CN107936477A - A kind of graphene/epoxy resin composite polymer material - Google Patents
A kind of graphene/epoxy resin composite polymer material Download PDFInfo
- Publication number
- CN107936477A CN107936477A CN201711253692.0A CN201711253692A CN107936477A CN 107936477 A CN107936477 A CN 107936477A CN 201711253692 A CN201711253692 A CN 201711253692A CN 107936477 A CN107936477 A CN 107936477A
- Authority
- CN
- China
- Prior art keywords
- graphene
- epoxy resin
- polymer material
- composite polymer
- resin composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of graphene/epoxy resin composite polymer material, cured by pentaerythrite four mercaptopropionic acid ester epoxy prepolymer (PPTM) curing agent of preparation, adjustment graphene dosage, hardener dose, curing agent species etc. optimize combination, prepare graphene/epoxy resin composite polymer material, 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, the features such as preparation method is simple, and environmental pollution is small.
Description
Technical field
The invention belongs to polymer material science field, more particularly, to a kind of graphene/epoxy resin composite high-molecular
Material.
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 graphene/epoxy resin composite polymer material of excellent performance, solves existing
Have that graphene reactivity in technology is low, and high molecular material poor compatibility, and then bad dispersibility, it is difficult to it is straight with high molecular material
Connect compound technical problem.Gained composite polymer material, which has, prepares simple, easy to use, tensile strength, elongation at break
It is short etc. excellent in mechanical performance, solidified forming time, lower-price characteristic.
The present invention adopt the following technical scheme that for：
A kind of graphene/epoxy resin composite polymer material, it is obtained by component A and B component composite curing；The A
Component includes graphene, epoxy resin (128), and the B component includes curing agent, catalyst, and the curing agent is pentaerythrite
Four mercaptopropionic acid ester epoxy prepolymers (PPTM), the dosage of the graphene are 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), and dosage is the 1%-5% of epoxy resin (128) quality.
The material was obtained through the curing of 99-261 seconds.
The tensile strength of the material is 6.75-28.29N/mm.
The present invention additionally provides the preparation method of the graphene/epoxy resin composite polymer material, the material passes through
Following steps are prepared：
The first step：By 3- mercaptopropionic acids, pentaerythrite, catalyst p-methyl benzenesulfonic acid, toluene, three-necked flask is put into after mixing
Carry out reflux water-dividing liquid into reaction bulb and be changed into limpid from muddiness, after reaction filter solution through funnel, after filtering
Object with neutralizing treatment to neutrality, be then evaporated under reduced pressure, obtain colourless oil liquid at this time, colourless oil liquid is through acetic acid
With petroleum ether (1:1) washing, purifying is carried out, then adds epoxy resin (128), condensing reflux stirs evenly at 100 DEG C,
Overnight, it is spin-dried for, up to four mercaptopropionic acid ester epoxy prepolymer (PPTM) of curing agent pentaerythrite；
Second step：Graphene is added in beaker with epoxy resin (128) and is mixed evenly, obtains component A；
3rd step：By above-mentioned four mercaptopropionic acid ester epoxy prepolymer (PPTM) of pentaerythrite and catalyst (three-(two
Methylamine ylmethyl) phenol) it is uniformly mixed, obtain component B；
4th step：Cured after component A and component B are mixed evenly, that is, it is compound to obtain graphene/epoxy resin
High 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), and dosage is the 1%-5% of epoxy resin (128) quality.
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 graphene/epoxy resin composite polymer material provided by the invention, passes through four mercapto of pentaerythrite of preparation
Base propionic ester epoxy prepolymer (PPTM) is cured, and is prepared graphene/epoxy resin composite polymer material and is cured speed
Degree is fast, and the composite polymer material graphene of acquisition is uniformly dispersed in graphene/epoxy resin composite material, graphene and ring
Oxygen resin compatible is good so that it can improve the mechanical property of material very well, and preparation method of the present invention is simple, prepare 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 is burnt for tri- mouthfuls to 250ml
Raw material 3- mercaptopropionic acids (44.48g, 0.42mol), pentaerythrite (15.13g, 0.11mol), catalyst pair are separately added into bottle
Toluenesulfonic acid (0.90g, 0.0052mol), solvent toluene (90.06mL, 1.13mol) and stirrer.Three-necked flask is put into oil
In pot, oil water separator, spherical condensation tube are put up successively, temperature control is at 110 DEG C in oil cauldron, and flow back 8h.When reaction carries out
Water appearance is had into oil water separator during about 2h, liquid is changed into limpid from muddiness with the carry out flask of reaction.
Solution is filtered through funnel after reaction, by the object after filtering with neutralizing treatment to neutrality, then it is molten after washing
Liquid is evaporated under reduced pressure, and obtains colourless oil liquid at this time.Solution is through acetic acid and petroleum ether (1:1) four mercapto of pentaerythrite is purified to obtain
Base propionic ester (PTM).Then the PTM of synthesis is added into the three-necked flask of 250mL, adds the epoxy resin of its quality 20%
(128), stirrer is added, the condensing reflux at 100 DEG C, overnight, is spin-dried for, up to four mercaptopropionic acid ester ring of curing agent pentaerythrite
Oxygen resin prepolymer (PPTM).
(2) preparation of graphene/epoxy resin composite polymer 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
It is more excellent to obtain the dosage of graphene/epoxy resin composite polymer material, 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 epoxy resin 128 its modest viscosity, graphene good dispersion wherein, gained graphene/epoxy
The comprehensive mechanical property of resin compounded high molecular 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:The comprehensive mechanical property of graphene/epoxy resin composite polymer material obtained by when 2 is most
It is excellent.
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/epoxy resin is multiple
Closing Polymer Mechanical performance, having for middle curing agent greatly improves 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 graphene/epoxy resin composite polymer material, it is obtained by component A and B component composite curing；The A groups
Dividing includes graphene, epoxy resin (128), and the B component includes curing agent, catalyst, and the curing agent is pentaerythrite four
Mercaptopropionic acid ester epoxy prepolymer (PPTM), the dosage of the graphene are the 5-15% of epoxy resin (128) quality.
A kind of 2. graphene/epoxy resin composite polymer material according to claim 1, 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. a kind of graphene/epoxy resin composite polymer material according to claim 1, the catalyst for (three-
(dimethylamino methyl) phenol), dosage is the 1%-5% of epoxy resin (128) quality.
A kind of 4. graphene/epoxy resin composite polymer material according to claim 1, it is characterised in that the material
Obtained through the curing of 99-261 seconds.
5. a kind of graphene/epoxy resin composite polymer material according to claim 1-4 any one, its feature exist
In the tensile strength of the material be 6.75-28.29N/mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711253692.0A CN107936477B (en) | 2017-12-02 | 2017-12-02 | Graphene/epoxy resin composite high polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711253692.0A CN107936477B (en) | 2017-12-02 | 2017-12-02 | Graphene/epoxy resin composite high polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107936477A true CN107936477A (en) | 2018-04-20 |
| CN107936477B CN107936477B (en) | 2020-05-22 |
Family
ID=61947394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711253692.0A Active CN107936477B (en) | 2017-12-02 | 2017-12-02 | Graphene/epoxy resin composite high polymer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107936477B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401555A (en) * | 2018-11-28 | 2019-03-01 | 天津宝坻紫荆创新研究院 | A kind of high-temperature and high-presure resistent graphene modified phenolic resin grease coating material |
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 |
| 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 CN201711253692.0A patent/CN107936477B/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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401555A (en) * | 2018-11-28 | 2019-03-01 | 天津宝坻紫荆创新研究院 | A kind of high-temperature and high-presure resistent graphene modified phenolic resin grease coating material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107936477B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101555386B (en) | Epoxy organosilicone ultraviolet curing coating modified by (methyl) acrylic acid and preparation method thereof | |
| CN110237725A (en) | Organic amine modified graphene oxide/composite membrane of polymer and its preparation and application | |
| CN109265922B (en) | High-toughness autocatalytic epoxy resin and preparation method thereof | |
| CN102786664A (en) | Low dielectric and high heat-resistant epoxy resin composition and its preparation method | |
| CN103641367B (en) | A kind of composite cement grinding aid and preparation method thereof | |
| CN113201207B (en) | Preparation method of high-toughness and high-strength carbon nanotube/epoxy resin composite material | |
| CN112980372B (en) | Adhesive and preparation method thereof | |
| CN107936477A (en) | A kind of graphene/epoxy resin composite polymer material | |
| CN107974043A (en) | A kind of preparation method of graphene/epoxy resin composite polymer material | |
| CN112679142B (en) | High-strength epoxy mortar and preparation method thereof | |
| CN111440511B (en) | High-thermal-conductivity nano Al2O3Modified epoxy resin super-hydrophobic coating and preparation method thereof | |
| CN104277069B (en) | Synthesis and application of new nano hybrid | |
| CN107955134A (en) | A kind of application of graphene in epoxy resin composite material | |
| CN116041966B (en) | Method for improving mechanical properties of material by adding nano particles | |
| CN108410138B (en) | Concrete | |
| CN105754451A (en) | Konjac fly powder based epoxy resin, preparation method thereof and coating prepared from konjac fly powder based epoxy resin | |
| CN115449053B (en) | Method for preparing lignin epoxy resin and toughening modification through chemical reaction | |
| CN112745649B (en) | Preparation method of unsaturated polyester-based composite material for surfboards | |
| CN109880293A (en) | Toughened epoxy resin and preparation method thereof | |
| CN112898516B (en) | Phenolic aldehyde modified amine and preparation method thereof | |
| CN106590729A (en) | Treatment technology for softening oil | |
| CN109553929B (en) | Nano flame-retardant epoxy resin composite material and preparation method thereof | |
| CN108659527B (en) | High-strength glass fiber composite material and preparation method thereof | |
| CN115232273B (en) | Carboxyl-containing benzoxazine oligomer biomass toughening agent and preparation method and application thereof | |
| CN1107688C (en) | Process for preparing solution of polyimid-base resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201223 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. |