CN109161202A - A kind of elastic composite and preparation method thereof and self-repair method - Google Patents
A kind of elastic composite and preparation method thereof and self-repair method Download PDFInfo
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides a kind of elastic composite and preparation method thereof and self-repair methods, the elastic composite includes inorganic nano-filler, ion network and silicon network, and the inorganic nano-filler is supported on the interpenetrating cross-linked network that the ion network and silicon network are formed；Wherein, the ion network is reacted with the dimethyl silicone polymer of carboxy blocking by 3- aminopropyltriethoxy-dimethyl (siloxanes with polysiloxanes) and is formed, and the silicon network is solidified to obtain by hydroxy-end capped dimethyl silicone polymer.The present invention provide elastic composite under the heat treatment of certain condition can with selfreparing, for the remediation efficiency after mechanically damaged up to 73-96%, for by the remediation efficiency after voltage breakdown up to 58-75%.
Description
Technical field
The invention belongs to technical field of composite materials, it is related to a kind of elastic composite and preparation method thereof and selfreparing
Method.
Background technique
Elastomer is referred to as because of it with excellent tensile property, high-energy density and quick stress reaction ability
" artificial-muscle ".It is well known that the skin and muscle of human body have the characteristics that it is maximum be exactly after being damaged can with self-regeneration,
Reach self healing.However at this stage, most elastomer is all very fragile, all can after by external force or high voltage
Damage, less serious case can be such that the performance of material declines, serious directly to damage product, cause the waste of resource.So designing machine
Tool performance is high, and can be just particularly important with the elastomer of selfreparing.
Selfreparing concept be earliest the 1980s mid-term propose that by US military, the purpose of selfreparing is to make high score
Crackle forms initial stage with the ability for preventing crackle from continuing extension, to prevent material damage, expansion material to sub- material inside it
Use scope and prolong the service life.The selfreparing research of early stage is concentrated on is with epoxy resin and epoxy vingl ester resin etc.
The composite material of matrix.In recent years, the research direction of self-repair material extends to elastomer, composite material conduct by composite material
Usually are there is micro-crack, and crack growth fast speed by foreign impacts effect moment in a kind of rigidity or fragile material,
Degree of expansion is larger, shorter the time required to destroying；It is formed with composite inner crackle and material damage mode is different, bullet
Property body be usually to lead to the fatigue crack of material under alternate stress effect, elastomer internal tiny crack increase and aggregate speed compared with
Slowly, longer the time required to elastomer failure, internal tiny crack reparation is carried out to composite material or elastomer using self-repair technology
It is all effective method.CN105504502A discloses one kind can selfreparing extrusion grade polypropylene composite material and its preparation
Method, by mass percentage, by polypropylene 43-96.8%, elastomer 2-20%, talcum powder 0-30%, fluoropolymer
Composition 1-5%, antioxidant 0.1-2%, in the fluoro-containing copolymer composition for wherein including during extrusion molding, it is intended to
It migrates to product surface, on the one hand prevents product surface from scratching, the microcosmic surface position on the other hand generated due to stress scratch
It moves and deforms available quick reparation.
In recent years, researcher is high to the concern enthusiasm of selfreparing dielectric elastomer material, not only because
It is very extensive for its application range, including the fields such as army's equipment, electronic product, automobile, aircraft, construction material, wherein in intelligence
Can above mobile phone and computer screen using of greatest concern, meanwhile, it also avoids the waste of resource and fund, this is for current
The status of china natural resources shortage and the policy for walking sustainable development path have very important significance.CN105440692A is disclosed
A kind of microcapsule-type selfreparing silicone elastomer and preparation method thereof, by percentage to the quality, each raw material group become α,
Alpha, omega-dihydroxy polydimethyl siloxane 45-68%, reinforcing agent 4.5-27%, silane compound 4.5-21%, organotin catalysts
1.4-7%, microcapsules 6-27%, wherein microcapsules are using polymethyl methacrylate as wall material, with α, the poly- diformazan of alpha, omega-dihydroxy
The mixture of radical siloxane and silane compound is core material, by realizing self-repair function, obtained material power with microcapsule-type
Performance is poor, preparation method is cumbersome, and remediation efficiency is slightly lower, and reparation number is limited, and when consolidant exhausts, material just can not
Self-repair procedure occurs.CN107903636A disclose it is a kind of based on PDMS can quick selfreparing Thin Elastic without environmental stimuli
Film and preparation method thereof, wherein elastic film includes 1-5 parts by weight hydroxyl or amino-terminated dimethyl silicone polymer, 4-5 weight
The polymer of acrylate copolymer of the part containing carboxyl or ester group, 1-2 parts by weight hydroxyl or amino is measured, selfreparing elastic film is
High molecular material based on hydrogen bond can repair breakage at room temperature, but the mechanical property of film is poor, can not
Meet application requirement.
It needs to develop a kind of selfreparing elastic composite at present, mechanical performance of elastomer etc. not only can be improved but also can
With with certain self-reparing capability, and before and after reparation, the performance of material is not much different.
Summary of the invention
The purpose of the present invention is to provide a kind of elastic composite and preparation method thereof and self-repair methods.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the elastic composite includes inorganic receives the present invention provides a kind of elastic composite
Rice filler, ion network and silicon network, the ion network and silicon network form interpenetrating cross-linked network, the inorganic nano-filler
It is supported on the interpenetrating cross-linked network；
Wherein, the ion network is by 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) and carboxy blocking
Dimethyl silicone polymer reacts to be formed, and the silicon network is solidified to obtain by hydroxy-end capped dimethyl silicone polymer.
In the present invention, amino and reacting for carboxyl are as follows:
-COOH+-NH2→COO-NH3 +
The ionic bond that amino interacts with carboxyl can be broken after by voltage breakdown or mechanical damage, be given suitable
When heat treatment, can regenerate, so that elastic composite be made to achieve the purpose that self-regeneration；Inorganic nano is filled out simultaneously
The mechanical performance of elastic composite can be enhanced in the addition of material.
In the present invention, the elastic composite includes following component in parts by weight:
Silicon network 70-100 parts by weight；
Ion network 5-40 parts by weight；
Inorganic nano-filler 5-30 parts by weight.
The additive amount of inorganic nano-filler should try to control in 5-30 parts by weight, if less than 5 parts by weight, additional amount mistake
It is few, the mechanical performance of elastic composite is promoted smaller；If additive amount is excessive, may hold because of inorganic nano-filler
Mechanical performance that is easy to reunite and influencing material.
In the present invention, the parts by weight of the silicon network be 70-100 parts by weight, such as 75 parts by weight, 80 parts by weight,
85 parts by weight, 90 parts by weight, 95 parts by weight etc..
In the present invention, the parts by weight of the ion network be 5-40 parts by weight, such as 10 parts by weight, 15 parts by weight,
20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight etc..
In the present invention, the parts by weight of the inorganic nano-filler are 5-30 parts by weight, such as 10 parts by weight, 15 weight
Part, 20 parts by weight, 25 parts by weight etc..
In the present invention, the weight ratio of the silicon network and ion network be (2-9): 1, for example, 3:1,4:1,5:1,6:1,
7:1,8:1 etc., preferably (4-6): 1.
In the present invention, the weight ratio of silicon network and ion network is at (2-9): when in 1 range, elasticity provided by the invention
Composite material has preferable self-reparing capability, and repair rate is higher, up to 83-96%；When the weight of silicon network and ion network
Amount is than being (4-6): when 1, repair rate is higher, and up to 94-96%, the performance change for repairing front and back material is smaller；And work as silicon network
When with the mass ratio of ion network not in range provided by the invention, if ion network additive amount is very few, repair rate is lower,
And if ion network additive amount is excessive, will lead to elastomer and relatively difficult, the elastomeric material finally obtained of molding is fully cured
It may be easily sticky liquid form.
Preferably, the number-average molecular weight of the 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) is 4000-
5000, such as 4200,4400,4600,4800 etc..
Preferably, the number-average molecular weight of the dimethyl silicone polymer of the carboxy blocking be 1000-1500, such as 1100,
1200,1300,1400 etc..
Preferably, the number-average molecular weight of the hydroxy-end capped dimethyl silicone polymer is 50000-70000, such as
55000,60000,65000 etc..
Preferably, the size of the inorganic nano-filler is 10-100nm, such as 20nm, 30nm, 50nm, 70nm, 90nm
Deng.
Preferably, the inorganic nano-filler includes the ceramic particle with perovskite structure, semiconductor grain, carbon nanometer
In material, silver nano-grain and boron nitride nanosheet any one or at least two combination.
Preferably, the ceramic particle with perovskite structure is barium titanate, Pb (Zr1-xTix)O3、Pb(Mg1/3Nb2/3)
TiO3-PbTiO3、Pb(Zn1/3Nb2/3)TiO3-PbTiO3、CaCu3Ti4O12、PbZrO3(BaySr1-y)TiO3In any one
Or at least two combination, wherein 0 < x < 1,0 < y < 1.
Preferably, the barium titanate is that barium titanate vinyl-bearing is taken on surface.
Surface carry can be surface grafting, surface cladding, adsorption etc. it is any make barium titanate have vinyl groups
Form, preferred surface grafting.
Preferably, the semiconductor grain is ZnO, ZnS, MgO, SiC, ZrO2、Al2O3And TiO2In any one or
At least two combination.
Preferably, the carbon nanomaterial is any one in carbon nanotube, graphene oxide and carbon graphite nanosheets
Kind or at least two combination.
Preferably, the partial size of the carbon nanomaterial is 0.5-10 μm, such as 1 μm, 3 μm, 5 μm, 7 μm, 9 μm etc..
Preferably, the carbon nanotube is the carbon nanotube of surface hydroxylation.
Preferably, the graphene oxide is that graphene oxide vinyl-bearing is taken on surface.
Preferably, the boron nitride nanosheet is removed by hexagonal boron nitride ultrasound and is prepared.
Preferably, the boron nitride nanosheet is the boron nitride nanosheet of surface amination.
The preferred surface of inorganic nano-filler carries the inorganic nano-filler of functional group, can increase inorganic nano-filler and silicon
The compatibility of network and ion network.
Preferably, the boron nitride nanosheet the preparation method comprises the following steps: by hexagonal boron nitride dispersion in a solvent, obtain six sides
Boron nitride dispersion, then ultrasound, centrifugation, drying obtain the boron nitride nanosheet.
Preferably, in hexagonal boron nitride dispersion liquid, the concentration of the hexagonal boron nitride is 2-3g/L, such as 2.2g/L,
2.4g/L, 2.6g/L, 2.8g/L etc..
Preferably, the solvent is isopropanol.
Preferably, the time of the ultrasound is 36-48h, such as 38h, 40h, 42h, 44h, 46h etc..
Preferably, the revolving speed of the centrifugation is 8000-8500r/min, such as 8100r/min, 8200r/min, 8300r/
Min, 8400r/min etc..
Second aspect, the present invention provides a kind of preparation method of elastic composite as described in relation to the first aspect, institutes
Preparation method is stated to include the following steps:
(1) hydroxy-end capped dimethyl silicone polymer and curing agent are mixed, obtains the raw material mixed liquor of silicon network；
(2) by the dimethyl silicone polymer of 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) and carboxy blocking
Mixing, obtains ion network；
(3) inorganic nano is added after mixing the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains
Then filler solidifies, obtain the elastic composite.
Provided by the invention preparation method is simple, the elastomer being prepared using preparation method provided by the invention
Composite material contains the interpenetrating cross-linked network that ion network and silicon network are formed, and inorganic nano-filler is supported on interpenetrating cross-linked network
On.
Preferably, step (1) curing agent is methyltrimethoxysilane.
It preferably, further include catalyst in step (1) the raw material mixed liquor.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the molar ratio of the hydroxy-end capped dimethyl silicone polymer, curing agent and catalyst is (10-12):
1:1, such as 10.5:1:1,11:1:1,11.5:1:1 etc..
Preferably, step (2) 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) and carboxy blocking is poly-
The molar ratio of dimethyl siloxane is (1.5-1.8): 1, such as 1.6:1,1.7:1 etc..
Step (3) the cured method is solidified 2-3 days under 120-130 DEG C (such as 122 DEG C, 124 DEG C, 128 DEG C etc.)
(such as 2.4 days, 2.8 days etc.), it is then in room temperature and solid under conditions of humidity is 75-85% (such as 78%, 80%, 82% etc.)
Change 3-4 days (such as 3.4 days, 3.8 days etc.).
Preferably, step (1), step (2) and step (3) it is described mixing each independently in high speed mixer into
Row.
Preferably, the mixing revolving speed mixed three times is each independently selected from 1800-2000r/min (such as 1850r/
Min, 1900r/min, 1950r/min etc.), the time mixed three times be each independently selected from 2-3min (such as 2.2min,
2.5min, 2.8min etc.).
As optimal technical scheme, the preparation method includes the following steps:
(1) by hydroxy-end capped dimethyl silicone polymer, curing agent and catalyst with molar ratio be (10-12): 1:1 exists
2-3min is mixed under 1800-2000r/min, obtains the raw material mixed liquor of silicon network；
(2) by the dimethyl silicone polymer of 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) and carboxy blocking
With molar ratio for (1.5-1.8): 1 mixes 2-3min at 1800-2000r/min, obtains ion network；
(3) by the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains at 1800-2000r/min
Inorganic nano-filler is added after mixing 2-3min, solidify 2-3 days at 120-130 DEG C, then in room temperature and humidity is 75-85%
Under conditions of solidify 3-4 days, obtain the elastic composite.
The third aspect, it is described the present invention provides the self-repair method of elastic composite as described in relation to the first aspect
Restorative procedure be by the selfreparing elastic composite after mechanically damaged and/or voltage breakdown 120-160 DEG C (such as
130 DEG C, 140 DEG C, 150 DEG C etc.) under heat 6-8h (such as 6.5h, 7h, 7.5h etc.).
Elastic composite provided by the invention is after mechanically damaged and/or voltage breakdown, by certain condition
Heat treatment after, can achieve the purpose of selfreparing, repair rate repairs the elastic composite of front and back up to 70-95%
Performance change is smaller.
Compared with the existing technology, the invention has the following advantages:
(1) elastic composite provided by the invention contains ion network, and the amino in ion network is formed with carboxyl
Ionic bond be broken after mechanically damaged and/or voltage breakdown, and can be regenerated after certain heat treatment, from
And elastic composite is made to achieve the purpose that self-regeneration；
(2) mechanical property, the machine of material can effectively be improved by inorganic nano-filler being added in elastic composite
Tool performance, electric conductivity etc.；
(3) present invention offer elastic composite can be with selfreparing, for by machine under the heat treatment of certain condition
Remediation efficiency after tool damage up to 73-96%, for by the remediation efficiency after voltage breakdown up to 58-75%.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of elastic composite is grouped as by following group in parts by weight:
80 parts by weight of silicon network；
16 parts by weight of ion network；
30 parts by weight of inorganic nano-filler；
Wherein, the weight ratio of silicon network and ion network is 5:1, and inorganic nano-filler is boron nitride nanosheet.
The preparation method is as follows:
(1) by hydroxy-end capped dimethyl silicone polymer (Mn=60000), curing agent and catalyst with molar ratio be 10:
1:1 mixes 2min at 2000r/min, obtains the raw material mixed liquor of silicon network；
(2) by poly- the two of 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) (Mn=4500) and carboxy blocking
Methylsiloxane (Mn=1000) is that 1.5:1 mixes 2min at 2000r/min with molar ratio, obtains ion network；
(3) the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains are mixed at 2000r/min
Inorganic nano-filler is added after 2min, solidifies 3 days at 120 DEG C, then solidifies 3 in room temperature and under conditions of humidity is 80%
It, obtains elastic composite.
Embodiment 2-7
Difference with embodiment 1 is only that the parts by weight of ion network are 20 parts by weight (silicon network and ion network
Weight ratio is 4:1, embodiment 2)；The parts by weight of ion network are the 13.3 parts by weight (weight ratio of silicon network and ion network
For 6:1, embodiment 3)；The parts by weight of ion network are that (weight ratio of silicon network and ion network is 2:1 to 40 parts by weight, real
Apply example 4)；The parts by weight of ion network are 8.9 parts by weight (weight ratio of silicon network and ion network is 9:1, embodiment 5)；
The parts by weight of ion network are 8 parts by weight (weight ratio of silicon network and ion network is 10:1, embodiment 6)；Ion network
Parts by weight be 80 parts by weight (weight ratio of silicon network and ion network is 1:1, embodiment 7).
Embodiment 8
A kind of elastic composite is grouped as by following group in parts by weight:
100 parts by weight of silicon network；
40 parts by weight of ion network；
20 parts by weight of inorganic nano-filler；
Wherein, the weight ratio of silicon network and ion network is 2.5:1, and inorganic nano-filler is barium titanate.
The preparation method is as follows:
(1) by hydroxy-end capped dimethyl silicone polymer (Mn=50000), curing agent and catalyst with molar ratio be 12:
1:1 mixes 3min at 1800r/min, obtains the raw material mixed liquor of silicon network；
(2) by poly- the two of 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) (Mn=4000) and carboxy blocking
Methylsiloxane (Mn=1500) is that 1.8:1 mixes 2.5min at 1900r/min with molar ratio, obtains ion network；
(3) the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains are mixed at 1800r/min
Inorganic nano-filler is added after 3min, solidifies 2 days at 130 DEG C, then solidifies 4 in room temperature and under conditions of humidity is 75%
It, obtains elastic composite.
Embodiment 9
A kind of elastic composite is grouped as by following group in parts by weight:
70 parts by weight of silicon network；
5 parts by weight of ion network；
5 parts by weight of inorganic nano-filler；
Wherein, the weight ratio of silicon network and ion network is 14:1, and inorganic nano-filler is graphene oxide.
The preparation method is as follows:
(1) by hydroxy-end capped dimethyl silicone polymer (Mn=70000), curing agent and catalyst with molar ratio be 11:
1:1 mixes 2.5min at 1900r/min, obtains the raw material mixed liquor of silicon network；
(2) by poly- the two of 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) (Mn=5000) and carboxy blocking
Methylsiloxane (Mn=1000) is that 1.6:1 mixes 3min at 1800r/min with molar ratio, obtains ion network；
(3) the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains are mixed at 1900r/min
Inorganic nano-filler is added after 2.5min, solidifies 2.5 days at 125 DEG C, it is then in room temperature and solid under conditions of humidity is 85%
Change 3 days, obtains elastic composite.
Comparative example 1
The selfreparing elastic film (elastic composite) that CN107903636A specific embodiment 1 provides.
Performance test
Embodiment 1-9 and comparative example 1 elastic composite provided are tested for the property:
(1) mechanical property: extension test is carried out to composite material using electronic universal material testing machine, during the test
Rate of extension be 40 mm/min；
(2) remediation efficiency: repair rate=T '/T × 100%；
Wherein, T ' is the tensile strength after sample is repaired, and T is the initial tensile strength of sample, units MPa, repair rate A generation
Table is remediation efficiency after sample is mechanically damaged, and what repair rate B was represented is sample by the reparation effect after voltage breakdown
Rate, the mechanical parameter of the mechanical damage that all samples are subject to, the parameters such as voltage of voltage breakdown are all the same；
Restorative procedure is that the sample after mechanically damaged and/or voltage breakdown is heated 6 h at 160 DEG C.
1 is shown in Table to the test result of embodiment 1-9 and comparative example 1 elastic composite provided:
Table 1
| Sample | Initial tensile strength/MPa | Elongation at break/% | Repair rate A/% | Repair rate B/% |
| Embodiment 1 | 3.72 | 857 | 95.6 | 74.8 |
| Embodiment 2 | 3.51 | 843 | 93.8 | 70.5 |
| Embodiment 3 | 3.06 | 855 | 94.2 | 70.2 |
| Embodiment 4 | 2.98 | 786 | 87.2 | 65.1 |
| Embodiment 5 | 2.29 | 723 | 83.5 | 60.9 |
| Embodiment 6 | 3.67 | 705 | 73.8 | 58.6 |
| Embodiment 7 | 2.58 | 859 | 77.4 | 60.7 |
| Embodiment 8 | 2.74 | 779 | 86.9 | 68.4 |
| Embodiment 9 | 3.49 | 698 | 74.3 | 58.9 |
| Comparative example 1 | 1.06 | 890 | 93.8 | 76.2 |
By embodiment and experiment test it is found that the initial tensile strength of elastic composite provided by the invention is in 2-4
Within the scope of MPa, selfreparing can be completed under the heat treatment of certain condition, it is reachable for the remediation efficiency after mechanically damaged
73-96%, for by the remediation efficiency after voltage breakdown up to 58-75%；By the comparison of embodiment 1-5 and embodiment 6-7
It is found that when the weight ratio of silicon network and ion network is at (2-9) in elastic composite provided by the invention: when in 1 range,
Elastic composite provided by the invention has preferable self-reparing capability, and repair rate is higher, after mechanically damaged
Remediation efficiency up to 83-96%, for by the remediation efficiency after voltage breakdown up to 60-75%；When silicon network and ion
The weight ratio of network is (4-6): when 1, repair rate is higher, right for the remediation efficiency after mechanically damaged up to 94-96%
In by the remediation efficiency after voltage breakdown, up to 70-75%, the performance change for repairing front and back material is smaller；By 1 He of embodiment
The comparison of comparative example 1 is it is found that the tensile strength of elastic composite provided by the invention is higher.
The Applicant declares that the present invention is explained by the above embodiments elastic composite and its preparation side of the invention
Method and self-repair method, but the invention is not limited to above-mentioned method detaileds, that is, it is above-mentioned detailed not mean that the present invention must rely on
Thin method could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and public affairs
Within the scope of opening.
Claims (10)
1. a kind of elastic composite, which is characterized in that the elastic composite includes inorganic nano-filler, ion net
Network and silicon network, the ion network and silicon network form interpenetrating cross-linked network, and the inorganic nano-filler is supported on described mutual
It wears on cross-linked network；
Wherein, the ion network is by 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) and poly- the two of carboxy blocking
Methylsiloxane reacts to be formed, and the silicon network is solidified to obtain by hydroxy-end capped dimethyl silicone polymer.
2. elastic composite according to claim 1, which is characterized in that the elastic composite is by weight
Number includes following component:
Silicon network 70-100 parts by weight；
Ion network 5-40 parts by weight；
Inorganic nano-filler 5-30 parts by weight.
3. elastic composite according to claim 1 or 2, which is characterized in that the silicon network and ion network
Weight ratio is (2-9): 1, preferably (4-6): 1.
4. elastic composite described in any one of -3 according to claim 1, which is characterized in that the 3- aminopropyl first
The number-average molecular weight of base-dimethyl (siloxanes and polysiloxanes) is 4000-5000；
Preferably, the number-average molecular weight of the dimethyl silicone polymer of the carboxy blocking is 1000-1500；
Preferably, the number-average molecular weight of the hydroxy-end capped dimethyl silicone polymer is 50000-70000.
5. elastic composite described in any one of -4 according to claim 1, which is characterized in that the inorganic nano is filled out
The size of material is 10-100nm；
Preferably, the inorganic nano-filler includes the ceramic particle with perovskite structure, semiconductor grain, carbon nanometer material
In material, silver nano-grain and boron nitride nanosheet any one or at least two combination；
Preferably, the ceramic particle with perovskite structure is barium titanate, Pb (Zr1-xTix)O3、Pb(Mg1/3Nb2/3)
TiO3-PbTiO3、Pb(Zn1/3Nb2/3)TiO3-PbTiO3、CaCu3Ti4O12、PbZrO3(BaySr1-y)TiO3In any one
Or at least two combination, wherein 0 < x < 1,0 < y < 1；
Preferably, the barium titanate is that barium titanate vinyl-bearing is taken on surface；
Preferably, the semiconductor grain is ZnO, ZnS, MgO, SiC, ZrO2、Al2O3And TiO2In any one or at least two
The combination of kind；
Preferably, the carbon nanomaterial be carbon nanotube, graphene oxide and carbon graphite nanosheets in any one or
At least two combination；
Preferably, the partial size of the carbon nanomaterial is 0.5-10 μm；
Preferably, the carbon nanotube is the carbon nanotube of surface hydroxylation；
Preferably, the graphene oxide is that graphene oxide vinyl-bearing is taken on surface；
Preferably, the boron nitride nanosheet is removed by hexagonal boron nitride ultrasound and is prepared；
Preferably, the boron nitride nanosheet is the boron nitride nanosheet of surface amination；
Preferably, the boron nitride nanosheet the preparation method comprises the following steps: by hexagonal boron nitride dispersion in a solvent, obtain six sides nitridation
Boron dispersion liquid, then ultrasound, centrifugation, drying obtain the boron nitride nanosheet；
Preferably, in hexagonal boron nitride dispersion liquid, the concentration of the hexagonal boron nitride is 2-3g/L；
Preferably, the solvent is isopropanol；
Preferably, the time of the ultrasound is 36-48h；
Preferably, the revolving speed of the centrifugation is 8000-8500r/min.
6. the preparation method of elastic composite described in any one of -5 according to claim 1, which is characterized in that described
Preparation method includes the following steps:
(1) hydroxy-end capped dimethyl silicone polymer and curing agent are mixed, obtains the raw material mixed liquor of silicon network；
(2) 3- aminopropyltriethoxy-dimethyl (siloxanes with polysiloxanes) and the dimethyl silicone polymer of carboxy blocking are mixed,
Obtain ion network；
(3) inorganic nano is added after mixing the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains to fill out
Material, then solidifies, obtains the elastic composite.
7. preparation method according to claim 6, which is characterized in that step (1) curing agent is methyl trimethoxy oxygroup
Silane；
It preferably, further include catalyst in step (1) the raw material mixed liquor；
Preferably, the catalyst is dibutyl tin dilaurate；
Preferably, the molar ratio of the hydroxy-end capped dimethyl silicone polymer, curing agent and catalyst is (10-12): 1:1；
Preferably, the poly- diformazan of step (2) 3- aminopropyltriethoxy-dimethyl (siloxanes and the polysiloxanes) and carboxy blocking
The molar ratio of radical siloxane is (1.5-1.8): 1；
Step (3) the cured method is to solidify at 120-130 DEG C 2-3 days, the item for being then 75-85% in room temperature and humidity
Solidify 3-4 days under part.
8. preparation method according to claim 6 or 7, which is characterized in that step (1), step (2) and step (3) are described
Mixing carries out in high speed mixer each independently；
Preferably, the mixing revolving speed mixed three times is each independently selected from 1800-2000r/min, and the time mixed three times is equal
It is each independently selected from 2-3min.
9. the preparation method according to any one of claim 6-8, which is characterized in that the preparation method includes as follows
Step:
(1) by hydroxy-end capped dimethyl silicone polymer, curing agent and catalyst with molar ratio be (10-12): 1:1 is in 1800-
2-3min is mixed under 2000r/min, obtains the raw material mixed liquor of silicon network；
(2) by 3- aminopropyltriethoxy-dimethyl (siloxanes and polysiloxanes) and the dimethyl silicone polymer of carboxy blocking to rub
You are than being (1.5-1.8): 1 mixes 2-3min at 1800-2000r/min, obtains ion network；
(3) the raw material mixed liquor that step (1) obtains and the ion network that step (2) obtains are mixed at 1800-2000r/min
Inorganic nano-filler is added after 2-3min, solidifies at 120-130 DEG C 2-3 days, the item for being then 75-85% in room temperature and humidity
Solidify 3-4 days under part, obtains the elastic composite.
10. the self-repair method of elastic composite described in any one of -5 according to claim 1, which is characterized in that
The restorative procedure is by the selfreparing elastic composite after mechanically damaged and/or voltage breakdown at 120-160 DEG C
Lower heating 6-8h.
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| CN107814937A (en) * | 2017-11-17 | 2018-03-20 | 四川大学 | The silicone elastomer and preparation method and application of a kind of repeatable processing of selfreparing |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
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| WO1996010595A1 (en) * | 1994-10-04 | 1996-04-11 | Minnesota Mining And Manufacturing Company | Reactive two-part polyurethane compositions and optionally self-healable and scratch-resistant coatings prepared therefrom |
| US20120277378A1 (en) * | 2011-04-29 | 2012-11-01 | John Keith Nelson | Self-healing electrical insulation |
| CN105440692A (en) * | 2015-12-14 | 2016-03-30 | 华南理工大学 | Microcapsule-type self-repairing polysiloxane elastomer and preparation method thereof |
| CN106496468A (en) * | 2016-10-12 | 2017-03-15 | 北京化工大学 | A kind of preparation method with self-healing and the silicone elastomer of shape-memory properties |
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