CN109161202B - Elastomer composite material and preparation method and self-repairing method thereof - Google Patents
Elastomer composite material and preparation method and self-repairing method thereof Download PDFInfo
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- 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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- 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
- C08K2201/00—Specific properties of additives
- 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 invention provides an elastomer composite material, a preparation method and a self-repairing method thereof, wherein the elastomer composite material comprises an inorganic nano filler, an ion network and a silicon network, wherein the inorganic nano filler is loaded on an interpenetrating cross-linked network formed by the ion network and the silicon network; wherein the ionic network is formed by the reaction of 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane, and the silicon network is obtained by curing hydroxyl-terminated polydimethylsiloxane. The elastomer composite material provided by the invention can self-repair under heat treatment under certain conditions, the repair efficiency after mechanical damage can reach 73-96%, and the repair efficiency after voltage breakdown can reach 58-75%.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to an elastomer composite material, a preparation method and a self-repairing method thereof.
Background
Elastomers are known as "artificial muscles" because of their excellent tensile properties, high energy density and rapid stress response capability. It is known that the skin and muscle of the human body have the greatest characteristic of self-repair after injury, so that self-healing is achieved. However, at present, most elastomers are very fragile and can be damaged after being subjected to external force or high voltage, so that the performance of the material is reduced by a light person, and the product can be directly damaged seriously, thereby causing resource waste. Therefore, it is important to design an elastomer with high mechanical properties and self-healing capability.
The self-repairing concept is firstly proposed by the American military in the middle of the 80 s of the 20 th century, and the self-repairing aims to enable the high polymer material to have the capability of preventing cracks from continuously expanding in the initial stage of crack formation in the high polymer material so as to prevent the material from being damaged, expand the use range of the material and prolong the service life. Early self-repair research focused on composite materials based on epoxy resins and epoxy vinyl resins. In recent years, the research direction of self-repairing materials extends from composite materials to elastomers, the composite materials are used as rigid or brittle materials, microcracks are usually generated instantly under the action of external impact, the crack growth speed is high, the expansion degree is large, and the time required for damage is short; different from the internal crack formation and material failure modes of the composite material, the elastomer usually causes fatigue cracks of the material under the action of alternating stress, the internal microcrack of the elastomer is slow in growth and combination speed, the failure of the elastomer needs long time, and the method for repairing the internal microcrack of the composite material or the elastomer by adopting the self-repairing technology is an effective method. CN105504502A discloses a self-repairable extrusion-grade polypropylene composite material and a preparation method thereof, wherein the self-repairable extrusion-grade polypropylene composite material comprises 43-96.8% by mass of polypropylene, 2-20% by mass of an elastomer, 0-30% by mass of talcum powder, 1-5% by mass of a fluorine-containing polymer composition and 0.1-2% by mass of an antioxidant, wherein the fluorine-containing polymer composition contained in the composite material tends to migrate to the surface of a product in the extrusion molding process, so that the surface of the product is prevented from being scratched, and the displacement deformation of a microscopic surface caused by stress scratches can be quickly repaired.
In recent years, researchers pay much attention to self-repairing dielectric elastomer materials not only because of wide application range, including military equipment, electronic products, automobiles, airplanes, building materials and other fields, wherein the self-repairing dielectric elastomer materials are most concerned in application on smart phones and computer screens, but also avoid waste of resources and funds, and have very important significance for the current situation of resource shortage and the policy of sustainable development roads in China. CN105440692A discloses a microcapsule type self-repairing polysiloxane elastomer and a preparation method thereof, wherein the microcapsule type self-repairing polysiloxane elastomer comprises, by mass, 45-68% of alpha, omega-dihydroxy polydimethylsiloxane, 4.5-27% of a reinforcing agent, 4.5-21% of a silane compound, 1.4-7% of an organic tin catalyst and 6-27% of a microcapsule, wherein the microcapsule takes polymethyl methacrylate as a wall material and a mixture of the alpha, omega-dihydroxy polydimethylsiloxane and the silane compound as a core material, and the microcapsule type self-repairing function is realized. CN107903636A discloses a PDMS-based elastic film capable of fast self-repairing without external stimulation and a preparation method thereof, wherein the elastic film comprises 1-5 parts by weight of hydroxyl or amino-terminated polydimethylsiloxane, 4-5 parts by weight of carboxyl or ester group-containing acrylic polymer and 1-2 parts by weight of hydroxyl or amino-containing polymer, and the self-repairing elastic film is a high molecular material based on hydrogen bonds and can repair damaged parts at room temperature, but the mechanical property of the film is poor and cannot meet the application requirements.
At present, a self-repairing elastomer composite material needs to be developed, which can improve the mechanical properties of elastomers and the like and has certain self-repairing capability, and the performance difference of the materials before and after repairing is not great.
Disclosure of Invention
The invention aims to provide an elastomer composite material, a preparation method and a self-repairing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an elastomer composite comprising an inorganic nanofiller, an ionic network, and a silicon network, the ionic network and the silicon network forming an interpenetrating cross-linked network, the inorganic nanofiller being supported on the interpenetrating cross-linked network;
wherein the ionic network is formed by the reaction of 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane, and the silicon network is obtained by curing hydroxyl-terminated polydimethylsiloxane.
In the present invention, the reaction of amino groups with carboxyl groups is as follows:
-COOH+-NH 2 →COO - NH 3 +
the ionic bond obtained by the interaction of the amino and the carboxyl can be broken after voltage breakdown or mechanical damage, and can be regenerated after proper heat treatment, so that the elastomer composite material achieves the self-repairing purpose; meanwhile, the mechanical property of the elastomer composite material can be enhanced by adding the inorganic nano filler.
In the invention, the elastomer composite material comprises the following components in parts by weight:
70-100 parts of silicon network;
5-40 parts of ion network;
5-30 parts of inorganic nano filler.
The addition amount of the inorganic nano filler is controlled to be 5-30 parts by weight as much as possible, and if the addition amount is less than 5 parts by weight, the addition amount is too small, so that the mechanical property of the elastomer composite material is improved slightly; if the amount is too large, the inorganic nanofiller may easily agglomerate to affect the mechanical properties of the material.
In the present invention, the silicon network is present in an amount of 70 to 100 parts by weight, for example 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, and the like.
In the present invention, the ionic network is present in an amount of 5 to 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, and the like.
In the present invention, the inorganic nanofiller is present in an amount of 5 to 30 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, and the like.
In the present invention, the weight ratio of the silicon network to the ionic network is (2-9):1, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, etc., preferably (4-6): 1.
In the invention, when the weight ratio of the silicon network to the ion network is (2-9):1, the elastomer composite material provided by the invention has better self-repairing capability and higher repairing rate which can reach 83-96%; when the weight ratio of the silicon network to the ion network is (4-6):1, the repair rate is higher and can reach 94-96%, and the performance change of the material before and after repair is small; when the mass ratio of the silicon network to the ion network is not within the range provided by the invention, if the addition amount of the ion network is too small, the repair rate is low, and if the addition amount of the ion network is too large, the elastomer is difficult to be completely cured and molded, and the finally obtained elastomer material may be in a liquid form which is extremely viscous.
Preferably, the number average molecular weight of the 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) is 4000-.
Preferably, the carboxyl-terminated polydimethylsiloxane has a number average molecular weight of 1000-1500, such as 1100, 1200, 1300, 1400, and the like.
Preferably, the hydroxyl-terminated polydimethylsiloxane has a number average molecular weight of 50000-70000, e.g., 55000, 60000, 65000, and the like.
Preferably, the size of the inorganic nanofiller is 10-100nm, such as 20nm, 30nm, 50nm, 70nm, 90nm, and the like.
Preferably, the inorganic nanofiller comprises any one of, or a combination of at least two of, ceramic particles having a perovskite structure, semiconductor particles, carbon nanomaterials, silver nanoparticles, and boron nitride nanosheets.
Preferably, the ceramic particles having a perovskite structure are barium titanate, Pb (Zr) 1-x Ti x )O 3 、Pb(Mg 1/3 Nb 2/3 )TiO 3 -PbTiO 3 、Pb(Zn 1/3 Nb 2/3 )TiO 3 -PbTiO 3 、CaCu 3 Ti 4 O 12 、PbZrO 3 And (Ba) y Sr 1-y )TiO 3 Any one or a combination of at least two of them, wherein 0<x<1，0<y<1。
Preferably, the barium titanate is barium titanate with vinyl groups on the surface.
The surface carrying may be any form of surface grafting, surface coating, surface adsorption, etc. which allows the barium titanate to carry a vinyl group, surface grafting being preferred.
Preferably, the semiconductor particles are ZnO, ZnS, MgO, SiC, ZrO 2 、Al 2 O 3 And TiO 2 Any one or a combination of at least two of them.
Preferably, the carbon nanomaterial is any one or a combination of at least two of carbon nanotubes, graphene oxide and carbon nano graphite micro-sheets.
Preferably, the particle size of the carbon nanomaterial is 0.5 to 10 μm, such as 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, and the like.
Preferably, the carbon nanotubes are surface hydroxylated carbon nanotubes.
Preferably, the graphene oxide is graphene oxide with vinyl groups carried on the surface.
Preferably, the boron nitride nanosheets are prepared by ultrasonic exfoliation of hexagonal boron nitride.
Preferably, the boron nitride nanosheets are surface aminated boron nitride nanosheets.
The inorganic nano-filler is preferably an inorganic nano-filler with a functional group on the surface, which can increase the compatibility of the inorganic nano-filler with a silicon network and an ion network.
Preferably, the preparation method of the boron nitride nanosheet comprises the following steps: and dispersing hexagonal boron nitride in a solvent to obtain a hexagonal boron nitride dispersion liquid, and then carrying out ultrasonic treatment, centrifugation and drying to obtain the boron nitride nanosheet.
Preferably, the concentration of the hexagonal boron nitride in the hexagonal boron nitride dispersion is in the range of 2 to 3g/L, such as 2.2g/L, 2.4g/L, 2.6g/L, 2.8g/L, and the like.
Preferably, the solvent is isopropanol.
Preferably, the time of the ultrasound is 36-48h, such as 38h, 40h, 42h, 44h, 46h, etc.
Preferably, the rotation speed of the centrifugation is 8000-8500r/min, such as 8100r/min, 8200r/min, 8300r/min, 8400r/min and the like.
In a second aspect, the present invention provides a process for the preparation of an elastomer composite as described in the first aspect, the process comprising the steps of:
(1) mixing hydroxyl-terminated polydimethylsiloxane and a curing agent to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane to obtain an ionic network;
(3) and (3) mixing the raw material mixed solution obtained in the step (1) and the ion network obtained in the step (2), adding an inorganic nano filler, and curing to obtain the elastomer composite material.
The preparation method provided by the invention is simple and feasible, the elastomer composite material prepared by the preparation method provided by the invention contains an interpenetrating cross-linked network formed by an ion network and a silicon network, and the inorganic nano-filler is loaded on the interpenetrating cross-linked network.
Preferably, the curing agent in the step (1) is methyltrimethoxysilane.
Preferably, the raw material mixed liquor in the step (1) further comprises a catalyst.
Preferably, the catalyst is dibutyltin dilaurate.
Preferably, the molar ratio of the hydroxyl-terminated polydimethylsiloxane, curing agent and catalyst is (10-12) to 1:1, e.g., 10.5:1:1, 11:1:1, 11.5:1:1, etc.
Preferably, the molar ratio of 3-aminopropylmethyl-dimethyl (siloxane to polysiloxane) and carboxyl-terminated polydimethylsiloxane described in step (2) is (1.5-1.8):1, e.g., 1.6:1, 1.7:1, etc.
The curing method in step (3) is to cure the mixture at 130 ℃ (e.g., 122 ℃, 124 ℃, 128 ℃, etc.) for 2-3 days (e.g., 2.4 days, 2.8 days, etc.), and then cure the mixture at room temperature and humidity of 75-85% (e.g., 78%, 80%, 82%, etc.) for 3-4 days (e.g., 3.4 days, 3.8 days, etc.).
Preferably, the mixing in step (1), step (2) and step (3) is carried out in a high-speed mixer independently.
Preferably, the mixing rotation speed of the three times of mixing is respectively and independently selected from 1800-2000r/min (such as 1850r/min, 1900r/min, 1950r/min, etc.), and the time of the three times of mixing is respectively and independently selected from 2-3min (such as 2.2min, 2.5min, 2.8min, etc.).
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing the hydroxyl-terminated polydimethylsiloxane, the curing agent and the catalyst for 2-3min at a molar ratio of (10-12) to 1:1 at 1800-2000r/min to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane in a molar ratio of (1.5-1.8) to 1 at 1800-;
(3) and (3) mixing the raw material mixed solution obtained in the step (1) and the ion network obtained in the step (2) at 1800-2000r/min for 2-3min, adding an inorganic nano filler, curing at 120-130 ℃ for 2-3 days, and then curing at room temperature and the humidity of 75-85% for 3-4 days to obtain the elastomer composite material.
In a third aspect, the present invention provides a method for self-healing an elastomer composite as described in the first aspect, wherein the self-healed elastomer composite after mechanical damage and/or voltage breakdown is heated at 160 ℃ (e.g., 130 ℃, 140 ℃, 150 ℃, etc.) for 6-8h (e.g., 6.5h, 7h, 7.5h, etc.).
After the elastomer composite material provided by the invention is subjected to mechanical damage and/or voltage breakdown and is subjected to heat treatment under certain conditions, the self-repairing purpose can be achieved, the repairing rate can reach 70-95%, and the performance change of the elastomer composite material before and after repairing is small.
Compared with the prior art, the invention has the following beneficial effects:
(1) the elastomer composite material provided by the invention contains an ion network, and an ionic bond formed by amino and carboxyl in the ion network is broken after mechanical damage and/or voltage breakdown, and can be regenerated after certain heat treatment, so that the elastomer composite material achieves the purpose of self-repairing;
(2) the inorganic nano filler is added into the elastomer composite material, so that the mechanical property, the conductivity and the like of the material can be effectively improved;
(3) the elastomer composite material provided by the invention can self-repair under heat treatment under certain conditions, the repair efficiency after mechanical damage can reach 73-96%, and the repair efficiency after voltage breakdown can reach 58-75%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
An elastomer composite material comprises the following components in parts by weight:
80 parts of silicon network;
16 parts of ion network;
30 parts of inorganic nano filler;
wherein the weight ratio of the silicon network to the ion network is 5:1, and the inorganic nano-filler is a boron nitride nano-sheet.
The preparation method comprises the following steps:
(1) mixing hydroxyl-terminated polydimethylsiloxane (Mn 60000), a curing agent and a catalyst at a molar ratio of 10:1:1 at 2000r/min for 2min to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane to polysiloxane) (Mn 4500) and a carboxyl-terminated polydimethylsiloxane (Mn 1000) in a molar ratio of 1.5:1 at 2000r/min for 2min to give an ionic network;
(3) and (3) mixing the raw material mixed solution obtained in the step (1) and the ion network obtained in the step (2) at 2000r/min for 2min, adding an inorganic nano filler, curing at 120 ℃ for 3 days, and curing at room temperature and 80% humidity for 3 days to obtain the elastomer composite material.
Examples 2 to 7
The only difference from example 1 is that the parts by weight of the ionic network is 20 parts by weight (weight ratio of silicon network to ionic network is 4:1, example 2); the weight part of the ionic network was 13.3 parts (weight ratio of silicon network to ionic network was 6:1, example 3); the weight part of the ionic network was 40 parts (weight ratio of silicon network to ionic network was 2:1, example 4); the weight part of the ionic network was 8.9 parts (weight ratio of silicon network to ionic network 9:1, example 5); the weight part of the ionic network was 8 parts (weight ratio of silicon network to ionic network was 10:1, example 6); the parts by weight of the ionic network was 80 parts by weight (weight ratio of silicon network to ionic network was 1:1, example 7).
Example 8
An elastomer composite material comprises the following components in parts by weight:
100 parts by weight of a silicon network;
40 parts of an ion network;
20 parts by weight of inorganic nano filler;
wherein the weight ratio of the silicon network to the ion network is 2.5:1, and the inorganic nano-filler is barium titanate.
The preparation method comprises the following steps:
(1) mixing hydroxyl-terminated polydimethylsiloxane (Mn: 50000), a curing agent and a catalyst at a molar ratio of 12:1:1 at 1800r/min for 3min to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane to polysiloxane) (Mn ═ 4000) and carboxy-terminated polydimethylsiloxane (Mn ═ 1500) at a molar ratio of 1.8:1 at 1900r/min for 2.5min to give an ionic network;
(3) and (3) mixing the raw material mixed liquor obtained in the step (1) and the ion network obtained in the step (2) at 1800r/min for 3min, adding inorganic nano filler, curing at 130 ℃ for 2 days, and then curing at room temperature and 75% humidity for 4 days to obtain the elastomer composite material.
Example 9
An elastomer composite material comprises the following components in parts by weight:
70 parts of silicon network;
5 parts of an ionic network;
5 parts of inorganic nano filler;
wherein the weight ratio of the silicon network to the ion network is 14:1, and the inorganic nano filler is graphene oxide.
The preparation method comprises the following steps:
(1) mixing hydroxyl-terminated polydimethylsiloxane (Mn 70000), a curing agent and a catalyst at a molar ratio of 11:1:1 at 1900r/min for 2.5min to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane to polysiloxane) (Mn ═ 5000) and carboxyl-terminated polydimethylsiloxane (Mn ═ 1000) at a molar ratio of 1.6:1 at 1800r/min for 3min to give an ionic network;
(3) and (3) mixing the raw material mixed liquor obtained in the step (1) and the ion network obtained in the step (2) at 1900r/min for 2.5min, adding an inorganic nano filler, curing at 125 ℃ for 2.5 days, and then curing at room temperature and 85% humidity for 3 days to obtain the elastomer composite material.
Comparative example 1
CN107903636A example 1 provides a self-healing elastic film (elastomer composite).
Performance testing
The elastomer composites provided in examples 1-9 and comparative example 1 were subjected to performance testing:
(1) mechanical properties: carrying out a tensile test on the composite material by using an electronic universal material testing machine, wherein the tensile rate in the test process is 40 mm/min;
(2) repairing efficiency: the repair rate is T'/T multiplied by 100%;
wherein T' is the tensile strength of the sample after being repaired, T is the initial tensile strength of the sample, the unit is MPa, the repairing rate A represents the repairing efficiency of the sample after being subjected to mechanical damage, the repairing rate B represents the repairing efficiency of the sample after being subjected to voltage breakdown, and the mechanical parameters, the voltage breakdown voltage and other parameters of the mechanical damage of all the samples are the same;
the repairing method is that the sample after mechanical damage and/or voltage breakdown is heated for 6 hours at 160 ℃.
The results of the tests on the elastomer composites provided in examples 1-9 and comparative example 1 are shown in table 1:
TABLE 1
| Sample (I) | Initial tensile strength/MPa | Elongation at break/% | Repair rate A/%) | Repair rate B/%) |
| Example 1 | 3.72 | 857 | 95.6 | 74.8 |
| Example 2 | 3.51 | 843 | 93.8 | 70.5 |
| Example 3 | 3.06 | 855 | 94.2 | 70.2 |
| Example 4 | 2.98 | 786 | 87.2 | 65.1 |
| Example 5 | 2.29 | 723 | 83.5 | 60.9 |
| Example 6 | 3.67 | 705 | 73.8 | 58.6 |
| Example 7 | 2.58 | 859 | 77.4 | 60.7 |
| Example 8 | 2.74 | 779 | 86.9 | 68.4 |
| Example 9 | 3.49 | 698 | 74.3 | 58.9 |
| Comparative example 1 | 1.06 | 890 | 93.8 | 76.2 |
According to the embodiment and experimental tests, the initial tensile strength of the elastomer composite material provided by the invention is within the range of 2-4 MPa, the elastomer composite material can complete self-repairing under heat treatment under certain conditions, the repairing efficiency after mechanical damage can reach 73-96%, and the repairing efficiency after voltage breakdown can reach 58-75%; as can be seen from the comparison between examples 1-5 and examples 6-7, when the weight ratio of the silicon network to the ion network in the elastomer composite material provided by the invention is within the range of (2-9):1, the elastomer composite material provided by the invention has better self-repairing capability and higher repairing rate, the repairing efficiency after mechanical damage can reach 83-96%, and the repairing efficiency after voltage breakdown can reach 60-75%; when the weight ratio of the silicon network to the ion network is (4-6):1, the repair rate is higher, the repair efficiency after mechanical damage can reach 94-96%, the repair efficiency after voltage breakdown can reach 70-75%, and the performance change of the material before and after repair is smaller; as can be seen from a comparison of example 1 and comparative example 1, the elastomer composite provided by the present invention has a higher tensile strength.
The applicant states that the present invention is illustrated by the above examples of the elastomer composite of the present invention and the method of making and self-healing thereof, but the present invention is not limited to the above detailed methods, i.e. it is not meant to imply that the present invention must rely on the above detailed methods to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (33)
1. An elastomer composite comprising an inorganic nanofiller, an ionic network, and a silicon network, the ionic network and the silicon network forming an interpenetrating cross-linked network, the inorganic nanofiller being supported on the interpenetrating cross-linked network;
wherein the ionic network is formed by the reaction of 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane, and the silicon network is obtained by curing hydroxyl-terminated polydimethylsiloxane.
2. The elastomer composite of claim 1, comprising in parts by weight:
70-100 parts of silicon network;
5-40 parts of ion network;
5-30 parts of inorganic nano filler.
3. The elastomer composite of claim 1 or 2, wherein the weight ratio of the silicon network to the ionic network is (2-9): 1.
4. The elastomer composite of claim 3, wherein the weight ratio of the silicon network to the ionic network is (4-6): 1.
5. The elastomer composite of claim 1, wherein the 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) has a number average molecular weight of 4000-.
6. The elastomer composite of claim 1, wherein the carboxyl terminated polydimethylsiloxane has a number average molecular weight of 1000-1500.
7. The elastomer composite of claim 1, wherein the hydroxyl terminated polydimethylsiloxane has a number average molecular weight of 50000-70000.
8. The elastomer composite of claim 1, wherein the inorganic nanofiller has a size of 10-100 nm.
9. The elastomer composite of claim 1, wherein the inorganic nanofiller comprises any one or a combination of at least two of ceramic particles having a perovskite structure, semiconductor particles, carbon nanomaterials, silver nanoparticles, and boron nitride nanoplates.
10. Elastomer composite according to claim 9, characterized in that the ceramic particles with perovskite structure are barium titanate, Pb (Zr) 1-x Ti x )O 3 、Pb(Mg 1/3 Nb 2/3 )TiO 3 -PbTiO 3 、Pb(Zn 1/3 Nb 2/3 )TiO 3 -PbTiO 3 、CaCu 3 Ti 4 O 12 、PbZrO 3 And (Ba) y Sr 1-y )TiO 3 Any one or a combination of at least two of them, wherein 0<x<1，0<y<1。
11. The elastomer composite of claim 10, wherein the barium titanate is a barium titanate having vinyl groups carried on a surface thereof.
12. Elastomer composite according to claim 9, characterized in that the semiconductor particles are ZnO, ZnS, MgO, SiC, ZrO 2 、Al 2 O 3 And TiO 2 Any one or a combination of at least two of them.
13. The elastomer composite of claim 9, wherein the carbon nanomaterial is any one of or a combination of at least two of carbon nanotubes, graphene oxide, and carbon nanographite nanoplatelets.
14. The elastomer composite of claim 9, wherein the carbon nanomaterial has a particle size of 0.5 to 10 μ ι η.
15. The elastomer composite of claim 13, wherein the carbon nanotubes are surface hydroxylated carbon nanotubes.
16. The elastomer composite of claim 13, wherein the graphene oxide is a graphene oxide with vinyl groups on the surface.
17. The elastomer composite of claim 9, wherein the boron nitride nanoplates are prepared by hexagonal boron nitride ultrasonic exfoliation.
18. The elastomer composite of claim 9, wherein the boron nitride nanoplates are surface aminated boron nitride nanoplates.
19. The elastomer composite of claim 9, wherein the method of preparing the boron nitride nanoplates is: and dispersing hexagonal boron nitride in a solvent to obtain a hexagonal boron nitride dispersion liquid, and then carrying out ultrasonic treatment, centrifugation and drying to obtain the boron nitride nanosheet.
20. The elastomer composite of claim 19, wherein the concentration of hexagonal boron nitride in the hexagonal boron nitride dispersion is 2-3 g/L.
21. The elastomer composite of claim 19, wherein the solvent is isopropanol.
22. The elastomer composite of claim 19, wherein the sonication time is 36-48 hours.
23. The elastomer composite of claim 19, wherein the rotation rate of the centrifuge is 8000-.
24. Process for the preparation of an elastomer composite according to any one of claims 1 to 23, characterized in that it comprises the following steps:
(1) mixing hydroxyl-terminated polydimethylsiloxane and a curing agent to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane to obtain an ionic network;
(3) and (3) mixing the raw material mixed solution obtained in the step (1) and the ion network obtained in the step (2), adding an inorganic nano filler, and curing to obtain the elastomer composite material.
25. The method according to claim 24, wherein the curing agent in step (1) is methyltrimethoxysilane.
26. The method according to claim 24, wherein the raw material mixture solution in the step (1) further contains a catalyst.
27. The method of claim 26, wherein the catalyst is dibutyltin dilaurate.
28. The method of claim 26, wherein the hydroxyl terminated polydimethylsiloxane, the curing agent, and the catalyst are present in a molar ratio of (10-12) to 1: 1.
29. The method of claim 24, wherein the molar ratio of 3-aminopropylmethyl-dimethyl (siloxane to polysiloxane) and carboxyl-terminated polydimethylsiloxane in step (2) is (1.5-1.8): 1;
the curing method in step (3) is curing at 120-130 ℃ for 2-3 days, and then curing at room temperature and humidity of 75-85% for 3-4 days.
30. The method according to claim 24, wherein the mixing in step (1), step (2) and step (3) is carried out independently in a high-speed mixer.
31. The method as claimed in claim 24, wherein the mixing speeds of the three mixing steps are respectively and independently selected from 1800-2000r/min, and the mixing times are respectively and independently selected from 2-3 min.
32. The method of manufacturing of claim 24, comprising the steps of:
(1) mixing hydroxyl-terminated polydimethylsiloxane, a curing agent and a catalyst for 2-3min at a molar ratio of (10-12) to 1:1 at 1800-2000r/min to obtain a raw material mixed solution of a silicon network;
(2) mixing 3-aminopropylmethyl-dimethyl (siloxane and polysiloxane) and carboxyl-terminated polydimethylsiloxane in a molar ratio of (1.5-1.8) to 1 at 1800-;
(3) and (3) mixing the raw material mixed solution obtained in the step (1) and the ion network obtained in the step (2) at 1800-2000r/min for 2-3min, adding an inorganic nano filler, curing at 120-130 ℃ for 2-3 days, and then curing at room temperature and the humidity of 75-85% for 3-4 days to obtain the elastomer composite material.
33. The self-healing method of the elastomer composite of any of claims 1 to 23, wherein the self-healing method comprises heating the self-healing elastomer composite after mechanical damage and/or voltage breakdown at 160 ℃ for 6 to 8 hours at 120 ℃.
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| US8796372B2 (en) * | 2011-04-29 | 2014-08-05 | Rensselaer Polytechnic Institute | Self-healing electrical insulation |
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