CN107312162A - A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof - Google Patents
A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof Download PDFInfo
- Publication number
- CN107312162A CN107312162A CN201710641058.8A CN201710641058A CN107312162A CN 107312162 A CN107312162 A CN 107312162A CN 201710641058 A CN201710641058 A CN 201710641058A CN 107312162 A CN107312162 A CN 107312162A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- drying
- epoxy resin
- dried
- preparation
- 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.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/00—Use of pretreated ingredients
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of epoxy curing agent, and the curing agent includes fluorocarbon material and amine curing agent, and the wherein mass fraction of fluorocarbon material is 0~20wt%, not including 0.The epoxy curing agent that the present invention is provided can effectively improve the performances such as the mechanical, corrosion-resistant of epoxide resin material, automatically cleaning.
Description
Technical field
The invention belongs to field of compound material, it is related to a kind of curing agent, more particularly to a kind of epoxy curing agent, one kind
Epoxide resin material and preparation method thereof.
Background technology
Epoxy resin is to refer to the organic compound containing two or more epoxide groups in molecule, in addition to indivedual,
Their relative molecular mass is not high.The molecular structure of epoxy resin is as it using in strand containing active epoxide group
Feature, epoxide group can be located at the end of strand, middle or circlewise structure.Due to containing active ring in molecular structure
Oxygen groups, make them to crosslink reaction with polytype curing agent and form the insoluble height with three-dimensional network structure
Polymers.The high-molecular compound containing epoxide group is referred to as epoxy resin in all molecular structures.Epoxy resin tool after solidification
There are good physics, chemical property, its surface to metal and nonmetallic materials has excellent adhesive strength, and dielectric properties are good
Good, deformation retract rate is small, and product size stability is good, and hardness is high, pliability preferably, to alkali and most of solvent-stable, thus
It is widely used in national defence, each department of national economy, pours into a mould, impregnates, the purposes such as lamination material, bonding agent, coating.
Although the curing agent species for epoxy resin is various, two classes are can be generally divided into.One class is can be with epoxy
Resin is synthesized, and it is crosslinked adult form network structure by the course of step-reaction polymerization.This kind of curing agent is also known as instead
Answering property curing agent, typically all contains active hydrogen atom, during the course of the reaction with the transfer of hydrogen atom, for example：Primary polyamine,
Polybasic carboxylic acid, multi-thiol and polyhydric phenols etc..Another kind of is the curing agent of catalytic, and it can trigger the epoxy radicals in molecular resin
Curing reaction is carried out by cation or the course of anionic polymerisation, such as tertiary amine, boron trifluoride complex.Two class curing agent are all
It is that the reaction of epoxy radicals by having in resinous molecular structure or secondary hydroxyl completes solidification process.
Fluorinated carbon material refers to add fluorinated carbon material to reach the material of the improved materials performance such as machinery in itself, matrix material
Material is often resin.Due to F-Strong oxidizing property, and low electronegativity causes to form extremely strong chemistry between fluorine atom and carbon atom
Key.Different fluorine carbon ratios can cause the difference of fluorinated carbon material performance, for example：CFx,x<0.1, material can show good lead
Electrical property；Fluorine carbon ratio is improved, and the electric conductivity of material can be worse and worse.Common fluorinated carbon material has fluorographite, fluorographite
Alkene, fluorination carbon black, fluorination coke, carbon fluoride nano-tube or fluorinated fullerene etc..Fluorographite and fluorinated graphene are in graphite
The popular research material of the latter two of alkene, fluorinated graphene is even more the Teflon for being known as two dimension, its chemical inertness, heat endurance with
And high resistant anti-performance causes it to be widely applied in electronic applications.Be fluorinated coke, fluorination carbon black, and carbon fluoride nano-tube and
Fluorinated fullerene is STRENGTH ON COKE, carbon black, and CNT and fullerene be fluorinated obtained product, possess low surface can, it is good
Good conductance, capacitive character.Fluorinated carbon material is specifically adapted to the reinforcing agent for doing various composites, especially resin material,
Applied on a large scale in coating industries as the epoxy resin of additive with fluorinated carbon material, such as：Mobile phone, glass
Glass curtain wall, machine components, automobile, ship, Aero-Space, building, transmission line of electricity etc..It is ornamental with protectiveness, tie simultaneously
Structure good stability of the dimension and the particular advantages for being easy to large area global formation, it is possible to increase the wearability and weatherability of material
Deng.But, fluorinated carbon material is mostly hydrophobic oleophobic, the material of low-surface-energy, it is difficult to find effective dispersant, this is also research
One of difficult point.On the other hand, because the mechanical strength that material can bear is not very big, such as its impact strength and stretching are strong
Degree, the shortcomings of anti-corrosion is resistance to, self-cleaning performance is also required to large increase all constrains its further expands and applied.
The content of the invention
For technical problem present in prior art, the present invention provides a kind of epoxy curing agent, and a kind of ring
Oxygen resin material and preparation method thereof, the epoxy curing agent that the present invention is provided can effectively improve the machine of epoxide resin material
The performance such as tool, corrosion-resistant, automatically cleaning.
For up to this purpose, the present invention uses following technical scheme：
One of the object of the invention is to provide a kind of epoxy curing agent, it is characterised in that the curing agent includes fluorine
The mass fraction of carbon material and amine curing agent, wherein fluorocarbon material is 0~20wt%, not including 0.
Wherein, the mass fraction of the fluorocarbon material can be 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%,
4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%,
15wt%, 16wt%, 17wt%, 18wt% or 19wt% etc., it is not limited to cited numerical value, in the number range its
His unrequited numerical value is equally applicable.
As currently preferred technical scheme, the mass fraction of fluorocarbon material is 2~6wt% in the curing agent.
Fluorographite loads amine curing agent, the asphalt mixtures modified by epoxy resin after solidifying with this as intermediate carrier (crosslink centers)
Fat, can both improve cross linking of epoxy resin degree, the performance of fluorocarbon material composite be possessed again, and can improve dispersiveness and remove
Complicated removes dissolving agent process.The performances such as mechanical, the corrosion-resistant, automatically cleaning of epoxy resin can be significantly improved.And controllable condition is done
Go out soft prepolymer.
As currently preferred technical scheme, the fluorocarbon material includes fluorographite, fluorinated graphene, fluorination charcoal
Any one in black, fluorination coke, carbon fluoride nano-tube, fiuorinated pitch or fluorinated fullerene or at least two combination, it is described
Combination is typical but non-limiting examples have：Combination, fluorinated graphene and the group for being fluorinated carbon black of fluorographite and fluorinated graphene
Conjunction, fluorographite and the combination of fluorination coke, the combination of fluorination carbon black and carbon fluoride nano-tube, carbon fluoride nano-tube and fluorination richness
Combination, the combination of fiuorinated pitch and fluorinated fullerene or combination of fluorinated fullerene and fluorographite of alkene etc. are strangled, it is further excellent
Elect fluorographite as.
Preferably, the amine curing agent includes any in polyetheramine, aromatic amine, amino alcohol, monoethanolamine or aminopropanol
It is a kind of or at least two combination, combination typical case but non-limiting examples have：The combination of polyetheramine and aromatic amine, aromatic amine
With the combination of the combination of the combination of amino alcohol, amino alcohol and monoethanolamine, monoethanolamine and aminopropanol, aminopropanol and polyetheramine
Combination or the combination of polyetheramine, aromatic amine and amino alcohol etc., more preferably polyetheramine.
Preferably, the polyetheramine includes polyetheramine D230 and/or polyetheramine D2000.
Preferably, the aromatic amine includes any one in aniline, p-phenylenediamine or m-phenylene diamine (MPD) or at least two group
Close, the combination is typical but non-limiting examples have：The group of the combination of aniline and p-phenylenediamine, p-phenylenediamine and m-phenylene diamine (MPD)
Conjunction, the combination or amine of m-phenylene diamine (MPD) and aniline, the combination of p-phenylenediamine and m-phenylene diamine (MPD) etc..
The two of the object of the invention are to provide a kind of epoxide resin material, and the epoxide resin material is above-mentioned epoxy resin
The epoxy resin of curing agent solidification.
The three of the object of the invention are to provide a kind of preparation method of above-mentioned epoxide resin material, and methods described includes following
Step：
(1) fluorinated material and amine curing agent are mixed and stirred for, dry, obtain epoxy curing agent；
(2) epoxy resin is mixed with the epoxy resin that step (1) is obtained, poured into mould, dried, obtain epoxy resin
Material.
As currently preferred technical scheme, time of step (1) described stirring is 1~3h, such as 1h, 1.2h, 1.5h,
1.8h, 2h, 2.2h, 2.5h, 2.8h or 3h etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value it is equally applicable, preferably 2h.
Preferably, the method for step (1) described drying include heat drying, natural drying, forced air drying, freeze-drying or
Any one or at least two combination are dried in vacuo, the combination is typical but non-limiting examples have：Heat drying and nature
Combination, freeze-drying and the vacuum of combination, forced air drying and the freeze-drying of dry combination, natural drying and forced air drying are dry
Dry combination, vacuum drying and the combination of heat drying or heat drying, forced air drying and vacuum drying combination etc., further
Preferably it is dried in vacuo.
It is above-mentioned to curing agent drying to no longer produce bubble untill.
Preferably, the vacuum drying temperature be 70~90 DEG C, such as 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C,
85 DEG C, 88 DEG C or 90 DEG C etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range
With.
As currently preferred technical scheme, epoxy resin is dried before step (2) described mixing.
Preferably, the method that epoxy resin is dried include heat drying, it is natural drying, forced air drying, cold
Freeze dry or be dried in vacuo any one or at least two combination, the combination is typical but non-limiting examples have：Heating is dry
Combination, the freeze-drying of combination, forced air drying and the freeze-drying of dry and natural drying combination, natural drying and forced air drying
With vacuum drying combination, vacuum drying and the combination of heat drying or heat drying, forced air drying and vacuum drying combination
Deng being more preferably dried in vacuo.
It is above-mentioned to epoxy resin drying to no longer produce bubble untill.
Preferably, the vacuum drying temperature be 70~85 DEG C, such as 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C or
85 DEG C etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, the mass ratio of step (2) epoxy curing agent and epoxy resin
For 1:(1~4), such as 1:1、1:1.5、1:2、1:2.5、1:3、1:3.5 or 1:4 etc., it is not limited to cited numerical value, should
Other unrequited numerical value are equally applicable in number range.
As currently preferred technical scheme, the method for step (2) described drying is to enter under present first drying temperature
Row drying, is dried under the second drying temperature.
Preferably, first drying temperature be 70~90 DEG C, such as 70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85
DEG C, 88 DEG C or 90 DEG C etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range
With.
Preferably, the time dried under first drying temperature be 1~3h, such as 1h, 1.2h, 1.5h, 1.8h, 2h,
2.2h, 2.5h, 2.8h or 3h etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is applicable.
Preferably, second drying temperature be 110~130 DEG C, such as 110 DEG C, 112 DEG C, 115 DEG C, 118 DEG C, 120 DEG C,
122 DEG C, 125 DEG C, 128 DEG C or 130 DEG C etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value is equally applicable.
Preferably, the time dried under first drying temperature be 1~3h, such as 1h, 1.2h, 1.5h, 1.8h, 2h,
2.2h, 2.5h, 2.8h or 3h etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is applicable.
As currently preferred technical scheme, it the described method comprises the following steps：
(1) fluorinated material and amine curing agent are mixed and stirred for 1~3h, dry, obtain epoxy curing agent；
(2) epoxy resin is mixed with the epoxy resin that step (1) is obtained, poured into mould, 1 is dried at 70~90 DEG C
~3h, 1~3h is dried at 110~130 DEG C, epoxide resin material is obtained.
It by epoxy resin and the method that the epoxy resin that step (1) is obtained is mixed is tentatively to mix that wherein step (2) is described
Epoxy resin after conjunction is added to curing agent to be preheated on 70~90 DEG C of Rotary Evaporators, is vacuumized, in 100~150rpm
2~3min of lower rotary evaporation, until well mixed.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention provides a kind of epoxy curing agent, and the curing agent can improve the mechanicalness of epoxide resin material
Energy, corrosion resistance and self-cleaning performance；
(2) present invention provides a kind of epoxide resin material, and the epoxide resin material possesses excellent mechanical performance, anti-impact
Hit intensity is up to more than 0.400J/cm, and tensile strength is up to more than 61MPa；
(3) present invention provides a kind of epoxide resin material, and the epoxide resin material possesses excellent corrosion resistance,
Water, sodium chloride solution, hydrochloric acid, potassium hydroxide solution, machine oil, acetone and tetrahydrofuran etc. be organic and inorganic solution in soak 24h,
Obvious quality increase is not had；
(4) present invention provides a kind of epoxide resin material, and the epoxide resin material possesses excellent self-cleaning performance；
(5) present invention provides a kind of preparation method of epoxide resin material, and the preparation method technique is simple, it is adaptable to work
Industry metaplasia is produced.
Brief description of the drawings
Fig. 1 is the optical microscope photograph of cured epoxy resin containing fluorocarbon material；
Fig. 2 is fluorocarbon material fine dispersion optical microscope photograph in epoxy resin after hardening；
Fig. 3 is Common curing agents (the first from left) and the cured epoxy resin of curing agent containing fluorocarbon material after hot-water soak 24 hours
Photo comparison schemes；
Fig. 4 is that Common curing agents (right side one) and the cured epoxy resin of curing agent containing fluorocarbon material are small in tetrahydrofuran immersion 24
When after photo comparison scheme；
Fig. 5 is that (upper one) is with the cured epoxy resin of curing agent containing fluorocarbon material after acetone soak 24 hours for Common curing agents
Photo comparison schemes；
Fig. 6 is water droplet contact angle photo figure on the cured epoxy resin of curing agent containing fluorocarbon material；
Fig. 7 is water droplet contact angle photo figure on Common curing agents cured epoxy resin；
Fig. 8 is Common curing agents with containing each ratio curing agent cured epoxy resin stretch modulus of fluorocarbon material and impact strength
Comparison diagram；
Fig. 9 is Common curing agents (comparative example 1) and the cured epoxy resin of curing agent containing fluorocarbon material (example 5,6) in hot water
24 hours quality increase ratio comparison diagrams of immersion；
Figure 10 is Common curing agents (comparative example 1) and the cured epoxy resin of curing agent containing fluorocarbon material (example 5,6) third
Ketone soaks 24 hours quality increase ratio comparison diagrams.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
A kind of preparation method of epoxide resin material, the described method comprises the following steps：
(1) 0.125g fluorographites and 25.000g polyetheramines D230 are mixed and stirred for being dried under vacuum to nothing at 2h, 80 DEG C
Bubble is produced, and obtains epoxy curing agent；
(2) the epoxy resin 75.000g that bubble-free is dried under vacuum at the 80 DEG C epoxy resin obtained with step (1) is mixed
Close, pour into mould, 2h is dried at 80 DEG C, dry 2h at 120 DEG C, obtain epoxide resin material.
Embodiment 2
A kind of preparation method of epoxide resin material, the described method comprises the following steps：
(1) 5.000g is fluorinated carbon black and 15.000g m-phenylene diamine (MPD)s and is mixed and stirred at 1h, 70 DEG C heat drying to without gas
Bubble is produced, and obtains epoxy curing agent；
Epoxy resin is mixed, and pours into mould, 3h is dried at 70 DEG C, 3h is dried at 110 DEG C, obtain epoxy resin material
Material.
Embodiment 3
A kind of preparation method of epoxide resin material, the described method comprises the following steps：
(1) 0.500g carbon fluoride nano-tubes and 49.500g monoethanolamines are mixed and stirred at 3h, 90 DEG C heat drying to nothing
Bubble is produced, and obtains epoxy curing agent；
(2) the epoxy resin 75.00g that bubble-free is dried under vacuum at the 85 DEG C epoxy resin obtained with step (1) is mixed
Close, pour into mould, 1h is dried at 90 DEG C, dry 1h at 130 DEG C, obtain epoxide resin material.
Embodiment 4
A kind of preparation method of epoxide resin material, the described method comprises the following steps：
(1) 2.000g fluorinated graphenes and 18.000g aminopropanols are mixed and stirred at 1.5h, 85 DEG C heat drying extremely
Bubble-free is produced, and obtains epoxy curing agent；
(2) the epoxy resin 75.00g that bubble-free is dried under vacuum at the 75 DEG C epoxy resin obtained with step (1) is mixed
Close, pour into mould, 2.5h is dried at 75 DEG C, dry 2.5h at 115 DEG C, obtain epoxide resin material.
Embodiment 5
A kind of preparation method of epoxide resin material, methods described except fluorographite addition be 0.253g in addition to, its
His condition is same as Example 1.
Embodiment 6
A kind of preparation method of epoxide resin material, methods described except fluorographite addition be 0.773g in addition to, its
His condition is same as Example 1.
Embodiment 7
A kind of preparation method of epoxide resin material, methods described except fluorographite addition be 1.316g in addition to, its
His condition is same as Example 1.
Comparative example 1
A kind of preparation method of epoxide resin material, methods described in addition to being added without fluorographite in curing agent, other
Condition is same as Example 1.
Comparative example 2
A kind of preparation method of epoxide resin material, methods described except fluorographite addition be 10.00g in addition to, its
His condition is same as Example 1.
Comparative example 3
A kind of preparation method of epoxide resin material, methods described by amino curing agent except replacing with maleic anhydride
Outside, other conditions are same as Example 1.
Comparative example 4
A kind of preparation method of epoxide resin material, methods described by amino curing agent except replacing with the methyl of 2- ethyls -4
Outside imidazoles, other conditions are same as Example 1.
Mechanical performance is carried out to embodiment 1,5,6,7 and the preparation-obtained epoxide resin material of comparative example 1 and from clearly
The test of clean performance, respectively test epoxy resin impact strength, tensile strength and surface contact angle, as a result as table 1, accompanying drawing 6,
7th, shown in 8.
The solvent resistance of embodiment 5,6 and the preparation-obtained epoxide resin material of comparative example 1 can be tested, surveyed
Test result is as shown in table 2, accompanying drawing 9,10, and wherein the mass concentration of NaCl solution, HCl solution and KOH solution is 3.5wt%.
Corrosion resistance to embodiment 5,6 and the preparation-obtained epoxide resin material of comparative example 1 is contrasted, and test result is for example attached
Shown in Fig. 4, accompanying drawing 5.
Table 1
Table 2
According to table 1 as can be seen that embodiment 1-7 epoxide resin material impact strength is up to more than 0.400J/cm, tension
Intensity is up to more than 61MPa, with excellent mechanical performance, and anti-solvent excellent performance, in water, sodium chloride solution, hydrochloric acid, hydrogen
Potassium oxide solution, machine oil, acetone and tetrahydrofuran etc. be organic and inorganic solution in soak 24h, do not have obvious quality and increase
Plus.And fluorographite is not used in comparative example 1, under causing the machinery system energy and solvent resistance of epoxide resin material to have substantially
Drop；Comparative example 2 is excessive using fluorographite, causes cross linking of epoxy resin excessively, on the contrary material fragility increase, and shock resistance system can have
Declined.Comparative example 3 and comparative example 4 replace amino to solidify using dicarboxylic anhydride and the methylimidazole of 2- ethyls -4 is wished along fourth respectively
Agent, causing the mechanical performance and solvent resistance of epoxy resin can all decline.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implemented.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention
And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and being open.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of epoxy curing agent, it is characterised in that the curing agent includes fluorocarbon material and amine curing agent, wherein fluorine
The mass fraction of carbon material is 0~20wt%, not including 0.
2. curing agent according to claim 1, it is characterised in that the mass fraction of fluorocarbon material is 2 in the curing agent
~6wt%.
3. curing agent according to claim 1 or 2, it is characterised in that the fluorocarbon material includes fluorographite, fluorination stone
Any one in black alkene, fluorination carbon black, fluorination coke, carbon fluoride nano-tube, fiuorinated pitch or fluorinated fullerene or at least two
Combination, more preferably fluorographite；
Preferably, the amine curing agent includes any one in polyetheramine, aromatic amine, amino alcohol, monoethanolamine or aminopropanol
Or at least two combination, more preferably polyetheramine；
Preferably, the polyetheramine includes polyetheramine D230 and/or polyetheramine D2000；
Preferably, the aromatic amine includes any one in aniline, p-phenylenediamine or m-phenylene diamine (MPD) or at least two combination.
4. a kind of epoxide resin material, it is characterised in that the epoxide resin material is any one of the claim 1-3 epoxy
The epoxy resin of resin curing agent solidification.
5. the preparation method of epoxide resin material described in a kind of claim 4, it is characterised in that methods described includes following step
Suddenly：
(1) fluorinated material and amine curing agent are mixed and stirred for, dry, obtain epoxy curing agent；
(2) epoxy resin is mixed with the epoxy resin that step (1) is obtained, poured into mould, dried, obtain epoxy resin material
Material.
6. preparation method according to claim 5, it is characterised in that the time of step (1) described stirring is 1~3h, excellent
Elect 2h as；
Preferably, the method for step (1) described drying includes heat drying, natural drying, forced air drying, freeze-drying or vacuum
Any one in drying or at least two combination, are more preferably dried in vacuo；
Preferably, the vacuum drying temperature is 70~90 DEG C.
7. the preparation method according to claim 5 or 6, it is characterised in that enter before step (2) described mixing to epoxy resin
Row drying；
Preferably, the method that epoxy resin is dried is dry including heat drying, natural drying, forced air drying, freezing
It is dry or be dried in vacuo any one or at least two combination, more preferably it is dried in vacuo；
Preferably, the vacuum drying temperature is 70~85 DEG C.
8. the preparation method according to claim any one of 5-7, it is characterised in that step (2) described epoxy resin cure
The mass ratio of agent and epoxy resin is 1:(1~4).
9. the preparation method according to claim any one of 5-8, it is characterised in that the method for step (2) described drying is
Dried, dried under the second drying temperature under present first drying temperature；
Preferably, first drying temperature is 70~90 DEG C；
Preferably, the time dried under first drying temperature is 1~3h；
Preferably, second drying temperature is 110~130 DEG C；
Preferably, the time dried under first drying temperature is 1~3h.
10. the preparation method according to claim any one of 5-9, it is characterised in that the described method comprises the following steps：
(1) fluorinated material and amine curing agent are mixed and stirred for 1~3h, dry, obtain epoxy curing agent；
(2) epoxy resin is mixed with the epoxy resin that step (1) is obtained, poured into mould, at 70~90 DEG C dry 1~
3h, 1~3h is dried at 110~130 DEG C, epoxide resin material is obtained.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710641058.8A CN107312162A (en) | 2017-07-31 | 2017-07-31 | A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof |
| PCT/CN2017/101683 WO2019024184A1 (en) | 2017-07-31 | 2017-09-14 | Epoxy resin curing agent, epoxy resin material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710641058.8A CN107312162A (en) | 2017-07-31 | 2017-07-31 | A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107312162A true CN107312162A (en) | 2017-11-03 |
Family
ID=60174927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710641058.8A Pending CN107312162A (en) | 2017-07-31 | 2017-07-31 | A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107312162A (en) |
| WO (1) | WO2019024184A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034078A (en) * | 2017-12-15 | 2018-05-15 | 深圳南科二维复材科技有限公司 | A kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and applications |
| CN111001615A (en) * | 2019-11-15 | 2020-04-14 | 沪东中华造船(集团)有限公司 | Novel method for cleaning fresh water tank of ship |
| CN111825832A (en) * | 2020-08-04 | 2020-10-27 | 江苏利宏科技发展有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN115141588A (en) * | 2022-06-29 | 2022-10-04 | 上海回天新材料有限公司 | Epoxy resin adhesive for Type C sealing and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3776845A (en) * | 1969-05-16 | 1973-12-04 | Nippon Paint Co Ltd | Dry film lubricant consisting of synthetic resin,fluorinated graphite,and solid lubricants such as molybdenum disulfide,graphite,and polytetrafluoroethylene |
| CN104788906A (en) * | 2015-04-10 | 2015-07-22 | 重庆交通大学 | Wear-resistant material for brake block of heavy duty automobile |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004124039A (en) * | 2002-08-07 | 2004-04-22 | Toshiba Corp | Cold-curing coating material, method for coating therewith, and article coated therewith |
| CN101423726A (en) * | 2008-12-04 | 2009-05-06 | 上海大学 | Molybdenum disulphide high dispersion modified epoxy resin wear-resistant coating material and preparation method thereof |
| CN103772981B (en) * | 2013-12-30 | 2016-05-04 | 四川大学 | Low dielectric constant polymer/fluorinated graphene composite and preparation method thereof |
| CN104888656B (en) * | 2015-05-13 | 2017-04-05 | 南方科技大学 | The method of purposes of the aminated compoundss in dispersion fluorocarbon material and dispersion fluorocarbon material |
| CN105353587B (en) * | 2015-12-15 | 2019-12-20 | 南方科技大学 | Nano-imprinting photoresist and preparation method thereof |
-
2017
- 2017-07-31 CN CN201710641058.8A patent/CN107312162A/en active Pending
- 2017-09-14 WO PCT/CN2017/101683 patent/WO2019024184A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3776845A (en) * | 1969-05-16 | 1973-12-04 | Nippon Paint Co Ltd | Dry film lubricant consisting of synthetic resin,fluorinated graphite,and solid lubricants such as molybdenum disulfide,graphite,and polytetrafluoroethylene |
| CN104788906A (en) * | 2015-04-10 | 2015-07-22 | 重庆交通大学 | Wear-resistant material for brake block of heavy duty automobile |
Non-Patent Citations (2)
| Title |
|---|
| A.P. KHARITONOV ET AL.: "Reinforcement of Bisphenol-F epoxy resin composites with fluorinated carbon nanotubes", 《COMPOSITES SCIENCE AND TECHNOLOGY》 * |
| 王登武 等: "环氧树脂/氟化碳纳米管复合材料的制备和性能", 《中国塑料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034078A (en) * | 2017-12-15 | 2018-05-15 | 深圳南科二维复材科技有限公司 | A kind of fluorinated carbon material/basic zirconium phosphate binary composite, preparation method and applications |
| WO2019114414A1 (en) * | 2017-12-15 | 2019-06-20 | 深圳南科二维复材科技有限公司 | Fluorinated carbon material/zirconium phosphate binary composite material, preparation method and application thereof |
| CN108034078B (en) * | 2017-12-15 | 2020-04-28 | 深圳南科二维复材科技有限公司 | Carbon fluoride material/zirconium phosphate binary composite material, preparation method and application thereof |
| CN111001615A (en) * | 2019-11-15 | 2020-04-14 | 沪东中华造船(集团)有限公司 | Novel method for cleaning fresh water tank of ship |
| CN111825832A (en) * | 2020-08-04 | 2020-10-27 | 江苏利宏科技发展有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN115141588A (en) * | 2022-06-29 | 2022-10-04 | 上海回天新材料有限公司 | Epoxy resin adhesive for Type C sealing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019024184A1 (en) | 2019-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107312162A (en) | A kind of epoxy curing agent, a kind of epoxide resin material and preparation method thereof | |
| JP5403184B1 (en) | Fiber reinforced composite material | |
| CN107353397B (en) | A kind of preparation method of ultra high strength concrete | |
| CN101104725A (en) | Preparation method for high-performance epoxy resin composite material | |
| CN106928809B (en) | Epoxy resin coating and preparation method thereof | |
| TW201841970A (en) | Epoxy resin composition for fiber-reinforced composite materials, fiber-reinforced composite material and molded body | |
| CN102181155B (en) | Preparation method of polytetrafluoroethylene and functionalized carbon fiber modified polyimide resin composite material | |
| CN105778424A (en) | Carbon nanotube and carbon fiber synergistically modified epoxy resin composite material and preparation method thereof | |
| CN109337066A (en) | One kind having reactivity, diffluent rigid chain polymer and preparation method thereof and composition | |
| CN113201207B (en) | Preparation method of high-toughness and high-strength carbon nanotube/epoxy resin composite material | |
| CN109880295A (en) | A kind of graphene oxide and its epoxy nano composite material of amino-terminated modification | |
| Wang et al. | New reactive rigid-rod aminated aromatic polyamide for the simultaneous strengthening and toughening of epoxy resin and carbon fiber/epoxy composites | |
| CN114015333A (en) | Modified graphene-reinforced impact-resistant polyurea coating and preparation method thereof | |
| CN101457019B (en) | Carbon nanotube/polysulfonamide nano composite material and preparation method thereof | |
| CN107880713A (en) | A kind of preparation method of epoxy coating | |
| CN104151827B (en) | The preparation method of carbon fiber/carbon nanotube/organic siliconresin multi-dimensional hybrid composite | |
| CN108084436A (en) | A kind of epoxy curing agent, its preparation method and application | |
| CN115948101B (en) | Waterproof and anticorrosive epoxy resin coating and preparation method thereof | |
| CN112029408A (en) | Environment-friendly waterproof coating and preparation method thereof | |
| KR101730437B1 (en) | Epoxy composites having enhanced thermal stability and mechnical behaviors and manufacturing method of the same | |
| CN109486266B (en) | Self-healing graphene composite material for anticorrosive coating and preparation method thereof | |
| CN116891565A (en) | Preparation method of bio-based high-toughness Vitimer crosslinked network | |
| CN113957721B (en) | Anti-wrinkle elastic silicone oil and preparation method thereof | |
| DE602004010598T2 (en) | Composite material, its production process and its use | |
| CN109369906B (en) | Polyether amine type waterborne epoxy curing agent for epoxy resin and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171103 |
|
| RJ01 | Rejection of invention patent application after publication |