CN109265930A - A kind of low-cost high-toughness self-lubricating epoxy resin and preparation method - Google Patents
A kind of low-cost high-toughness self-lubricating epoxy resin and preparation method Download PDFInfo
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- CN109265930A CN109265930A CN201810818846.4A CN201810818846A CN109265930A CN 109265930 A CN109265930 A CN 109265930A CN 201810818846 A CN201810818846 A CN 201810818846A CN 109265930 A CN109265930 A CN 109265930A
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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
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
Abstract
The present invention relates to a kind of low-cost high-toughness self-lubricating epoxy resin and preparation method thereof, it is characterised in that: the resin is that 3~15 parts of epoxy group hyperbranched polyorganosiloxanes, 10~40 parts of multiple functionality epoxide resins and 60~90 parts of bisphenol A type epoxy resin and 25~40 parts of amine curing agent form by mass fraction.The resin has many characteristics, such as that coefficient of friction is low, bearing capacity is strong, good toughness has a wide range of applications in resin matrix of the fields such as aerospace, electric mechanical, nuclear industry as electronic package material, wear-resistant coating, structural composite material etc..The impact strength > 33.0KJ/m of its casting matrix2, 220 DEG C of bending strength > 150MPa, coefficient of friction < 0.25, glass transition temperature >.
Description
Technical field
The invention belongs to advanced field of high-polymer material science, are related to a kind of low-cost high-toughness self-lubricating asphalt mixtures modified by epoxy resin
Rouge and preparation method.
Background technique
Epoxy resin is a kind of general thermosetting resin, has excellent adhesion energy, chemical stability, molding add
Work has a large amount of application in fields such as space flight and aviation, electronics industry, automobile manufactures.But it is led when being applied to new and high technology
When domain, the solidfied material of epoxy resin there are brittleness it is big, toughness is insufficient, coefficient of friction is larger the problems such as, need to be modified it.
Currently, mainly have modified rubber, thermoplastic resin modified, liquid crystal polymer modified to epoxy resin modification and
Core-shell polymer modification etc..On the one hand rubber-toughened epoxy resin is to utilize phase of the rubber grain in epoxy resin continuous phase
Separation；On the other hand, using rubber active end group participate in epoxy resin curing reaction so that improve itself and resin matrix it
Between interface bond strength.When by external force, two-phase interface can generate plastic deformation, and Anticrack plays the effect of toughening
Fruit.End hydroxy butadiene, carboxyl-terminated polybutadiene, hydroxy'terminated butadiene nitrile rubber, nbr carboxyl terminal and epoxy terminated butyronitrile
A variety of rubber such as rubber are all used for the toughening modifying of epoxy resin.But rubber is improving epoxy resin cured product toughness
Meanwhile it can frequently result in being decreased obviously for solidfied material thermal stability and modulus.
Compared to rubber elastomer, the modulus and heat resistance of thermoplastic resin are relatively high, and being added in epoxy resin can not only
Improve the toughness of material, moreover it is possible to keep or be promoted the modulus and thermal stability of material.Thermoplastic resin energy when by external force
It enough generates moderate finite deformation and absorbs energy to failure, to hinder the extension of crackle, improve the toughness of epoxy resin.Polysulfones, polyethers
A variety of thermoplastic resins such as sulfone, polyetherimide, polyether-ketone, polyether-ether-ketone and polycarbonate can be used in the increasing of epoxy resin
Tough modification.In thermoplastic resin modified epoxy-resin systems, the control of phase separation and phase structure is the key that modified.
Can thermoplastic resin occur phase reversal to form continuous phase structure in forming process, can directly influence the effect of toughening
Fruit；Can whether its solubility parameter matches with epoxy resin, the curing agent of selection, control its phase process, is all to obtain
The premise of high-toughness epoxy resin.Also, thermoplastic resin modified epoxy resin can make the viscosity of epoxy resin become larger, and exist
Complex process is difficult to the problem of controlling.
Liquid crystal polymer is a kind of polymer being made of a large amount of rigid mesogenic units and partially flexible segment.Rigid mesomorphic
Unit assigns its high modulus and excellent heat resistance, therefore liquid crystal polymer also can while improving epoxy resin toughness
Improve its thermal stability and modulus.Soft segment can generate certain Relaxation Phenomena in stress transfer, inhibit crackle
Extension.Meanwhile liquid crystal polymer has the advantages that self-reinforcing, easily orientation, particle or fento easy to form in epoxy matrix again
To further increase the toughness of epoxy resin.But liquid crystal polymer synthesis and raw material sources difficulty, higher cost, and it is thermotropic
Property liquid crystal heat distortion temperature it is very high, hardly possible matched with common substrate polymer, cause machine-shaping difficulty.
When core-shell polymer is as toughener, usually soft core-monocoque, stratum nucleare is the rubber with toughening effect
Body, shell are the polymer that can be mixed and be reacted with epoxy resin, and usually having can be with epoxy resin-matrix precursor reactant
Functional group.The feature of core-shell polymer flexibilizing epoxy maximum is that solidification front and back particle shape is held essentially constant, can be homogeneous
It is dispersed in resin matrix, so that toughening effect is obvious, but the coefficient of friction of epoxy resin can be made to become larger, wearability
It reduces.
Dissaving polymer has many advantages, such as that viscosity is low, degree of functionality is high, chain entanglement is few and dissolubility is good, can significantly mention
The toughness and craftsmanship of high epoxy resin.It is added in epoxy resin, forms homogeneous system both when beginning, when solidification
Generation mutually separates, to achieve the purpose that toughening.With On Epoxy Resin Modified By Hyperbranched Polymers, there are also following two advantages:
(1) its chondritic can reduce the shrinkage of curable epoxide product；(2) its active end group such as amino, epoxy group, carboxyl etc. can
Directly to participate in the solidification that curing cross-linking reaction even promotes epoxy resin.Based on the above advantage, in recent years with hyperbranched polymerization
The epoxy resin toughened research report of object gradually increases.But the method for preparing dissaving polymer at present, universal preparation step are numerous
It is trivial, solvent and catalyst are largely used, the large-scale promotion production of business is not suitable for.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention propose a kind of low-cost high-toughness self-lubricating epoxy resin and
Preparation method.
Technical solution
A kind of low-cost high-toughness self-lubricating epoxy resin, it is characterised in that the mass fraction of component are as follows: 3~15 parts of epoxies
Base hyperbranched polyorganosiloxane, 10~40 parts of multi-functional epoxies and 60~90 parts of bisphenol A type epoxy resin and 25~40
The amine curing agent of part；The structural formula of the epoxy group hyperbranched polyorganosiloxane are as follows:
The structural formula of the multi-functional epoxy are as follows:
The structural formula of the bisphenol A type epoxy resin are as follows:
The amine curing agent includes ethylenediamine, triethylene tetramine, 4,4'- diaminodiphenylmethane or 4,4'- diamino
Diphenyl sulphone (DPS).
The epoxy group hyperbranched polyorganosiloxane is with molar ratio for (2~1): 3 3- glycydoxy three
Methoxy silane and neopentyl glycol are sloughed methanol polycondensation in the case where heating temperature is 80~160 DEG C of reaction condition and are formed.
A method of preparing any one of described low-cost high-toughness self-lubricating epoxy resin, it is characterised in that step is such as
Under:
Step 1:10~40 part multi-functional epoxy monomer and 60~90 parts of bisphenol A type epoxy resin and 25~40
The amine curing agent of part prepares resin prepolymer in 80~140 DEG C of 1~2h of stirring；
Step 2: adding 3~15 parts of hyperbranched polyorganosiloxanes, stir 10~30min, pour at 100~140 DEG C
In the mold of preheating, in 100~140 DEG C of vacuum tank, removing bubble is vacuumized, air dry oven is put into and carries out stage liter
Temperature solidification, curing process is 110~150 DEG C/2h+150~170 DEG C/2h, cooling, after demoulding, then at 200~230 DEG C after
Handle 2h to obtain the final product.
Beneficial effect
A kind of low-cost high-toughness self-lubricating epoxy resin proposed by the present invention and preparation method, using one kind to multifunctional
The epoxy group hyperbranched polyorganosiloxane of degree is modified bisphenol A type epoxy resin, while assigning epoxy resin toughness,
Its coefficient of friction can be reduced；Meanwhile in order to avoid the heat resistance of resin is affected, while multi-functional epoxy and its are added
It is copolymerized, to improve its crosslink density.It is sealed by " one kettle way " by Novel ring oxygroup prepared by ester exchange polycondensation using one kind
The hyperbranched polyorganosiloxane at end carries out toughening modifying to epoxy resin.In addition to having common dissaving polymer flexibilizing epoxy tree
Outside the characteristics of rouge, and utilization has the characteristics of low-surface-energy of poly- silicon, assigns modified resin self-lubricating property, while having and rubbing
The features such as low, the strong, good toughness of bearing capacity of coefficient are wiped, and preparation process is simple, it is easy to industrialized production, in aerospace, electricity
Resin matrix of the fields such as handset tool, nuclear industry as electronic package material, wear-resistant coating, structural composite material etc. has wide
General application.The impact strength > 33KJ/m of its casting matrix2, bending strength > 150MPa, coefficient of friction < 0.25, vitrifying
200 DEG C of transition temperature >.
The present invention is with multi-functional epoxy monomer and epoxy group hyperbranched polyorganosiloxane while modified bisphenol A type asphalt mixtures modified by epoxy resin
Rouge under the high temperature conditions, makes amino and epoxy group that ring-opening polymerisation occur, forms 3 D stereo knot using polynary amine as curing agent
Structure；The hybrid resin has lower viscosity in wider temperature range, is conducive to cast molding.In addition, epoxy group is overspend
Change polysiloxanes by " one kettle way " it is solvent-free, without catalyst under conditions of be prepared by polycondensation, and epoxy group surpasses
Branched polysiloxane and epoxy resin-base have good compatibility, and a large amount of epoxy group in periphery can be with amine curing agent
It is reacted, to obtain the low epoxy resin cured product of heat-resist, excellent in mechanical performance, coefficient of friction.
Specific embodiment
Now in conjunction with embodiment, the invention will be further described:
Due to traditional dissaving polymer preparation method complex steps, using a large amount of solvents and catalyst, therefore business is big
Scale preparation is difficult；Bisphenol A type epoxy resin crosslink density is big, and toughness is insufficient, and coefficient of friction is larger, and heat resistance is not high.Cause
This, will improve the toughness and heat resistance of epoxy resin, and assign its self-lubrication, it is important to select and synthesize low-surface-energy
Hyperbranched polyorganosiloxane, to epoxy resin-base carry out toughening modifying while, assign its self-lubrication, and do not influence
Its heat resistance.The present invention utilizes the low viscosity of hyperbranched polyorganosiloxane, low-surface-energy, high reaction activity, contains a large amount of free bodies
Long-pending feature is modified epoxy resin, while by multiple functionality epoxide resin monomer and bisphenol A type epoxy resin and amine
Curing agent mixes according to a certain percentage, is copolymerized, solidifies and obtain, and to improve crosslink density, assigns epoxy resin excellent hot
Can, so that the epoxy resin modification system being prepared has excellent mechanical property, thermal stability and greasy property.
The specific method is as follows:
Mix 10~40 parts of multi-functional epoxy monomers and 60~90 parts of bisphenol A type epoxy resin and 25~40 parts
Amine curing agent prepare resin prepolymer in 80~140 DEG C of 1~2h of stirring.Then, by 3~15 parts of hyperbranched poly silicon oxygen
Alkane is added in above-mentioned performed polymer, stirs 10~30min, is poured into hot mold, in 100~140 DEG C of vacuum tank,
Vacuumize removing bubble, be put into air dry oven carry out step-up temperature solidification, curing process be 110~150 DEG C/2 h+150~
It is 170 DEG C/2h, cooling, after demoulding, then at 200~230 DEG C post-process 2h to obtain the final product.
Embodiment 1:
Mix the 4,4'- diamino of 10 parts of multi-functional epoxy monomers and 90 parts of bisphenol A type epoxy resin and 25 parts
Base diphenyl sulphone (DPS), until it is melted, prepares resin prepolymer in 120 DEG C of stirring 1h.Then, by 3 parts of hyperbranched polyorganosiloxanes 120
It DEG C is added in above-mentioned performed polymer, stirs 15min, pour into hot mold, in 120~130 DEG C of vacuum tank, take out true
Sky removes bubble, is put into air dry oven and carries out step-up temperature solidification, curing process is 150 DEG C/2 h+170 DEG C/2h, then certainly
It is so cooling, after demoulding, then at 230 DEG C post-process 2h to obtain the final product.
Embodiment 2:
Mix the 4,4'- diamino of 20 parts of multi-functional epoxy monomers and 80 parts of bisphenol A type epoxy resin and 30 parts
Base diphenyl-methane, until it is melted, prepares resin prepolymer in 130 DEG C of stirring 1h.Then, 3 parts of hyperbranched polyorganosiloxanes are existed
130 DEG C are added in above-mentioned performed polymer, stir 10min, pour into hot mold, in 130 DEG C of vacuum tank, vacuumize
Bubble is removed, air dry oven is put into and carries out step-up temperature solidification, curing process is 150 DEG C/2 h+170 DEG C/2h, then natural
It is cooling, after demoulding, then at 230 DEG C post-process 2h to obtain the final product.
Embodiment 3:
Mix the 4,4'- diamino of 30 parts of multi-functional epoxy monomers and 70 parts of bisphenol A type epoxy resin and 35 parts
Base diphenyl sulphone (DPS), until it is melted, prepares resin prepolymer in 110 DEG C of stirring 2h.Then, by 3 parts of hyperbranched polyorganosiloxanes 110
It DEG C is added in above-mentioned performed polymer, stirs 30min, pour into hot mold, in 130 DEG C of vacuum tank, vacuumize removing
Bubble is put into air dry oven and carries out step-up temperature solidification, and curing process is 150 DEG C/2 h+170 DEG C/2h, then naturally cold
But, after demoulding, then at 230 DEG C post-process 2h to obtain the final product.
Embodiment 4:
Mix the 4,4'- diamino of 40 parts of multi-functional epoxy monomers and 60 parts of bisphenol A type epoxy resin and 40 parts
Base diphenyl-methane, until it is melted, prepares resin prepolymer in 120 DEG C of stirring 2h.Then, 6 parts of hyperbranched polyorganosiloxanes are existed
120 DEG C are added in above-mentioned performed polymer, stir 20min, pour into hot mold, in 130 DEG C of vacuum tank, vacuumize
Bubble is removed, air dry oven is put into and carries out step-up temperature solidification, curing process is 150 DEG C/2 h+170 DEG C/2h, then natural
It is cooling, after demoulding, then at 230 DEG C post-process 2h to obtain the final product.
Embodiment 5:
Mix the 4,4'- diamino of 20 parts of multi-functional epoxy monomers and 80 parts of bisphenol A type epoxy resin and 30 parts
Base diphenyl sulphone (DPS), until it is melted, prepares resin prepolymer in 120 DEG C of stirring 1h.Then, by 8 parts of hyperbranched polyorganosiloxanes 120
It DEG C is added in above-mentioned performed polymer, stirs 30min, pour into hot mold, in 130 DEG C of vacuum tank, vacuumize removing
Bubble is put into air dry oven and carries out step-up temperature solidification, and curing process is 150 DEG C/2 h+170 DEG C/2h, then naturally cold
But, after demoulding, then at 230 DEG C post-process 2h to obtain the final product.
Embodiment 6:
Mix the 4,4'- diamino of 20 parts of multi-functional epoxy monomers and 80 parts of bisphenol A type epoxy resin and 30 parts
Base diphenyl sulphone (DPS), until it is melted, prepares resin prepolymer in 120 DEG C of stirring 1h.Then, 10 parts of hyperbranched polyorganosiloxanes are existed
120 DEG C are added in above-mentioned performed polymer, stir 30min, pour into hot mold, in 130 DEG C of vacuum tank, vacuumize
Bubble is removed, air dry oven is put into and carries out step-up temperature solidification, curing process is 150 DEG C/2 h+170 DEG C/2h, then natural
It is cooling, after demoulding, then at 230 DEG C post-process 2h to obtain the final product.
Embodiment 7:
Mix the triethylene four of 20 parts of multi-functional epoxy monomers and 80 parts of bisphenol A type epoxy resin and 30 parts
Amine, in 100 DEG C of stirring 1h, until its homogeneous transparent, prepares resin prepolymer.Then, by 3 parts of hyperbranched polyorganosiloxanes at 100 DEG C
It is added in above-mentioned performed polymer, stirs 30min, pour into hot mold, in 110 DEG C of vacuum tank, vacuumize except degassing
Bubble is put into air dry oven and carries out step-up temperature solidification, and curing process is 120 DEG C/2 h+150 DEG C/2h, then natural cooling,
After demoulding, then at 200 DEG C post-process 2h to obtain the final product.
Embodiment 8:
20 parts of multi-functional epoxy monomers and 80 parts of bisphenol A type epoxy resin and 30 parts of ethylenediamine are mixed,
80 DEG C of stirring 1h, until its homogeneous transparent, prepares resin prepolymer.Then, 6 parts of hyperbranched polyorganosiloxanes are added at 100 DEG C
In above-mentioned performed polymer, 30min is stirred, is poured into hot mold, in 100 DEG C of vacuum tank, is vacuumized removing bubble, put
Enter air dry oven and carry out step-up temperature solidification, curing process is 110 DEG C/2h+150 DEG C/2 h, it is cooling, after demoulding, then
Post-process 2h at 200 DEG C to obtain the final product.
Claims (4)
1. a kind of low-cost high-toughness self-lubricating epoxy resin, it is characterised in that the mass fraction of component are as follows: 3~15 parts of epoxy groups
Hyperbranched polyorganosiloxane, 10~40 parts of multi-functional epoxies and 60~90 parts of bisphenol A type epoxy resin and 25~40 parts
Amine curing agent；The structural formula of the epoxy group hyperbranched polyorganosiloxane are as follows:
The structural formula of the multi-functional epoxy are as follows:
The structural formula of the bisphenol A type epoxy resin are as follows:
2. low-cost high-toughness self-lubricating epoxy resin according to claim 1, it is characterised in that: the amine curing agent packet
Include ethylenediamine, triethylene tetramine, 4,4'- diaminodiphenylmethane or 4,4' diaminodiphenyl sulfone.
3. low-cost high-toughness self-lubricating epoxy resin according to claim 1 or claim 2, it is characterised in that: the epoxy group is super
Branched polysiloxane is with molar ratio for (2~1): 3 3- glycidyl ether oxypropyltrimethoxysilane and neopentyl glycol,
Methanol polycondensation is sloughed in the case where heating temperature is 80~160 DEG C of reaction condition to form.
4. a kind of method for preparing the claim 1~6 any one low-cost high-toughness self-lubricating epoxy resin, feature exist
In steps are as follows:
Step 1:10~40 part multi-functional epoxy monomer and 60~90 parts of bisphenol A type epoxy resin and 25~40 parts
Amine curing agent prepares resin prepolymer in 80~140 DEG C of 1~2h of stirring；
Step 2: adding 3~15 parts of hyperbranched polyorganosiloxanes, stir 10~30min, pour into and preheated at 100~140 DEG C
Mold in, in 100~140 DEG C of vacuum tank, vacuumize removing bubble, being put into air dry oven, to carry out step-up temperature solid
Change, curing process is 110~150 DEG C/2h+150~170 DEG C/2h, cooling, after demoulding, then at 200~230 DEG C post-processes 2h
To obtain the final product.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591501A (en) * | 2019-09-15 | 2019-12-20 | 西北工业大学 | Hyperbranched polysiloxane-containing epoxy bonding type solid lubricating material, preparation method and coating method |
| CN111057218A (en) * | 2019-12-31 | 2020-04-24 | 达森(天津)材料科技有限公司 | Preparation method of special anti-corrosion high-temperature-resistant epoxy resin for oil extraction sucker rod |
| CN111454672A (en) * | 2020-05-25 | 2020-07-28 | 湖北航泰科技有限公司 | Adhesive film for bonding rubber material and preparation method thereof |
| CN113201266A (en) * | 2021-06-20 | 2021-08-03 | 西北工业大学 | High-performance epoxy bonding type solid self-lubricating coating and preparation and use method thereof |
| CN113549299A (en) * | 2021-07-22 | 2021-10-26 | 泉州师范学院 | Preparation method of high-wear-resistance and high-toughness graphene nanosheet/epoxy resin composite material |
| CN114800295A (en) * | 2022-03-30 | 2022-07-29 | 郑州九天工贸有限公司 | Self-lubricating resin cutting sheet and preparation method thereof |
| CN116285572A (en) * | 2023-02-24 | 2023-06-23 | 上海骋润高分子材料有限公司 | High-lubrication coating and preparation method thereof |
| CN117285872A (en) * | 2023-11-27 | 2023-12-26 | 杭州本创科技有限公司 | Hyperbranched epoxy graphene anticorrosive paint and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591501A (en) * | 2019-09-15 | 2019-12-20 | 西北工业大学 | Hyperbranched polysiloxane-containing epoxy bonding type solid lubricating material, preparation method and coating method |
| CN110591501B (en) * | 2019-09-15 | 2021-05-18 | 西北工业大学 | Epoxy bonding type solid lubricating material containing hyperbranched polysiloxane, preparation method and coating method |
| CN111057218A (en) * | 2019-12-31 | 2020-04-24 | 达森(天津)材料科技有限公司 | Preparation method of special anti-corrosion high-temperature-resistant epoxy resin for oil extraction sucker rod |
| CN111454672A (en) * | 2020-05-25 | 2020-07-28 | 湖北航泰科技有限公司 | Adhesive film for bonding rubber material and preparation method thereof |
| CN113201266A (en) * | 2021-06-20 | 2021-08-03 | 西北工业大学 | High-performance epoxy bonding type solid self-lubricating coating and preparation and use method thereof |
| CN113549299A (en) * | 2021-07-22 | 2021-10-26 | 泉州师范学院 | Preparation method of high-wear-resistance and high-toughness graphene nanosheet/epoxy resin composite material |
| CN114800295A (en) * | 2022-03-30 | 2022-07-29 | 郑州九天工贸有限公司 | Self-lubricating resin cutting sheet and preparation method thereof |
| CN114800295B (en) * | 2022-03-30 | 2023-12-26 | 郑州九天工贸有限公司 | Self-lubricating resin cutting sheet and preparation method thereof |
| CN116285572A (en) * | 2023-02-24 | 2023-06-23 | 上海骋润高分子材料有限公司 | High-lubrication coating and preparation method thereof |
| CN116285572B (en) * | 2023-02-24 | 2024-03-26 | 上海骋润高分子材料有限公司 | High-lubrication coating and preparation method thereof |
| CN117285872A (en) * | 2023-11-27 | 2023-12-26 | 杭州本创科技有限公司 | Hyperbranched epoxy graphene anticorrosive paint and preparation method and application thereof |
| CN117285872B (en) * | 2023-11-27 | 2024-02-06 | 杭州本创科技有限公司 | Hyperbranched epoxy graphene anticorrosive paint and preparation method and application thereof |
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Application publication date: 20190125 |