CN105968808B - A kind of self-repair resin based composites and preparation method thereof - Google Patents
A kind of self-repair resin based composites and preparation method thereof Download PDFInfo
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- CN105968808B CN105968808B CN201610521940.4A CN201610521940A CN105968808B CN 105968808 B CN105968808 B CN 105968808B CN 201610521940 A CN201610521940 A CN 201610521940A CN 105968808 B CN105968808 B CN 105968808B
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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Abstract
The invention discloses a kind of self-repair resin based composites and preparation method thereof.Using bimaleimide resin, epoxy resin, curing agent and mesoporous silicon oxide as raw material, using in resin molding process resin in-situ polymerization to be impregnated with epoxy resin renovation agent mesoporous silicon oxide duct carry out sealing of hole, Self-repair Composites are prepared.Self-repair Composites prepared by technical solution of the present invention, need not be added the microcapsules containing renovation agent, and preparation process is simple, and prepared Self-repair Composites have excellent mechanical property and hot property, can be used for the fields such as Aeronautics and Astronautics, electronics.
Description
Technical field
The present invention relates to a kind of self-repair resin based composites and preparation method thereof, belong to high performance resin base composite wood
Material field.
Background technology
Bimaleimide resin is as a kind of typical high-performance thermosetting resin, with excellent mechanical property,
High heat resistance, low dielectric properties etc., is widely used in the fields such as Aeronautics and Astronautics, electronics.But since bismaleimide resin cures
Object have apparent brittleness so that bismaleimide resin sill using use during be also easy to produce crackle, to make its application by
Limit and safety reduction, therefore simultaneously repair crack has positive anticipate for the application field and safety that increase span material for inhibition
Justice.
Currently, the self-repair technology of material is widely studied, for polymer matrix composite, using heeling-in
Microcapsules technology containing renovation agent is a kind of common method for preparing self-repair material, and repair mechanisms mainly pass through micro- glue
Capsule discharges renovation agent, under controlled conditions, repairs and polymerisation occurs, to bond the mesh that crackle reaches restorer performance
's.But the self-repair material of this microcapsule-type may cause certain mechanical properties of material for example strong due to the addition of microcapsules
Degree and heat resistance decline.And traditional self-repair material for preparing microcapsule-type first has to prepare microcapsules, this allows for making
Standby microcapsule-type self-repair material process becomes more complicated, in addition it is also necessary to from multi-faceted angle consider microcapsules with
Interface interaction relationship between resin matrix avoids the usability that material is influenced because of the addition of microcapsules.Therefore how using letter
Easy method, which obtains the heat-resist microcapsule-type containing renovation agent, to be reviewed one's lessons by oneself high-performance and answers material for promoting material being applied to
It closes important.
Mesoporous silicon oxide have orderly pore passage structure, larger specific surface area, narrow and adjustable pore-size distribution, compared with
The features such as good biocompatibility and nonhazardous, have caused the great interest of researcher.Currently, different pore passage structures, shape
The mesoporous silicon material of looks is widely used in catalysis, absorption, separation, the fields such as especially medical controlled release.The above situation is shown
Potential ability of the mesoporous silicon material in control release application aspect.Therefore, mesoporous silicon oxide has natural storage capacity, and
By being blocked to its duct, then it provides possibility for encapsulated materials.In addition, under condition of negative pressure, it can greatly improve Jie
The storage capacity and sustained release performance of hole silica.In recent years using mesoporous silicon oxide as the research of drug delivery system by
To extensive concern.However, using stored in polymer matrix composites forming process renovation agent in mesoporous silicon oxide duct and
The method that resin polymerization blocks duct in situ has not been reported to prepare high-performance Self-repair Composites.
Invention content
The present invention is directed to limitation of the existing technology, in view of mesoporous silicon oxide multi-pore channel advantage and its in drug control
Application precedent in system release, the high-adhesion having in conjunction with epoxy resin, excellent mechanical property and hot property, utilization are mesoporous
It is multiple to provide a kind of high-performance selfreparing bimaleimide resin using epoxy resin as renovation agent for the storage capacity of silica
Condensation material and preparation method thereof.
To achieve the above object of the invention, the technical solution adopted by the present invention is to provide a kind of self-repair resin based composites
And preparation method thereof, include the following steps：
1, by weight, 20~50 parts of epoxy resin and 0.2~4.5 part of mesoporous silicon oxide are mixed, is 100 in temperature
~130 DEG C, vacuum degree be -0.6~-0.1MPa under conditions of handle 0.5~1h；
2, it is 130~140 DEG C, under stirring condition in temperature, 20~80 parts of bimaleimide resins is added, wait for that span comes
3~30 parts of curing agent are added after imide resin melting completely, the pre-polymerization 0.5 under conditions of stirring, temperature are 140~150 DEG C
After~1h, then deaeration processing is carried out under conditions of temperature is 140~150 DEG C；The bimaleimide resin includes N,
N'- (4,4'- methylenediphenyl) bismaleimide, Diphenyl Ether Bismaleimide；The curing agent includes 4,4'-
Diaminodiphenylsulfone, 3,3'- diaminodiphenylsulfones, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl ethers, N, N- diformazans
Base -1,6- hexamethylene diamine, piperazine, m-phenylene diamine (MPD), two methanediamine of isophthalic, imidazoles, 2- ethyl imidazol(e)s, 2-methylimidazole, 2- ethyls -4-
Methylimidazole；
3, the product for obtaining step 2 carries out curing process, obtains a kind of self-repair resin based composites.
One preferred embodiment of curing process condition of the present invention is：160℃/2h+180℃/2h+200℃/
2h。
The epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, hydrogen
Change bisphenol A type epoxy resin, novolac epoxy resin, resorcinol bisglycidyl ether type epoxy resin, double resorcinol contracting first
Four glycidol ether of aldehyde, phosphatized epoxy resin, brominated epoxy resin.
The aperture of the mesoporous silicon oxide is 2nm~9nm, and grain size is 20~100nm.Can be specifically：
Two-dimentional hexagonal structure, specific surface area are 500~800m2/ g, the mesoporous silicon oxide that aperture is 7~9nm；
Three-dimensional bicontinuous cubic structure, specific surface area 600m2/ g, the mesoporous silicon oxide that aperture is 7nm；
Three-dimensional body-centered cubic, specific surface area 700m2/ g, the mesoporous silicon oxide that aperture is 6nm；
Three-dimensional face-centered cubic, specific surface area 600m2/ g, the mesoporous silicon oxide that aperture is 5nm；
Two-dimentional hexagonal structure, specific surface area 1200m2/ g, the mesoporous silicon oxide that aperture is 2nm；
Two-dimentional hexagonal structure, specific surface area 1300m2/ g, the mesoporous silicon oxide that aperture is 2nm.
Technical solution of the present invention further includes a kind of self-repair resin based composites that the method that is prepared as described above obtains.
The principle of the present invention is：Application in view of mesoporous silicon oxide multi-pore channel advantage and its in drug controlled release is first
Example, the high-adhesion having in conjunction with epoxy resin, excellent mechanical property and hot property, the present invention utilize mesoporous silicon oxide
Storage capacity prepares a kind of high-performance selfreparing bismaleimide resin composite material using epoxy resin as renovation agent.It is making
In standby materials process, epoxy resin and mesoporous silicon oxide are mixed first, under heating and condition of negative pressure, renovation agent asphalt mixtures modified by epoxy resin
Fat viscosity becomes smaller, and easily injects mesoporous silicon oxide duct and is difficult to by the renovation agent in injection mesoporous silicon oxide duct on normal pressure
Release, other liquids are to be difficult to further diffuse into duct；Bimaleimide resin is then added, waits for bismaleimide resin
After melting, curing agent is added, bimaleimide resin reacts to form polymer with curing agent at this time, the polymer or solid
Agent can also react with the remaining renovation agent for not penetrating into mesoporous silicon oxide duct generates polymer, above-mentioned polymer
Barrier is formed in the mesoporous silicon oxide duct periphery and surface for penetrating into epoxy resin, realizes and mesopore orbit is blocked, meeting in this way
Inhibiting the exudation of epoxy resin or prevents foreign substance from penetrating into so that epoxy resin can be retained in mesoporous silicon oxide duct,
For this part epoxy, in the case where no initiator and curing agent have effect, the temperature of very height is needed（It is higher than
200℃）It is likely to that self-polymeric reaction occurs, therefore it is at a lower temperature（≤200℃）Certain chemical reaction can still be retained to live
Property.When material after molding cracks in use, meso-porous titanium dioxide silicon particle may rupture, under heat,
The effect for the epoxy resin amino-contained and its derivative in resin matrix that epoxy resin in duct can release, and release
Under polymerisation can occur to bond repair crack, achieve the purpose that restorer performance.
The beneficial effects of the invention are as follows：It is encapsulated and is repaired in situ using the polymerisation of resin in composite material shaping process
Agent prepares the polymer matrix composites with self-repair function, avoids because of the separately synthesized cumbersome technique of the microcapsules containing renovation agent
And because microcapsules introduce the complex effects to polymer matrix composites process and performance.Selfreparing composite wood provided by the invention
Preparation method for material has the characteristics that applicability is wide, easy to operate.
Description of the drawings
Fig. 1~4 are the surface sweeping Electronic Speculum of the front and back plane of disruption of self-repair material system healing prepared by various embodiments of the present invention
（SEM）Figure.
Specific implementation mode
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples.
Embodiment 1
The preparation of self-repair material：By the 20g bisphenol A type epoxy resin (trades mark：) and 0.2g mesoporous silicon oxides E-44（Two
Tie up hexagonal structure, specific surface area is 500~800m2/ g, aperture are 7~9nm, and product category is denoted as UC-S-1）Mixing, 130
DEG C, handle 1h under -0.1MPa vacuum pressure conditions；20gN, N'- (4,4'- methylenediphenyls) span are added under stirring condition
Carry out acid imide（BDM）, 130 DEG C are heated, and 10g4,4'- diamino hexichol are added after bimaleimide resin completely melting
Sulfone, under stirring condition, under the conditions of 140 DEG C of pre-polymerization 0.5h, 140 DEG C after deaeration is handled, by 160 DEG C/2h+180 DEG C/2h+200
DEG C/2h cured, obtain self-repair material system（It is denoted as：BDM/E-44/ E-44@UC-S-1）.
Comparative example 1
Not plus the preparation of Metaporous silicon dioxide material：By the 20g bisphenol A type epoxy resin (trades mark：) and 20gN, N'- E-44
(4,4'- methylenediphenyls) bismaleimide（BDM）Mixing heats at 130 DEG C, waits for that bimaleimide resin is complete
Add 10g4 after melting, 4'- diaminodiphenylsulfones are handled at 140 DEG C through deaeration in 140 DEG C of pre-polymerization 0.5h under stirring condition
Afterwards, cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h, obtain material system（It is denoted as：BDM/E-44）.
The preparation of containing mesopore earth silicon material：By the 20g bisphenol A type epoxy resin (trades mark：E-44), the mesoporous dioxies of 0.2g
SiClx（UC-S-1）And 20gN, N'- (4,4'- methylenediphenyls) bismaleimide（BDM）Mixing is heated at 130 DEG C,
10g4 is added after bimaleimide resin completely melting, 4'- diaminodiphenylsulfones, in 140 DEG C of pre-polymerizations under stirring condition
0.5h is cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h at 140 DEG C after deaeration is handled, obtains composite bodies
System（It is denoted as：BDM/E-44/UC-S-1）.
Three kinds of materials of above-mentioned preparation are cut into required size on cutting machine respectively and carry out fracture toughness test.It is broken tough
Property test after sample fixed through high temperature gummed tape, it is ensured that the plane of disruption comes into full contact with, and then handle 2 hours at 200 DEG C, then survey
Try its healing fracture value.It is the performance data of each material in the present embodiment referring to table 1.Referring to attached drawing 1, it is the present embodiment system
The surface sweeping Electronic Speculum of the standby front and back plane of disruption of self-repair material system BDM/E-44/E-44@UC-S-1 healings（SEM）Figure；Wherein, scheme
(a) it is before healing, figure (b) is after healing.
Table 1：Each material characteristic data
。
From table 1 it follows that the mechanical property of material system BDM/E-44/E-44@UC-S-1 and BDM/E-44/UC-S-1
Energy and hot property are good compared with material system BDM/E-44, main reason is that mesoporous silicon oxide has high mechanical property and heat
Performance, meso-porous titanium dioxide silicon particle can inhibit and be passivated the extension of crackle, reference can be made to Fig. 1 (a), is conducive to the mechanics for improving material
Performance.But comparison BDM/E-44/E-44@UC-S-1 and BDM/E-44/UC-S-1, it can be found that self-repair material system
BDM/E-44/E-44@UC-S-1 have apparent self-repair function.Comparison diagram 1 (a) and (b), there it can be seen that callus-wood
The plane of disruption of material has apparent bonding splitting traces, and this is mainly due to preparing self-repair material BDM/E-44/E-44@UC-
When S-1, epoxy resin penetrates into mesoporous silicon oxide duct, and duct is blocked and is protected during material preparation.
After material fracture, in a heated condition, the epoxy resin in fracture mesoporous silicon oxide duct can release and and resin matrix
Middle amino-contained and its derivative effect occur polymerisation and play the purpose of restorer performance to bond crack surface.
Embodiment 2
The preparation of self-repair material：By the 30g bisphenol A type epoxy resin (trades mark：) and 1.5g mesoporous silicon oxides E-51（Two
Tie up hexagonal structure, specific surface area is 500~800m2/ g, aperture are 7~9nm, and product category is denoted as UC-S-1）Mixing, 130
DEG C, handle 0.5h under -0.1MPa vacuum pressures, 30gN is then added under stirring condition, N'- (4,4'- methylenediphenyl) is double
Maleimide (BDM) is heated at 140 DEG C, and 20g4,4'- diamino are added after bimaleimide resin completely melting
Diphenyl-methane, in 150 DEG C of pre-polymerization 1h under stirring condition, at 150 DEG C after deaeration is handled, by 160 DEG C/2h+180 DEG C/2h+200
DEG C/2h cured, obtain self-repair material system（It is denoted as：BDM/E-51/E-51@UC-S-1）.
Comparative example 2
Not plus the preparation of Metaporous silicon dioxide material：By the 30g bisphenol A type epoxy resin (trades mark：) and 30gN, N'- E-51
(4,4'- methylenediphenyl) bismaleimide (BDM) heats at 140 DEG C, waits for that bimaleimide resin melts completely
After add 20g4,4'- diaminodiphenylmethane is pressed in 150 DEG C of pre-polymerization 1h at 150 DEG C after deaeration is handled under stirring condition
160 DEG C/2h+180 DEG C/2h+200 DEG C/2h is cured, and material system is obtained（It is denoted as：BDM/E-51）.
The preparation of containing mesopore earth silicon material：By the 30g bisphenol A type epoxy resin (trades mark：) and 1.5g mesoporous two E-51
Silica（UC-S-1）Mixing, handles 0.5h under 130 DEG C, -0.1MPa vacuum pressure conditions, is then added under stirring condition
30gN, N'- (4,4'- methylenediphenyl) bismaleimide (BDM) heats at 140 DEG C, waits for bimaleimide resin
20g4 is added after melting, 4'- diaminodiphenylmethane, in 150 DEG C of pre-polymerization 1h under stirring condition, at 150 DEG C through deaeration completely
After processing, is cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h, obtain composite system（It is denoted as：BDM/E-51/
UC-S-1）.
The material prepared is cut on cutting machine to required size respectively and carries out fracture toughness test.Fracture toughness test
Sample afterwards is fixed through high temperature gummed tape, it is ensured that the plane of disruption comes into full contact with, and is then handled 2 hours at 200 DEG C, then tests it and be cured
Make and break splits value.Table 2 is the performance data of each material in the present embodiment.Fig. 2 is self-repair material system BDM/E- in the present embodiment
The surface sweeping Electronic Speculum of the front and back plane of disruption of 51/E-51@UC-S-1 healings（SEM）Figure；Wherein, before figure (a) is healing, figure (b) is healing
Afterwards.
Material characteristic data in 2 embodiment 2 of table
| Performance | BDM/E-51/E-51@UC-S-1 | BDM/E-51 | BDM/E-51/UC-S-1 |
| Bending strength/MPa | 155 | 115 | 146 |
| Initial collapse toughness (KICOriginal)/MPa·m1/2 | 1.97 | 1.3 | 1.87 |
| Fracture toughness (K after healingIC Healed)/MPa·m1/2 | 1.36 | / | / |
| Fracture toughness healing efficiency (η=(KICOriginal/ KIC Healed)×100%)/% | 69% | / | / |
| 5wt% weightless temperatures（TGA methods, heating rate：10min/℃）/℃ | 391 | 390 | 391 |
From Table 2, it can be seen that the mechanical property of material system BDM/E-51/E-51@UC-S-1 and BDM/E-51/UC-S-1
Energy and hot property are good compared with material system BDM/E-51, main reason is that mesoporous silicon oxide has high mechanical property and heat
Performance, meso-porous titanium dioxide silicon particle can inhibit and be passivated the extension of crackle, reference can be made to Fig. 2 (a), is conducive to the mechanics for improving material
Performance.But comparison BDM/E-51/E-51@UC-S-1 and BDM/E-51/UC-S-1, it can be found that self-repair material system
BDM/E-51/E-51@UC-S-1 have apparent self-repair function.(a) and (b) of comparison diagram 2, from (a) it can be seen that
The trace that liquid E-51 is spread on section, and the plane of disruption (b) has apparent bonding splitting traces, this is mainly due to making
When standby self-repair material BDM/E-51/E-51@UC-S-1, epoxy resin penetrates into mesoporous silicon oxide duct, and in material system
Duct is blocked and is protected during standby.After material fracture, in a heated condition, in fracture mesoporous silicon oxide duct
Epoxy resin can release and polymerisation occurs with amino-contained in resin matrix and its derivative effect, to bond crackle
The purpose of restorer performance is played in face.
Embodiment 3：
The preparation of self-repair material：By the 50g bisphenol f type epoxy resin (trades mark：) and 4.5g meso-porous titanium dioxides NPEF-170
Silicon（Three-dimensional body-centered cubic, specific surface area 700m2/ g, aperture 6nm, product category are denoted as UC-S-3）It mixes, is in temperature
100 DEG C, vacuum degree be -0.6MPa under conditions of handle 0.6h, 80gN, N'- (4,4'- methylene are then added under stirring condition
Diphenyl) bismaleimide (BDM), it is heated at 135 DEG C, 30g4 is added after bimaleimide resin completely melting,
4'- diaminodiphenylsulfones, in 145 DEG C of pre-polymerization 0.6h under stirring condition, at 145 DEG C after deaeration is handled, by 160 DEG C/2h+180
DEG C/2h+200 DEG C/2h cured, self-repair material system can be obtained and (be denoted as：BDM/ NPEF-170/NPEF-170@UC-S-
3)。
Comparative example 3
Not plus the preparation of Metaporous silicon dioxide material：By the 50g bisphenol f type epoxy resin (trades mark：) and 80gN, NPEF-170
N'- (4,4'- methylenediphenyl) bismaleimide (BDM) is heated at 135 DEG C, waits for that bimaleimide resin is completely molten
Add 30g4 after melting, 4'- diaminodiphenylsulfones, in 145 DEG C of pre-polymerization 0.6h under stirring condition, at 145 DEG C after deaeration is handled,
Cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h, material system can be obtained and (be denoted as：BDM/ NPEF-170).
The preparation of containing mesopore earth silicon material：By the 50g bisphenol f type epoxy resin (trades mark：NPEF-170), 4.5g is mesoporous
Silica (UC-S-3) and 80gN, N'- (4,4'- methylenediphenyl) bismaleimide (BDM) are heated at 135 DEG C,
30g4 is added after bimaleimide resin completely melting, 4'- diaminodiphenylsulfones, in 145 DEG C of pre-polymerizations under stirring condition
0.6h is cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h at 145 DEG C after deaeration is handled, composite material can be obtained
System (is denoted as：BDM/NPEF-170/UC-S-3).
The material prepared is cut on cutting machine to required size respectively and carries out fracture toughness test.Fracture toughness test
Sample afterwards is fixed through high temperature gummed tape, it is ensured that the plane of disruption comes into full contact with, and is then handled 2 hours at 150 DEG C, then tests it and be cured
Make and break splits value.Table 3 is material characteristic data in embodiment 3.It is self-repair material BDM/NPEF- in the present embodiment referring to attached drawing 3
The surface sweeping Electronic Speculum of the front and back plane of disruption of 170/NPEF-170@UC-S-3 healings（SEM）Figure；Wherein, before figure (a) is healing, scheme (b)
After healing.
Table 3：Each material characteristic data
。
From table 3 it is observed that material system BDM/ NPEF-170/E-51@UC-S-3 and BDM/NPEF-170/UC-S-
3 mechanical property and hot property is good compared with material system BDM/NPEF-170, main reason is that mesoporous silicon oxide has height
Mechanical property and hot property, meso-porous titanium dioxide silicon particle can inhibit and be passivated the extension of crackle, reference can be made to attached drawing 3 (a), favorably
In the mechanical property for improving material.But comparison BDM/NPEF-170/NPEF-170@UC-S-3 and BDM/ NPEF-170/UC-
S-3, it can be found that self-repair material system BDM/NPEF-170/NPEF-170@UC-S-3 have apparent self-repair function.It is right
(a) and (b) than Fig. 3, the trace spread on section from (a) it can be seen from the figure that liquid-state epoxy resin NPEF-170, and
(b) plane of disruption of figure has apparent bonding splitting traces, and this is mainly due to preparing self-repair material BDM/NPEF-170/
When NPEF-170@UC-S-3, epoxy resin penetrates into mesoporous silicon oxide duct, and duct is blocked during material preparation
And it is protected.After material fracture, in a heated condition, the epoxy resin in fracture mesoporous silicon oxide duct can release simultaneously
With amino-contained in resin matrix and its lower generation polymerisation of derivative effect restorer is played to bond crack surface
The purpose of energy.
Embodiment 4
The preparation of self-repair material：By the 40g bisphenol A type epoxy resin (trades mark：) and 2g mesoporous silicon oxides E-51（Two dimension
Hexagonal structure, specific surface area 1200m2/ g, aperture 2nm, product category are denoted as UC-S-5）Mixing, in 130 DEG C, -0.9MPa
1h is handled under vacuum pressure condition, 40g Diphenyl Ether Bismaleimides (BDME) are then added under stirring condition, is added at 140 DEG C
Heat adds 3g imidazoles, in 150 DEG C of pre-polymerization 0.5h under stirring condition, at 150 DEG C after bimaleimide resin completely melting
After deaeration is handled, cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h, self-repair material system can be obtained（It is denoted as：
BDME/E-51/E-51@UC-S-5）.
Comparative example 4
Not plus the preparation of Metaporous silicon dioxide material：By the 40g bisphenol A epoxide resin (trades mark：E-51) and 40g diphenyl ether is double
Maleimide (BDME) is heated at 140 DEG C, and 3g imidazoles, stirring bar are added after bimaleimide resin completely melting
In 150 DEG C of pre-polymerization 0.5h under part, at 150 DEG C after deaeration is handled, cured by 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h,
Material system can be obtained（It is denoted as：BDME/E-51）.
The preparation of containing mesopore earth silicon material：By 40g bisphenol A type epoxy resins (E-51), 2g mesoporous silicon oxides
（UC-S-5）, 40g Diphenyl Ether Bismaleimides (BDME), at 140 DEG C heat, after bimaleimide resin completely melting after
Add 3g imidazoles, in 150 DEG C of pre-polymerization 0.5h under stirring condition, at 150 DEG C after deaeration is handled, by 160 DEG C/2h+180 DEG C/
2h+200 DEG C/2h is cured, and composite system is obtained（It is denoted as：BDME/E-51/UC-S-5）.
The material prepared is cut on cutting machine to required size respectively and carries out fracture toughness test.Fracture toughness test
Sample afterwards is fixed through high temperature gummed tape, it is ensured that the plane of disruption comes into full contact with, and is then handled 2 hours at 150 DEG C, then tests it and be cured
Make and break splits value.Table 4 is each material characteristic data in the present embodiment.Fig. 4 is self-repair material system BDME/E- in the present embodiment
The surface sweeping Electronic Speculum of the front and back plane of disruption of 51/E-51@UC-S-5 healings（SEM）Figure；Wherein, before figure (a) is healing, figure (b) is healing
Afterwards.
Table 4：Each material characteristic data
。
As can be seen from Table 4, the mechanics of material system BDMEE-51/E-51@UC-S-5 and BDME/E-51/UC-S-5
Performance and hot property are good compared with material system BDME/E-51, main reason is that mesoporous silicon oxide has high mechanical property
And hot property, meso-porous titanium dioxide silicon particle can inhibit and are passivated the extension (Fig. 4 (a)) of crackle, be conducive to the mechanics for improving material
Performance.But comparison BDME/E-51/E-51@UC-S-5 and BDME/E-51/UC-S-5, it can be found that self-repair material system
BDME/E-51/E-51@UC-S-5 have apparent self-repair function.(a) and (b) of comparison diagram 4, can from (a) figure
Go out the trace spread on section to liquid E-51, and (b) plane of disruption of figure has apparent bonding splitting traces, this is mainly
Since when preparing self-repair material BDME/E-51/E-51@UC-S-5, epoxy resin penetrates into mesoporous silicon oxide duct, and
Duct is blocked and is protected during material preparation.After material fracture, in a heated condition, it is broken mesoporous silicon oxide
Epoxy resin in duct can release and polymerisation occurs under amino-contained in resin matrix and its derivative effect, to
Crack surface is bonded, the purpose of restorer performance is played.
Claims (6)
1. a kind of preparation method of self-repair resin based composites, it is characterised in that include the following steps：
（1）By weight, 20~50 parts of epoxy resin and 0.2~4.5 part of mesoporous silicon oxide are mixed, temperature be 100~
130 DEG C, vacuum degree be 0.01~0.06MPa under conditions of handle 0.5~1h；
（2）It is 130~140 DEG C, under stirring condition in temperature, 20~80 parts of bimaleimide resins is added, wait for that span carrys out acyl
Imide resin completely melting after be added 3~30 parts of curing agent, stirring, temperature be 140~150 DEG C under conditions of pre-polymerization 0.5~
After 1h, then deaeration processing is carried out under conditions of temperature is 140~150 DEG C；The bimaleimide resin is N, N'-
(4,4'- methylenediphenyl) bismaleimide, one kind in Diphenyl Ether Bismaleimide；The curing agent is 4,
4'- diaminodiphenylsulfones, 3,3'- diaminodiphenylsulfones, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl ethers, N, N-
Dimethyl -1,6- hexamethylene diamine, piperazine, m-phenylene diamine (MPD), imidazoles, 2- ethyl imidazol(e)s, 2-methylimidazole, 2-ethyl-4-methylimidazole
In one kind；
（3）By step（2）Obtained product carries out curing process, obtains a kind of self-repair resin based composites.
2. a kind of preparation method of self-repair resin based composites according to claim 1, it is characterised in that：Described
Curing process condition is 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h.
3. a kind of preparation method of self-repair resin based composites according to claim 1, it is characterised in that：Described
Epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, hydrogenated bisphenol A type asphalt mixtures modified by epoxy resin
Fat, novolac epoxy resin, resorcinol bisglycidyl ether type epoxy resin, double four glycidol ethers of resorcinol formal,
One kind in phosphatized epoxy resin or brominated epoxy resin.
4. a kind of preparation method of self-repair resin based composites according to claim 1, it is characterised in that：Described
The aperture of mesoporous silicon oxide is 2nm~9nm, and grain size is 20~100nm.
5. a kind of preparation method of self-repair resin based composites according to claim 1 or 4, it is characterised in that：Institute
The mesoporous silicon oxide stated is selected from：
Two-dimentional hexagonal structure, specific surface area are 500~800m2/ g, the mesoporous silicon oxide that aperture is 7~9nm；
Three-dimensional bicontinuous cubic structure, specific surface area 600m2/ g, the mesoporous silicon oxide that aperture is 7nm；
Three-dimensional body-centered cubic, specific surface area 700m2/ g, the mesoporous silicon oxide that aperture is 6nm；
Three-dimensional face-centered cubic, specific surface area 600m2/ g, the mesoporous silicon oxide that aperture is 5nm；
Two-dimentional hexagonal structure, specific surface area 1200m2/ g, the mesoporous silicon oxide that aperture is 2nm；
Two-dimentional hexagonal structure, specific surface area 1300m2/ g, the mesoporous silicon oxide that aperture is 2nm.
6. a kind of self-repair resin based composites obtained by claim 1 preparation method.
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| CN108659462B (en) * | 2016-12-12 | 2020-06-19 | 苏州大学 | Self-repairing type remoldable multiple deformation thermosetting shape memory resin material |
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| CN102161829A (en) * | 2011-03-12 | 2011-08-24 | 苏州大学 | Bismaleimide resin system and preparation method thereof |
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