CN104893246A - Preparation method of graphene-based hyperbranched perylene imide/epoxy composite - Google Patents
Preparation method of graphene-based hyperbranched perylene imide/epoxy composite Download PDFInfo
- Publication number
- CN104893246A CN104893246A CN201510262030.4A CN201510262030A CN104893246A CN 104893246 A CN104893246 A CN 104893246A CN 201510262030 A CN201510262030 A CN 201510262030A CN 104893246 A CN104893246 A CN 104893246A
- Authority
- CN
- China
- Prior art keywords
- graphene
- perylene diimide
- pbi
- hpg
- perylene
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparation method of a graphene-based hyperbranched perylene imide/epoxy composite. The preparation method comprises the steps of reacting carboxyl-terminated perylene bisimide, N, N'-dimethylformamide and an alkaline solution for 1-3 hours while stirring at the temperature of 70-100 DEG C, then, dropwise adding glycidol, reacting for 8-12 hours, then, settling, filtering, and drying the sediment to obtain hyperbranched perylene imide; ultrasonically dispersing high-temperature reduced graphene into N, N'-dimethylformamide for 5-6 hours, then, adding hyperbranched perylene imide, reacting at the temperature of 80-100 DEG C for 20-24 hours, then, carrying out centrifugal separation to obtain a product, drying the product at the temperature of 60 DEG C to obtain graphene-based hyperbranched perylene imide, adding graphene-based hyperbranched perylene imide into epoxy resin, and pouring graphene-based hyperbranched perylene imide into a die to cure and mold by taking 4, 4'-diaminodiphenyl sulfone as a curing agent to obtain the graphene-based hyperbranched perylene imide/epoxy composite. The preparation method disclosed by the invention is simple in process, low in production cost, little in pollution and wide in applicability.
Description
Technical field
The invention belongs to hyperbranched polymer technical field of modification, be specifically related to a kind of preparation method of graphene-based Chao Zhiization perylene diimide/epoxy composite material.
Background technology
Since Friedlander in 1913 synthesizes perylene diimide, ， perylene diimide derivative receives much concern in fields such as n-type semiconductor, organic electro-optic device and Supramolecular Assemblings as a kind of dyestuff and optical material.On the one hand, this mainly has good light, thermostability, chemical resistant properties and fluorescence quantum yield advantages of higher Yin perylene diimide; You Yu perylene diimide compounds has large common phenyl ring two dimensional structure on the other hand, it is stacking to there is π-π by noncovalent interaction power in the molecule can same with some other with conjugated structure, thus forms supramolecular structure, makes it be widely used in Supramolecular Assembling.Ran Er perylene diimide compounds solvability is poor, for solving this difficult problem, the bay position of Haag seminar perylene diimide being introduced hyperbranched polymer and preparing water-soluble perylene diimide, thus improve its solvability.
Hyperbranched polymer has a large amount of surface functional groups, highly regular branched structure and intramolecule and there is the features such as cavity, thus there is the advantages such as viscosity is low, solvability is good, just because of the molecular structure of its uniqueness, hyperbranched polymer is widely used in the fields such as bio-medical material, speciality coating, tensio-active agent, nano material by people.And the synthesis technique of hyperbranched polymer is comparatively simple, and generally adopt one-step synthesis, products therefrom only needs simple purifying, greatly reduces the large-scale production cost of enterprise.
Graphene is by a kind of new carbon of six tightly packed side's polynuclear planes of monolayer carbon atom, causes " carbon " upsurge of scientific circles' new round.Graphene has the advantages such as excellent heat-conductivity conducting performance, large specific surface, tensile modulus are large, is therefore widely used in the fields such as energy storage material, conducing composite material, super capacitor and heat-stable material.In fact, Graphene blemish in an otherwise perfect thing be that it is easy to assemble and form fold, for the excellent performance of Graphene can be made full use of, just must overcome the difficult problem of its easy gathering by carrying out chemical modification to it.On the one hand, the covalent modified electronic configuration structure that can change Graphene, thus improve its physicals; On the other hand, non-covalent modification can not change the conjugated structure of Graphene, interaction as stacking in π-π.Research shows: its perveance is 10
4s/m, Young's modulus is 1000GPa, and ultimate strength is 116 GPa, as material firmly the thinnest in the world at present, has high mechanical property.
Epoxy resin is typical thermosetting polymer, has good electrical insulating property, chemical stability, excellent cementability and mechanical stability, is applied in corrosion resistant coating, insulating material and structural bond material etc.But form crosslinked three-dimensional net structure after epoxy resin cure, internal stress be large, Anticrack ability and the shortcoming such as shock-resistance is poor, thus be difficult to meet industrial requirement, therefore modified epoxy becomes the focus of research.At present mainly adopt that rubber elastomer is toughness reinforcing, inorganic nano-particle toughening, thermoplastic polymer are toughness reinforcing and hyperbranched polymer is toughness reinforcing etc. that method carries out toughening modifying to epoxy resin.Wherein adopt study on hyperbranched polymer modified epoxy resins can not only improve its toughness, also do not reduce the performances such as its thermotolerance, therefore hyperbranched polymer makes the over-all properties of epoxy resin be enhanced.
Yin Meizhen etc. report patent of invention " a kind of synthesis of difunctional water-soluble perylene diimide derivatives and application thereof " (CN103755703A); use and carry four aldehyde radical perylene fluorescent core, prepare difunctional water-soluble perylene diimide derivatives by the protective reaction of sulfydryl to aldehyde radical.Chen Runfeng etc. report patent of invention " perylene diimide type photonic functional material and preparation method thereof " (CN102070771A); prepared the polymkeric substance of a series of different content by Suzuki polymerization, Yamamoto polymerization and Stille polymerization, this material has good photo and thermal stability.Liu Kuo etc. report patent of invention " method of modifying epoxy resin through amino-terminated hyperbranched polymer-grafted graphene oxide " (CN102504147A), utilize hyperbranched polymer to carry out modified epoxy, research shows that a small amount of hyperbranched polymer can increase substantially thermal characteristics and the mechanical property of epoxy resin.Recklessly to invite etc. in " hyperbranched polymer is to the Progress In Functionalized Treatment of Graphene " paper, review the performance and application of the graphene-based matrix material of hyperbranched polymer functionalization.But it is core that these researchs above-mentioned all do not relate to Yi perylene diimide, Hyperbranched Polymer with Terminal Amido is shell, Graphene is matrix, change a perylene diimide by super of the stacking synthetic graphite thiazolinyl of π-π, and graphene-based super propping up prepared by its and epoxy resin compound and change perylene diimide/epoxy resin composite material.The matrix material utilizing the method to prepare has no bibliographical information at present.
Summary of the invention
The object of this invention is to provide a kind of preparation method of graphene-based Chao Zhiization perylene diimide/epoxy composite material.
Thinking of the present invention: utilize Chao Zhiization perylene diimide and the stacking effect of Graphene π-π, solve Graphene easy technological difficulties such as reunion, difficulties in dispersion in epoxy resin-base, and improve the interface bond strength of itself and epoxy resin, thus the matrix material of processability excellence.
Concrete steps are:
(1) 0.1 ~ 0.8g Duan Suo Ji perylene diimide, 20 ~ 40ml N is taken, N '-dimethyl formamide and 5 ~ 8ml basic solution, mix and blend reaction 1 ~ 3h at 70 ~ 100 DEG C, slowly drip 2 ~ 3ml R-GLYCIDOL again, continue reaction 8 ~ 12h, then precipitate, filter, throw out is dried, and obtained Chao Zhiization perylene diimide, is PBI-HPG.
(2) Graphene of 0.05 ~ 0.08g through high temperature reduction process is taken, be dispersed in 5 ~ 8ml N, in N '-dimethyl formamide, ultrasonic disperse 5 ~ 6h obtains mixed solution, then in mixed solution, add the PBI-HPG that 0.5 ~ 1g step (1) is obtained, and 20 ~ 24h is reacted at 80 ~ 100 DEG C, then centrifugation, products therefrom is dried at 60 DEG C, obtained graphene-based Chao Zhiization perylene diimide, is PBI-HPG-g-RGO.
(3) PBI-HPG-g-RGO getting 0.026 ~ 0.08g step (2) obtained joins in 26g epoxy resin, decompression is bled, add 7.8g solidifying agent 4 again, 4 '-diaminodiphenylsulfone(DDS), curing molding under 140 DEG C/2h+160 DEG C/2h+180 DEG C/2h is poured in the steel die scribbling silicone grease together into, i.e. obtained graphene-based Chao Zhiization perylene diimide/epoxy composite material after mixing.
Described basic solution is one or more in sodium hydride aqueous solution, the potassium hydride KH aqueous solution and the potassium methylate aqueous solution.
The inventive method has the following advantages:
(1) raw material sources are extensive, and industrial cost is low, and environmental pollution is little.
(2) synthesis technique is simple, is applicable to industrial mass production.
(3) Chao Zhiization perylene diimide by noncovalent interaction and Graphene π-π stacking, solve the technical barrier that Graphene is easily assembled, graphene-based for product Chao Zhiization perylene diimide is used for modified epoxy, the dispersed of itself and resin matrix can be realized, and effectively can improve mechanical property and the thermal characteristics of matrix material.
Embodiment
Following examples main raw material used is as follows: Duan Suo Ji perylene diimide (technical grade), Graphene (technical grade), N, N '-dimethyl formamide (analytical pure), R-GLYCIDOL (analytical pure), epoxy resin E-44 (technical grade), 4,4′ diaminodiphenyl sulfone (technical grade).
embodiment 1:
(1) 0.1g Duan Suo Ji perylene diimide (PBI-COOH), 20ml N is taken, N '-dimethyl formamide and 5ml sodium hydride aqueous solution (mass percent concentration is 15%), mix and blend reaction 2h at 70 DEG C, slowly drip 2ml R-GLYCIDOL again, continue reaction 10h, then precipitate, filter, throw out is dried, and obtained Chao Zhiization perylene diimide, is PBI-HPG.
(2) Graphene of 0.05g through high temperature reduction process is taken, be dispersed in 8ml N, in N '-dimethyl formamide, ultrasonic disperse 5h obtains mixed solution, then in mixed solution, add the PBI-HPG that 0.5g step (1) is obtained, and 20h is reacted at 100 DEG C, then centrifugation, products therefrom is dried at 60 DEG C, obtained graphene-based Chao Zhiization perylene diimide, is PBI-HPG-g-RGO.
(3) PBI-HPG-g-RGO getting 0.026g step (2) obtained joins in 26g epoxy resin, decompression is bled, add 7.8g solidifying agent 4 again, 4 '-diaminodiphenylsulfone(DDS), curing molding under 140 DEG C/2h+160 DEG C/2h+180 DEG C/2h is poured in the steel die scribbling silicone grease together into, i.e. obtained graphene-based Chao Zhiization perylene diimide/epoxy composite material after mixing.
The shock strength of graphene-based Chao Zhiization perylene diimide/epoxy composite material that the present embodiment obtains is by the 26.25kJ/m of pure epoxy resin
2bring up to 30.33kJ/m
2, improve 15.54%, tensile strength improves 15.00%, and flexural strength adds 29.43%, and heat decomposition temperature improves 10 DEG C.
embodiment 2:
(1) 0.5g Duan Suo Ji perylene diimide (PBI-COOH), 20ml N is taken, N '-dimethyl formamide and 5ml sodium hydride aqueous solution (mass percent concentration is 15%), mix and blend reaction 2h at 70 DEG C, slowly drip 3ml R-GLYCIDOL again, continue reaction 12h, then precipitate, filter, throw out is dried, and obtained Chao Zhiization perylene diimide, is PBI-HPG.
(2) Graphene of 0.07g through high temperature reduction process is taken, be dispersed in 8ml N, in N '-dimethyl formamide, ultrasonic disperse 5h obtains mixed solution, then in mixed solution, add the PBI-HPG that 0.7g step (1) is obtained, and 20h is reacted at 100 DEG C, then centrifugation, products therefrom is dried at 60 DEG C, obtained graphene-based Chao Zhiization perylene diimide, is PBI-HPG-g-RGO.
(3) PBI-HPG-g-RGO getting 0.042g step (2) obtained joins in 26g epoxy resin, decompression is bled, add 7.8g solidifying agent 4 again, 4 '-diaminodiphenylsulfone(DDS), curing molding under 140 DEG C/2h+160 DEG C/2h+180 DEG C/2h is poured in the steel die scribbling silicone grease together into, i.e. obtained graphene-based Chao Zhiization perylene diimide/epoxy composite material after mixing.
The shock strength of graphene-based Chao Zhiization perylene diimide/epoxy composite material that the present embodiment obtains is by the 26.25kJ/m of pure epoxy resin
2bring up to 39.58kJ/m
2, improve 50.78%, tensile strength improves 62.28%, and flexural strength adds 52.96%, and heat decomposition temperature improves 25 DEG C.
embodiment 3:
(1) 0.8g Duan Suo Ji perylene diimide (PBI-COOH), 30ml N is taken, N '-dimethyl formamide and 5ml sodium hydride aqueous solution (mass percent concentration is 15%), mix and blend reaction 2h at 70 DEG C, slowly drip 3ml R-GLYCIDOL again, continue reaction 12h, then precipitate, filter, throw out is dried, and obtained Chao Zhiization perylene diimide, is PBI-HPG.
(2) Graphene of 0.07g through high temperature reduction process is taken, be dispersed in 8ml N, in N '-dimethyl formamide, ultrasonic disperse 5h obtains mixed solution, then in mixed solution, add the PBI-HPG that 0.8g step (1) is obtained, and 24h is reacted at 80 DEG C, then centrifugation, products therefrom is dried at 60 DEG C, obtained graphene-based Chao Zhiization perylene diimide, is PBI-HPG-g-RGO.
(3) PBI-HPG-g-RGO getting 0.05g step (2) obtained joins in 26g epoxy resin, decompression is bled, add 7.8g solidifying agent 4 again, 4 '-diaminodiphenylsulfone(DDS), curing molding under 140 DEG C/2h+160 DEG C/2h+180 DEG C/2h is poured in the steel die scribbling silicone grease together into, i.e. obtained graphene-based Chao Zhiization perylene diimide/epoxy composite material after mixing.
The shock strength of graphene-based Chao Zhiization perylene diimide/epoxy composite material that the present embodiment obtains is by the 26.25kJ/m of pure epoxy resin
2bring up to 34.95kJ/m
2, improve 33.14%, tensile strength improves 48.85%, and flexural strength adds 47.67%.Heat decomposition temperature improves 21 DEG C.
Claims (1)
1. a preparation method for graphene-based super change perylene diimide/epoxy composite material, is characterized in that concrete steps are:
(1) 0.1 ~ 0.8g Duan Suo Ji perylene diimide, 20 ~ 40ml N is taken, N '-dimethyl formamide and 5 ~ 8ml basic solution, mix and blend reaction 1 ~ 3h at 70 ~ 100 DEG C, slowly drip 2 ~ 3ml R-GLYCIDOL again, continue reaction 8 ~ 12h, then precipitate, filter, throw out is dried, and obtained Chao Zhiization perylene diimide, is PBI-HPG;
(2) Graphene of 0.05 ~ 0.08g through high temperature reduction process is taken, be dispersed in 5 ~ 8ml N, in N '-dimethyl formamide, ultrasonic disperse 5 ~ 6h obtains mixed solution, then in mixed solution, add the PBI-HPG that 0.5 ~ 1g step (1) is obtained, and 20 ~ 24h is reacted at 80 ~ 100 DEG C, then centrifugation, products therefrom is dried at 60 DEG C, obtained graphene-based Chao Zhiization perylene diimide, is PBI-HPG-g-RGO;
(3) PBI-HPG-g-RGO getting 0.026 ~ 0.08g step (2) obtained joins in 26g epoxy resin, decompression is bled, add 7.8g solidifying agent 4 again, 4 '-diaminodiphenylsulfone(DDS), curing molding under 140 DEG C/2h+160 DEG C/2h+180 DEG C/2h is poured in the steel die scribbling silicone grease together into, i.e. obtained graphene-based Chao Zhiization perylene diimide/epoxy composite material after mixing;
Described basic solution is one or more in sodium hydride aqueous solution, the potassium hydride KH aqueous solution and the potassium methylate aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262030.4A CN104893246B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of graphene-based hyperbranched acid imide/epoxy composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262030.4A CN104893246B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of graphene-based hyperbranched acid imide/epoxy composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104893246A true CN104893246A (en) | 2015-09-09 |
| CN104893246B CN104893246B (en) | 2016-09-28 |
Family
ID=54026235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510262030.4A Active CN104893246B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of graphene-based hyperbranched acid imide/epoxy composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104893246B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883557A (en) * | 2017-04-06 | 2017-06-23 | 桂林理工大学 | The method that Li perylene acid anhydride non-covalent modification Graphenes prepare epoxy matrix composite |
| CN107236199A (en) * | 2017-07-26 | 2017-10-10 | 云南电网有限责任公司电力科学研究院 | A kind of modified EPT rubber and preparation method |
| CN108948622A (en) * | 2018-06-28 | 2018-12-07 | 合肥艾飞新材料有限公司 | A kind of epoxy-modified graphene film and preparation method thereof |
| CN110240892A (en) * | 2019-07-03 | 2019-09-17 | 桂林理工大学 | A kind of bionic laminar graphene/imide derivative thermally conductive film and preparation method thereof |
| CN110317582A (en) * | 2019-07-03 | 2019-10-11 | 桂林理工大学 | A kind of imide derivative functionalization graphene/carbon nanotube composite heat-conducting film and preparation method thereof |
| CN116332212A (en) * | 2023-04-13 | 2023-06-27 | 衡阳市建衡实业有限公司 | Preparation method of polyaluminum chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063401A (en) * | 2005-08-31 | 2007-03-15 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| CN103194165A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | Method for preparing high-heat-conductivity conductive adhesive containing graphene |
| CN104059395A (en) * | 2014-06-29 | 2014-09-24 | 桂林理工大学 | Preparation method for perylene bisimide polyurethane liquid crystal non-covalent modified graphene |
-
2015
- 2015-05-21 CN CN201510262030.4A patent/CN104893246B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007063401A (en) * | 2005-08-31 | 2007-03-15 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| CN103194165A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | Method for preparing high-heat-conductivity conductive adhesive containing graphene |
| CN104059395A (en) * | 2014-06-29 | 2014-09-24 | 桂林理工大学 | Preparation method for perylene bisimide polyurethane liquid crystal non-covalent modified graphene |
Non-Patent Citations (1)
| Title |
|---|
| DANIEL GöRL ET AL.: ""Molecular Assemblies of Perylene Bisimide Dyes in Water"", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883557A (en) * | 2017-04-06 | 2017-06-23 | 桂林理工大学 | The method that Li perylene acid anhydride non-covalent modification Graphenes prepare epoxy matrix composite |
| CN107236199A (en) * | 2017-07-26 | 2017-10-10 | 云南电网有限责任公司电力科学研究院 | A kind of modified EPT rubber and preparation method |
| CN107236199B (en) * | 2017-07-26 | 2019-11-29 | 云南电网有限责任公司电力科学研究院 | A kind of modified EPT rubber and preparation method |
| CN108948622A (en) * | 2018-06-28 | 2018-12-07 | 合肥艾飞新材料有限公司 | A kind of epoxy-modified graphene film and preparation method thereof |
| CN110240892A (en) * | 2019-07-03 | 2019-09-17 | 桂林理工大学 | A kind of bionic laminar graphene/imide derivative thermally conductive film and preparation method thereof |
| CN110317582A (en) * | 2019-07-03 | 2019-10-11 | 桂林理工大学 | A kind of imide derivative functionalization graphene/carbon nanotube composite heat-conducting film and preparation method thereof |
| CN116332212A (en) * | 2023-04-13 | 2023-06-27 | 衡阳市建衡实业有限公司 | Preparation method of polyaluminum chloride |
| CN116332212B (en) * | 2023-04-13 | 2024-06-04 | 衡阳市建衡实业有限公司 | Preparation method of polyaluminum chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104893246B (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104893246A (en) | Preparation method of graphene-based hyperbranched perylene imide/epoxy composite | |
| Mohamed et al. | Solid-state chemical transformations to enhance gas capture in benzoxazine-linked conjugated microporous polymers | |
| Samy et al. | Pyrene-functionalized tetraphenylethylene polybenzoxazine for dispersing single-walled carbon nanotubes and energy storage | |
| CN102604332B (en) | Method for grafting SiO2 nanoparticles with graphene oxide modified epoxy resin | |
| CN102642830A (en) | Method for preparing graphene modified by silane coupling agent | |
| CN103819880B (en) | Method for modifying graphene modified epoxy resin by amphiphilic copolymer | |
| CN106243715B (en) | A kind of high heat conduction polyimides/boron nitride composite and preparation method thereof | |
| CN104262588A (en) | Graphene oxide-based curing agent as well as preparation and use thereof | |
| CN102443247A (en) | Preparation method of graphene oxide grafted POSS modified epoxy resin | |
| CN104861650A (en) | Heat-resistant benzoxazine resin and preparation method thereof | |
| CN102504252B (en) | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof | |
| CN102504147A (en) | Method for modifying epoxy resin through amino-terminated hyperbranched polymer-grafted graphene oxide | |
| CN102875973B (en) | Modified carbon nanotube/thermosetting resin composite and preparation method thereof | |
| CN101955631A (en) | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material | |
| WO2022062370A1 (en) | Dielectricity and thermal conductivity enhanced bio-based high-temperature-resistant epoxy resin, preparation method therefor, and application thereof | |
| CN110330649B (en) | Remodelable bismaleimide resin and application thereof | |
| CN103073889B (en) | Flame retardant thermosetting resin and preparation method thereof | |
| CN103848993A (en) | Preparation method for hollow TiO2 microsphere surface grafted polyimide composite particles | |
| CN104356388A (en) | Flame-retardant bismaleimide resin and preparation method thereof | |
| CN101891936B (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN105086449A (en) | Phosphorus-containing POSS (polyhedral oligomeric silsesquioxane) flame-retardant bismaleimide resin and preparation method thereof | |
| CN104448823A (en) | Flame-retardant bismaleimide resin composition and preparation method thereof | |
| Selvaraj et al. | Development of high-performance hybrid sustainable bio-composites from biobased carbon reinforcement and cardanol-benzoxazine matrix | |
| CN101602856A (en) | Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes | |
| CN104277069A (en) | Synthesis and application of new nano hybrid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190305 Address after: 312000 West Side of Shangma Bay Village East Ring Line, Fuquan Street, Keqiao District, Shaoxing City, Zhejiang Province Patentee after: Shaoxing Guenot SuperLing Lubrication Material Co., Ltd. Address before: No. 12, Jian Gong Road, Guilin, the Guangxi Zhuang Autonomous Region Patentee before: Guilin University of Technology |
|
| TR01 | Transfer of patent right |