B,
(4) fully cured after component A is mixed evenly with component B, obtain the compound height of graphene-epoxy resin
Molecular material.
The dosage of the graphene is the 5-15% of epoxy resin (128) quality.
The quality of curing agent (PPTM) and epoxy resin (128) in the graphene/epoxy resin composite polymer material
Than for 1：1-1:3.
The catalyst is (three-(dimethylamino methyl) phenol) or benzyl dimethylamine, and dosage is epoxy resin (128) matter
The 1%-5% of amount.
The graphene/epoxy resin composite material hardening time is 99-261 seconds.
A kind of graphene/epoxy resin composite polymer material tensile strength is 6.75-28.29N/mm.
The method have the benefit that：
By the present invention in that be curing agent with four mercaptopropionic acid ester epoxy prepolymer (PPTM) of pentaerythrite, Ke Yifang
Just the viscosity of adjustment curing agent, facilitates subsequent construction.Due to containing epoxide group in the curing agent, its phase with epoxy resin
Capacitive is good, and then also improves amount ratio of the graphene in compound system, has relative to other curing agent in the prior art
There is more preferable mechanical property while also there is the features such as hardening time is short, and production efficiency is high.
The application is by using epoxy resin 128, its modest viscosity, the dispersiveness of graphene wherein is best, gained stone
The mechanical property of black alkene/epoxy resin composite polymer material is preferably also.
The application not only increases the compound high score of graphene/epoxy resin by selecting the suitable amount ranges of graphene
The mechanical property of sub- material, has been also convenient for follow-up curing molding.
A kind of application of the graphene provided by the invention in epoxy resin composite material, passes through the Ji Wusi of preparation
Four mercaptopropionic acid ester epoxy prepolymer (PPTM) of alcohol is cured, and prepares graphene/epoxy resin composite polymer material
Curing rate is fast, and the composite polymer material graphene of the acquisition graphene dispersion in graphene composite material is uniform, graphene
It is good with epoxy resin compatibility so that it can improve the mechanical property of material very well, and preparation method of the present invention is simple, prepare price
Cheap and environmental pollution is small.
Brief description of the drawings
Fig. 1, pentaerythrite four mercaptopropionic acid ester epoxy prepolymer (PPTM) nuclear magnetic spectrum
Fig. 2, pentaerythrite four mercaptopropionic acid ester epoxy prepolymer (PPTM) infared spectrum
The curing schematic diagram of Fig. 3, epoxy resin
The tensile strength curve of Fig. 4, different graphene content composite polymer materials
Sample section scanning electron microscope (SEM) photograph when Fig. 5, graphene content are epoxy resin (128) quality 15%
Embodiment
With reference to embodiment, the present invention will be further described：
Embodiment 1
(1) synthesis of four mercaptopropionic acid ester epoxy prepolymer (PPTM) of curing agent pentaerythrite
Raw material 3- mercaptopropionic acids (44.48g, 0.42mol), pentaerythrite are separately added into 250ml three-necked flasks
(15.13g, 0.11mol), catalyst p-methyl benzenesulfonic acid (0.90g, 0.0052mol), solvent toluene (90.06mL, 1.13mol)
And stirrer.Three-necked flask is put into oil cauldron, oil water separator, spherical condensation tube are put up successively, temperature control in oil cauldron
At 110 DEG C, flow back 8h.Water appearance is had in oil water separator when reaction proceeds to about 2h, with the carry out flask of reaction
Interior liquid is changed into limpid from muddiness.Solution is filtered through funnel after reaction, by the object after filtering with neutralizing treatment to neutrality,
The solution after washing is evaporated under reduced pressure again, obtains colourless oil liquid at this time.Solution is through acetic acid and petroleum ether (1:1) purify
Four mercaptopropionic acid ester of pentaerythrite (PTM).Then the PTM of synthesis is added into the three-necked flask of 250mL, adds its quality
20% epoxy resin (128), adds stirrer, the condensing reflux at 100 DEG C, overnight, is spin-dried for, up to curing agent pentaerythrite
Four mercaptopropionic acid ester epoxy prepolymers (PPTM).
(2) application of the graphene in epoxy resin composite material
Component A：Institute's graphene is added in beaker with epoxy resin (128) and is mixed evenly, the addition of graphene
Measure as the 15% of epoxy resin (128) quality.
Component B：By prepared four mercaptopropionic acid ester epoxy prepolymer PPTM of curing agent pentaerythrite and catalyst
(three-(dimethylamino methyl) phenol), which is added in beaker, to be mixed evenly, the dosage and asphalt mixtures modified by epoxy resin of the curing agent PPTM
The mass ratio of fat (128) is 1：2, the dosage of the catalyst is the 2% of epoxy resin (128) quality, by component A and component B
Sample preparation bar in tetrafluoroethene mould plate is added to after mixing, and prepared batten is tested into tensile property after fully curing.
Embodiment 2
In the case where not changing other ratios of embodiment 1, only change graphene and account for the hundred of epoxy resin (128) weight
Fraction is 0%, and component A is uniformly mixed with component B, is added to sample preparation bar in tetrafluoroethene mould plate, by institute after fully curing
The batten test tensile property of preparation.
Embodiment 3
In the case where not changing other ratios of embodiment 1, only change graphene and account for the hundred of epoxy resin (128) weight
Fraction is 5%, and component A is uniformly mixed with component B, is added to sample preparation bar in tetrafluoroethene mould plate, by institute after fully curing
The batten test tensile property of preparation.
Embodiment 4
In the case where not changing other ratios of embodiment 1, only change graphene and account for the hundred of epoxy resin (128) weight
Fraction is 10%, and component A is uniformly mixed with component B, is added to sample preparation bar in tetrafluoroethene mould plate, by institute after fully curing
The batten test tensile property of preparation.
Embodiment 5
In the case where not changing other ratios of embodiment 1, only change graphene and account for the hundred of epoxy resin (128) weight
Fraction is 20%, and component A is uniformly mixed with component B, is added to sample preparation bar in tetrafluoroethene mould plate, by institute after fully curing
The batten test tensile property of preparation.
1 extension test of table
Graphene can be obviously improved the tensile strength of system after being added to epoxy curing systems, but work as graphene dosage
After 20%, tensile strength can decline on the contrary, this is probably that system viscosity is too high, stone because when graphene dosage is too high
Black alkene cannot effectively disperse caused.In addition, without substantial connection, concrete reason between the dosage and elongation at break of graphene
It is unknown.Summary mechanical property and curing performance analysis, it is considered herein that when the percetage by weight of graphene is 5-15%, institute
Obtaining graphene applies the dosage in epoxy resin composite polymer material more excellent, can preferably meet the needs of practical application.
Embodiment 6
In the case where not changing other ratios of embodiment 1, change epoxy resin species be 6101, by component A with
Component B is uniformly mixed, and is added to sample preparation bar in tetrafluoroethene mould plate, and prepared batten is tested draftability after fully curing
Energy.
Embodiment 7
In the case where not changing other ratios of embodiment 1, change epoxy resin species be 6445, by component A with
Component B is uniformly mixed, and is added to sample preparation bar in tetrafluoroethene mould plate, and prepared batten is tested draftability after fully curing
Energy.
The application selects its modest viscosity of epoxy resin 128, and graphene wherein apply by good dispersion, gained graphene
Comprehensive mechanical property in epoxy resin composite polymer material is optimal.
Embodiment 8
In the case where not changing other ratios of embodiment 1, four mercaptopropionic acid ester epoxy prepolymer of pentaerythrite
(PPTM) ratio of curing agent and epoxy resin (128) is 2:1, component A is uniformly mixed with component B, is added to tetrafluoroethene
Sample preparation bar in mould plate, tensile property is tested after fully curing by prepared batten.
Embodiment 9
In the case where not changing other ratios of embodiment 1, four mercaptopropionic acid ester epoxy prepolymer of pentaerythrite
(PPTM) ratio of curing agent and epoxy resin (128) is 1:1, component A is uniformly mixed with component B, is added to tetrafluoroethene
Sample preparation bar in mould plate, tensile property is tested after fully curing by prepared batten.
Embodiment 10
In the case where not changing other ratios of embodiment 1, four mercaptopropionic acid ester epoxy prepolymer of pentaerythrite
(PPTM) ratio of curing agent and epoxy resin (128) is 1:3, component A is uniformly mixed with component B, is added to tetrafluoroethene
Sample preparation bar in mould plate, tensile property is tested after fully curing by prepared batten.
Embodiment 11
In the case where not changing other ratios of embodiment 1, four mercaptopropionic acid ester epoxy prepolymer of pentaerythrite
(PPTM) ratio of curing agent and epoxy resin (128) is 1:4, component A is uniformly mixed with component B, is added to tetrafluoroethene
Sample preparation bar in mould plate, tensile property is tested after fully curing by prepared batten.
The application selects the ring of four mercaptopropionic acid ester epoxy prepolymer (PPTM) curing agent of pentaerythrite and (PPTM)
The ratio of oxygen tree fat (128) is 1:1-1:When 3, graphene can strengthen the average tensile strength of composite material, but select
PPTM/ content of epoxy resin ratios are 1:Resultant force of the gained graphene after the application of epoxy resin composite polymer material when 2
Learn best performance.
Comparative example 1
In the case where not changing other ratios of embodiment 1, the curing agent used is diethylaminopropylamine, by component A
It is uniformly mixed with component B, is added to sample preparation bar in tetrafluoroethene mould plate, prepared batten is tested into stretching after fully curing
Performance.
Comparative example 2
In the case where not changing other ratios of embodiment 1, the curing agent used is tetrahydrophthalic anhydride, by component A and group
Divide B to be uniformly mixed, be added to sample preparation bar in tetrafluoroethene mould plate, prepared batten is tested into draftability after fully curing
Energy.
By embodiment 1 and comparative example 1,2, using curing agent of the present invention, gained graphene is in epoxy resin
Using rear mechanical property, having for middle curing agent greatly improves composite polymer material compared with the prior art.
The foregoing is merely the preferred embodiment of the invention, is not intended to limit the invention, to the technology of this area
For personnel, it can still modify technical solution described in foregoing embodiments, or to which part skill
Art feature carries out equivalent substitution.Within the spirit and principles of the invention, any modification, equivalent substitution, improvement and etc. done,
It should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of application of graphene in epoxy resin composite material, the epoxy resin composite material is by component A and B groups
Composite curing is divided to obtain, the component A includes graphene, epoxy resin (128), and the B component includes curing agent, catalyst,
The curing agent is four mercaptopropionic acid ester epoxy prepolymer (PPTM) of pentaerythrite, and the dosage of the graphene is asphalt mixtures modified by epoxy resin
The 5-15% of fat (128) quality.
2. application of the graphene according to claim 1 in epoxy resin composite material, it is characterised in that the graphite
The mass ratio of curing agent (PPTM) and epoxy resin (128) is 1 in alkene/epoxy resin composite polymer material：1-1:3.
3. application of the graphene according to claim 1 in epoxy resin composite material, its feature is in the catalyst
For (three-(dimethylamino methyl) phenol), dosage is the 1%-5% of epoxy resin (128) quality.
4. application of the graphene according to claim 1 in epoxy resin composite material, it is characterised in that the curing
Time is 99-261 seconds.
5. application process of a kind of graphene in epoxy resin composite material, it is characterised in that the application process includes as follows
Step：
(1) by 3- mercaptopropionic acids, pentaerythrite, catalyst p-methyl benzenesulfonic acid, is put into three-necked flask after toluene mixing and flows back
Divide water liquid into reaction bulb to be changed into limpid from muddiness, after reaction filter solution through funnel, the object after filtering is used
Then neutralizing treatment is evaporated under reduced pressure to neutrality, obtains colourless oil liquid, colourless oil liquid is through acetic acid and petroleum ether (1:
1) washing, purifying is carried out, then adds 20% epoxy resin, condensing reflux stirs evenly at 100 DEG C, overnight, is spin-dried for,
Up to four mercaptopropionic acid ester epoxy prepolymer curing agent (PPTM) of pentaerythrite,
(2) above-mentioned four mercaptopropionic acid ester epoxy prepolymer curing agent (PPTM) of pentaerythrite is uniformly mixed with catalyst,
Component A is obtained,
(3) graphene is added in beaker with epoxy resin (128) and is mixed evenly, obtain component B,
(4) fully cured after component A is mixed evenly with component B, obtain graphene-epoxy resin composite high-molecular
Material.
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| CN201711253684.6A CN107955134B (en) | 2017-12-02 | 2017-12-02 | Application of graphene in epoxy resin composite material |
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|---|---|---|---|
| CN201711253684.6A CN107955134B (en) | 2017-12-02 | 2017-12-02 | Application of graphene in epoxy resin composite material |
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|---|---|---|---|---|
| CN1288481A (en) * | 1998-01-16 | 2001-03-21 | 洛克泰特(R&D)有限公司 | Curable epoxy-based compositions |
| CN101987908A (en) * | 2010-09-21 | 2011-03-23 | 中国科学院长春应用化学研究所 | Method for preparing graphene-epoxy resin composite material |
| CN102443139A (en) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | Polymercaptan curing agent and preparation method thereof |
| CN103396653A (en) * | 2013-07-12 | 2013-11-20 | 浙江大学宁波理工学院 | Preparation method of graphene nanoplatelet/epoxy resin nanocomposite material |
| JP2013253194A (en) * | 2012-06-08 | 2013-12-19 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
| CN104797623A (en) * | 2012-11-28 | 2015-07-22 | 味之素株式会社 | Resin curing agent and one-pack type epoxy resin composition |
-
2017
- 2017-12-02 CN CN201711253684.6A patent/CN107955134B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288481A (en) * | 1998-01-16 | 2001-03-21 | 洛克泰特(R&D)有限公司 | Curable epoxy-based compositions |
| CN101987908A (en) * | 2010-09-21 | 2011-03-23 | 中国科学院长春应用化学研究所 | Method for preparing graphene-epoxy resin composite material |
| CN102443139A (en) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | Polymercaptan curing agent and preparation method thereof |
| JP2013253194A (en) * | 2012-06-08 | 2013-12-19 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
| CN104797623A (en) * | 2012-11-28 | 2015-07-22 | 味之素株式会社 | Resin curing agent and one-pack type epoxy resin composition |
| CN103396653A (en) * | 2013-07-12 | 2013-11-20 | 浙江大学宁波理工学院 | Preparation method of graphene nanoplatelet/epoxy resin nanocomposite material |
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Effective date of registration: 20201228 Address after: 224001 room 106, photoelectric R & D center, No.66 Lijiang Road, Yancheng Economic and Technological Development Zone, Jiangsu Province Patentee after: Yancheng baijiashidai Film Technology Co., Ltd Address before: 213100 West Taihu Science and Technology Industrial Park, Changzhou City, Jiangsu Province, No. 8 Lanxiang Road Patentee before: CHANGZHOU BAOLIMEI GRAPHENE Co.,Ltd. |