CN113980359B - Modified MXene-loaded metal oxide composite and preparation method and application thereof - Google Patents

Modified MXene-loaded metal oxide composite and preparation method and application thereof Download PDF

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CN113980359B
CN113980359B CN202111384606.6A CN202111384606A CN113980359B CN 113980359 B CN113980359 B CN 113980359B CN 202111384606 A CN202111384606 A CN 202111384606A CN 113980359 B CN113980359 B CN 113980359B
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mxene
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CN113980359A (en
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孟庆函
阳杰
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Beijing University of Chemical Technology
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    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract

The invention relates to the technical field of high polymer materials, in particular to a modified MXene loaded metal oxide composite material, and a preparation method and application thereof. The modified MXene supported metal oxide composite material provided by the invention comprises a modified MXene carrier and metal oxide, wherein the mass ratio of the modified MXene carrier is 25-60wt%, and the mass ratio of the metal oxide is 40-75wt%. The material of the invention can be uniformly dispersed in a polymer matrix, and a heat-resistant network is introduced into the silicon rubber as a heat-resistant filler.

Description

Modified MXene-loaded metal oxide composite and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified MXene loaded metal oxide composite material, and a preparation method and application thereof.
Background
The silicone rubber is an organic rubber taking Si-O as a main chain, is widely applied to the fields of aerospace, national defense and the like, and along with the continuous development of technology, the requirement on the heat resistance of the silicone rubber is higher and higher, one of the main ways of improving the heat resistance of the silicone rubber at present is to add a heat-resistant auxiliary agent, and the most commonly used way is to add metal oxides such as ferric oxide, copper oxide and the like.
Many studies on the use of metal oxides as heat-resistant additives to enhance the heat resistance of polymers have been conducted, and patent CN104725686a uses iron oxide, antimony oxide and zinc oxide compounded with styrene-butadiene rubber in a mixing manner with accelerators, vulcanizing agents, antioxidants, etc. at a use temperature of 145±5 ℃. Patent CN103965641a uses a spherical polysiloxane powder loaded iron oxide or cerium oxide as a heat-resistant agent, platinum as a catalyst, and methylbutynol and white carbon black as an inhibitor and a reinforcing agent respectively, and the like, and the addition type heat-resistant liquid silicone rubber composition is obtained by means of solution polymerization, and the use temperature is 270-350 ℃. The patent CN1912005A takes iron oxide red and mixed rare earth oxide as a heat resistant agent, takes organic guanidine as a catalyst, and obtains a product through vacuum stirring reaction, wherein the use temperature reaches 300 ℃, but the catalyst is easy to poison and the like. The patent CN101735620A prepares the high temperature resistant methyl vinyl silicone rubber by mixing cerium oxide and polyimide as heat-resistant additives, hydroxyl silicone oil and dimethyl silicone oil as oil-resistant additives and adding a silane coupling agent, wherein the use temperature is above 300 ℃.
The problems commonly existing in the researches are that the preparation process is complex, catalyst poisoning is possibly caused, the dispersibility of the heat-resistant filler in the rubber matrix is poor, agglomeration is easily caused, and when the addition amount is too large, the mechanical and heat resistance of the rubber matrix are negatively affected, so that the use of a certain carrier for improving the compatibility and dispersibility of the metal oxide and the rubber matrix is a hopeful way for solving the problems.
MXene is a two-dimensional layered transition metal carbon/nitride, has a two-dimensional lamellar structure similar to graphene, and has a structural general formula of Mn+1XnTx. Wherein T represents a terminating functional group such as-OH, -F, =o; m is an early transition metal element such as Ti, V, cr, zr, nb, etc.; x refers to C or N element. theconventionalpreparationmethodoftheMXenematerialistoetchMAXphase,breakM-AbondpreferentiallyandkeepM-Xbond,sothatthesurfaceofthepreparedMXenehasalargenumberoffunctionalgroups,andthecompatibilityanddispersibilityoftheMXenewithasiliconrubbermatrixcanbeimprovedbyusingtheMXeneasametaloxidecarrier.
Many studies on the use of MXene as a metal oxide carrier have been conducted, and patent CN108511733A is to mix and dissolve a MXene film and two acetylacetone metal salts in a dibenzyl ether solvent and then to generate a bimetallic oxide on the surface of MXene by in-situ pyrolysis, however, in the preparation process, a toxic solvent dibenzyl ether needs to be added, and centrifugal separation, suction filtration, washing and reduced pressure rotary evaporation are required to remove the solvent, so that the process is complicated. The patent CN107221428A directly mixes the MXene two-dimensional nano-sheet solution with the metal oxide for vacuum suction filtration to obtain the metal oxide/MXene two-dimensional nano-composite, but the uniformity of the mixed solution cannot be ensured, which can lead to uneven distribution of the metal oxide on the MXene nano-sheet and influence the performance of the final product. In the process of preparing MXene, the patent CN109904426A adds an intercalating agent of tetramethyl ammonium hydroxide, then adds an iron salt solution and an alkali solution into a product solution, and carries out in-situ growth to obtain a target product.
The common problem in the above-mentioned researches is that the preparation process is complicated, the addition and recovery of the organic solvent are required, and some solvents are toxic; or other auxiliary agents and fillers are needed to be added, the post-treatment process is complex, the environmental pollution is serious, and the production cost is high.
Disclosure of Invention
The invention aims to provide a modified MXene-loaded metal oxide composite material, a preparation method and application thereof, wherein the surface of the modified material is uniformly loaded with metal oxide and can be uniformly dispersed in a polymer matrix, a heat-resistant network is introduced into the polymer, and the heat resistance of the polymer, especially rubber, is enhanced.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the modified MXene loaded metal oxide composite material comprises a modified MXene carrier and a metal oxide, wherein the mass ratio of the modified MXene carrier is 25-60wt%, and the mass ratio of the metal oxide is 40-75wt%.
The modified MXene carrier is of a lamellar structure, nano-scale protrusions are distributed on the surface of the modified MXene carrier, and the size of the lamellar structure is 10-100nm.
The modified MXene carrier is prepared by carboxyl grafting of an MXene material, and the surface of the modified MXene carrier is provided with a functional group capable of reacting with a polymer.
The metal oxide comprises a transition metal oxide and/or a rare earth metal oxide;
preferably, the transition metal oxide comprises iron oxide and/or copper oxide;
preferably, the rare earth metal oxide includes cerium oxide.
The invention also provides a preparation method of the modified MXene-loaded metal oxide composite material, which comprises the following steps:
s1: etching the transition metal carbon/nitride with an etchant to obtain an MXene material and preparing the MXene material into an MXene solution;
the etching includes the steps of:
(1) Slowly adding transition metal carbon/nitride into the etchant, and uniformly stirring to obtain dispersion;
(2) The dispersion liquid in the step (1) is subjected to constant temperature water bath for T3 time at the temperature of T1 to prepare reaction liquid;
(3) Washing and centrifuging the reaction liquid in the step (2), and freeze-drying the precipitate to obtain an MXene material;
wherein the transition metal carbo/nitride in step (1) comprises Ti 3 AlC 2 ；
The etchant comprises hydrofluoric acid and/or a mixture of hydrochloric acid and lithium fluoride;
preferably, the etchant comprises a mixture of hydrochloric acid and lithium fluoride;
compared with the etchant directly using hydrofluoric acid as the etchant, the etchant prepared by mixing hydrochloric acid and lithium fluoride has reduced toxicity to the environment and human body, and is a preferable etchant;
the molar mass ratio of the Ti3AlC2 to the hydrofluoric acid is 1:20-40;
preferably, the molar mass ratio of the Ti3AlC2 to the hydrofluoric acid is 1:20;
the molar mass ratio of the Ti3AlC2 to the lithium fluoride to the hydrochloric acid is 1:20-40:1-3;
preferably, the molar mass ratio of the Ti3AlC2, the lithium fluoride and the hydrochloric acid is 1:20:1.6
The temperature of T1 in the step (2) is 35-45 ℃;
preferably, the T1 temperature is 40 ℃;
the t3 time in the step (2) is 24-48h;
preferably, the t3 time is 36h;
the washing agent in the step (3) is deionized water, the washing is carried out until the PH of the solution is 5.5-6.5, and preferably, the washing is carried out until the PH of the solution is 6;
the freezing temperature is-50 to-70 ℃;
the drying temperature is 50-60 ℃.
S2: adding a modifier into the MXene solution in the step S1, and freeze-drying after full reaction to obtain modified MXene powder;
the modifier comprises chloroacetic acid and/or sodium hydroxide;
30-50 parts by mass of an MXene material in the MXene solution, and 60-80 parts by mass of a modifier;
the freezing temperature is-50 to-70 ℃, preferably-60 ℃;
the drying temperature is 50-60 ℃.
In the step, the modifier is used for carrying out carboxyl grafting modification on the MXene material, the number of-COOH functional groups on the surface of the MXene material is increased, and compared with other functional groups on the surface of the MXene material, such as-NH 2 and-OH, -COOH, the compatibility between the composite material and silicone rubber is better, and a large number of-COOH on the surface of the composite material and the high polymer of the silicone rubber matrix interact to carry out esterification reaction, so that the compatibility with the silicone rubber matrix is improved, and the composite material can be better dispersed in the silicone rubber matrix. The nano-scale protrusions are distributed on the surface of the modified MXene material, so that the interaction between MXene sheets can be obviously weakened, the carboxylated MXene has a unique two-dimensional nano structure, metal oxide can be uniformly and controllably attached to the surface of the MXene sheets through Van der Waals force, the metal oxide is better loaded on the modified MXene material, and the dispersibility of the metal oxide in a modified MXene carrier is improved.
S3: preparing an ethanol solution of metal salt, adding the modified MXene powder in the step S2, and stirring for ultrasonic treatment for t1 time to obtain a precursor solution;
the metal salts comprise transition metal salts and/or rare earth metal salts;
preferably, the transition metal salt comprises an iron salt and/or a copper salt;
more preferably, the iron salt comprises ferric nitrate, ferric oxalate and/or ferric chloride;
more preferably, the copper salt comprises copper nitrate, copper oxalate and/or copper chloride;
preferably, the rare earth metal salt comprises cerium nitrate, cerium oxalate and/or cerium chloride;
30-50 parts by mass of modified MXene powder, 50-100 parts by mass of ethanol solution of metal salt, and 3-20mmol/L of metal ions in the ethanol solution of metal salt;
the time t1 is 5-9h;
preferably, the t1 time is 6-6.5h.
S4: and (3) adding an active agent into the precursor solution in the step (S3), stirring for t2 time, washing, vacuum drying and calcining to obtain the modified MXene loaded metal oxide composite material.
The active agent comprises one or more of inorganic acids, alkalis, metal cations, alkaline earth metal cations, sulfides and organic compounds;
preferably, the activator comprises sodium dodecyl benzene sulfonate and ammonia water;
30-50 parts by mass of modified MXene powder in the precursor solution, and 30-50 parts by mass of activator;
the time t2 is 6-10h;
preferably, the t2 time is 7-8h;
the washing agent is deionized water;
the calcination temperature is 500-700 ℃ and the calcination time is 6-8h.
The invention also provides application of the modified MXene-loaded metal oxide composite material in the aspect of being used as a rubber heat-resistant filler, in particular to application of being used as a heat-resistant filler of silicon rubber, fluororubber or acrylic rubber.
The method comprises the following specific steps:
a) Dissolving rubber in Tetrahydrofuran (THF) solution, and mechanically stirring for 30-60min to obtain rubber/THF solution;
b) Dissolving a modified MXene loaded metal oxide composite material accounting for 0.2-0.3% of the rubber mass ratio in Tetrahydrofuran (THF) solution, and carrying out ultrasonic treatment for 30-60min to obtain a MXene/THF solution;
c) Dropping the MXene/THF solution into the stirred rubber/THF solution, stirring for 4-6h, and performing ultrasonic treatment for 1-2h;
d) Adding 5phr of ethyl orthosilicate and 2phr of dibutyl tin dilaurate into the product of the step c), stirring for 5-10min, performing ultrasonic treatment for 5-10min, defoaming, and curing at room temperature to obtain the rubber with the modified MXene loaded metal oxide composite material as the heat-resistant filler.
Compared with the prior art, the invention has the following advantages:
(1) The composite material provided by the invention adopts the modified MXene material with a lamellar structure and carboxylation to load the metal oxide, the metal oxide is uniformly and controllably loaded on the surface, and the surface of the material has a large number of active functional groups, especially-COOH content, so that the compatibility with a silicon rubber polymer matrix is enhanced;
(2) According to the preparation method provided by the invention, the metal salt solution and the carboxylated MXene are used as raw materials, and the metal oxide is introduced by using the metal salt solution, so that the nano metal particles can be promoted to be dispersed more uniformly on the MXene carrier, and then the impurities are removed by a calcination method.
Drawings
FIG. 1 is a silicone rubber thermal weight loss curve;
FIG. 2 (a) is an SEM of the MXene material before modification, and (b) is an SEM of the MXene material after modification;
fig. 3 (a) is an SEM of a pure silicone rubber, (b) is an SEM of a silicone rubber to which 0.1% by mass of the modified MXene-loaded metal oxide composite material is added, (c) is an SEM of a silicone rubber to which 0.2% by mass of the modified MXene-loaded metal oxide composite material is added, and (d) is an SEM of a silicone rubber to which 0.3% by mass of the modified MXene-loaded metal oxide composite material is added.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The technical solution of the present invention will be described in detail with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
As shown in FIG. 2, a modified MXene-loaded metal oxide composite material comprises a modified MXene carrier and ferric oxide, wherein the mass ratio of the modified MXene carrier is 38wt%, and the mass ratio of the ferric oxide is 62wt%.
The modified MXene carrier is a lamellar structure, nano-scale protrusions are distributed on the surface of the modified MXene carrier, and the size of the lamellar structure is 47nm.
The preparation method of the modified MXene-loaded metal oxide composite material comprises the following steps:
s1: for Ti with a mixture of lithium fluoride and hydrochloric acid 3 AlC 2 Etching to obtain an MXene material and preparing an MXene solution;
the method comprises the following specific steps:
(1) Will be 0.5 g of Ti 3 AlC 2 (2.57 mmol) in a plastic beaker containing 1.34g lithium fluoride (51.4 mmol) and 20mL hydrochloric acid (4.1 mmol) was slowly added over 10min and stirred well to obtain a dispersion;
(2) The dispersion liquid in the step (1) is subjected to constant temperature water bath for 36 hours at 40 ℃ to prepare a reaction liquid;
(3) Washing the reaction solution in the step (2) with deionized water until the pH value is 6, centrifuging, taking out the sediment at the lower layer, freezing at the temperature of minus 60 ℃, and drying at the temperature of 55 ℃ to prepare an MXene material and preparing an MXene solution;
s2: adding 70 parts by mass of chloroacetic acid and sodium hydroxide into the MXene solution in the step S1, fully reacting, freezing at-60 ℃, and drying at 50 ℃ to obtain modified MXene powder;
s3: using absolute ethyl alcohol as a solvent, performing ultrasonic dispersion, preparing 70 parts by mass of 10mmol/L ferric nitrate solution, adding the modified MXene powder obtained in the step S2, and stirring and performing ultrasonic treatment for 6 hours to obtain a precursor solution;
s4: and (3) adding 40 parts by mass of sodium dodecyl benzene sulfonate into the precursor solution in the step (S3), stirring for 8 hours, washing with deionized water, drying in vacuum, and calcining at 600 ℃ for 7 hours to obtain the modified MXene-loaded metal oxide composite material.
The modified MXene loaded metal oxide composite material is added into silicon rubber to be used as heat-resistant filler, and the specific steps are as follows:
a) Weighing 20g of silicone rubber, dissolving in 20ml of Tetrahydrofuran (THF) solution, and mechanically stirring for 30min to obtain silicone rubber/THF solution;
b) Weighing 0.05g of modified MXene-loaded metal oxide composite material, dissolving the modified MXene-loaded metal oxide composite material in 40ml of Tetrahydrofuran (THF), and carrying out ultrasonic treatment for 30min to obtain a MXene/THF solution;
c) Dropwise adding the MXene/THF solution into the stirred silicone rubber/THF solution, stirring for 5h, and carrying out ultrasonic treatment for 1h;
d) 5phr of ethyl orthosilicate and 2phr of dibutyl tin dilaurate are added to the mixed solution in the step c), stirred for 5min, ultrasonic treated for 5min, and cured at room temperature after defoaming, so as to obtain the silicone rubber (shown in figure 3) with the modified MXene-loaded metal oxide composite material as the heat-resistant filler.
Example 2
The modified MXene supported metal oxide composite material comprises a modified MXene carrier and copper oxide, wherein the mass ratio of the modified MXene carrier is 25wt%, and the mass ratio of the copper oxide is 75wt%.
The modified MXene carrier is a lamellar structure, nano-scale protrusions are distributed on the surface of the modified MXene carrier, and the size of the lamellar structure is 15nm.
The preparation method of the modified MXene-loaded metal oxide composite material comprises the following steps:
s1: for Ti with hydrofluoric acid 3 AlC 2 Etching to obtain an MXene material and preparing an MXene solution;
the method comprises the following specific steps:
(1) Will be 0.5 g of Ti 3 AlC 2 (2.57 mmol) was slowly added to a plastic beaker containing 30mL of hydrofluoric acid (51.4 mmol) over 10min and stirred well to obtain a dispersion;
(2) The dispersion liquid in the step (1) is subjected to constant temperature water bath for 24 hours at 35 ℃ to prepare a reaction liquid;
(3) Washing the reaction solution in the step (2) with deionized water until the pH value is 5.5, centrifuging, taking out the sediment at the lower layer, freezing at the temperature of minus 50 ℃, and drying at the temperature of 50 ℃ to prepare an MXene material and preparing the MXene material into an MXene solution;
s2: adding 60 parts by mass of chloroacetic acid and sodium hydroxide into the MXene solution in the step S1, fully reacting, freezing at-50 ℃, and drying at 50 ℃ to obtain modified MXene powder;
s3: using absolute ethyl alcohol as a solvent, performing ultrasonic dispersion, preparing 100 parts by mass of copper oxalate solution with the concentration of 3mmol/L, adding the modified MXene powder obtained in the step S2, and stirring and performing ultrasonic treatment for 5 hours to obtain a precursor solution;
s4: and (3) adding 30 parts by mass of ammonia water into the precursor solution in the step (S3), stirring for 6 hours, washing with deionized water, drying in vacuum, and calcining at 500 ℃ for 6 hours to obtain the modified MXene-loaded metal oxide composite material.
The modified MXene loaded metal oxide composite material is added into silicon rubber to be used as heat-resistant filler, and the specific steps are as follows:
a) Weighing 20g of fluororubber, dissolving in 20ml of Tetrahydrofuran (THF) solution, and mechanically stirring for 45min to obtain fluororubber/THF solution;
b) 0.04g of the modified MXene-loaded metal oxide composite material is weighed and dissolved in 40ml of Tetrahydrofuran (THF), and ultrasonic treatment is carried out for 45min to obtain MXene/THF solution;
c) Dropping the MXene/THF solution into the stirring fluororubber/THF solution, stirring for 4 hours, and carrying out ultrasonic treatment for 1.5 hours;
d) Adding 5phr of ethyl orthosilicate and 2phr of dibutyl tin dilaurate into the mixed solution in the step c), stirring for 8min, performing ultrasonic treatment for 8min, defoaming, and curing at room temperature to obtain the fluororubber with the modified MXene-loaded metal oxide composite material as the heat-resistant filler.
Example 3
A modified MXene supported metal oxide composite material comprises a modified MXene carrier and cerium oxide, wherein the mass ratio of the modified MXene carrier is 60wt%, and the mass ratio of the cerium oxide is 40wt%.
The modified MXene carrier is a lamellar structure, nano-scale protrusions are distributed on the surface of the modified MXene carrier, and the size of the lamellar structure is 47nm.
The preparation method of the modified MXene-loaded metal oxide composite material comprises the following steps:
s1: for Ti with a mixture of lithium fluoride and hydrochloric acid 3 AlC 2 Etching to obtain an MXene material and preparing an MXene solution;
the method comprises the following specific steps:
(1) Will be 0.5 g of Ti 3 AlC 2 (2.57 mmol) in a plastic beaker containing 2.68g lithium fluoride (102.8 mmol) and 50mL hydrochloric acid (7.7 mmol) was slowly added over 10min and stirred well to obtain a dispersion;
(2) The dispersion liquid in the step (1) is subjected to constant temperature water bath for 48 hours at 45 ℃ to prepare a reaction liquid;
(3) Washing the reaction solution in the step (2) with deionized water until the pH value is 6.5, centrifuging to remove the precipitate at the lower layer, freezing at the temperature of-70 ℃, and drying at the temperature of 60 ℃ to obtain an MXene material;
s2: adding 80 parts by mass of chloroacetic acid and sodium hydroxide into the MXene solution in the step S1, fully reacting, freezing at-70 ℃, and drying at 50 ℃ to obtain modified MXene powder;
s3: (4) Taking 50 parts by mass of an MXene material, adding absolute ethyl alcohol, carrying out ultrasonic stirring for 1h, preparing 50 parts by mass of a 20mmol/L cerium chloride solution prepared from the MXene solution, adding the modified MXene powder obtained in the step S2, and carrying out ultrasonic stirring for 9h to obtain a precursor solution;
s4: and (3) adding 50 parts by mass of ammonia water into the precursor solution in the step (S3), stirring for 10 hours, washing with deionized water, drying in vacuum, and calcining at 700 ℃ for 8 hours to obtain the modified MXene-loaded metal oxide composite material.
The modified MXene loaded metal oxide composite material is added into silicon rubber to be used as heat-resistant filler, and the specific steps are as follows:
a) Weighing 20g of acrylic rubber, dissolving in 20ml of Tetrahydrofuran (THF) solution, and mechanically stirring for 60min to obtain an acrylic rubber/THF solution;
b) Weighing 0.06g of modified MXene-loaded metal oxide composite material, dissolving the modified MXene-loaded metal oxide composite material in 40ml of Tetrahydrofuran (THF), and carrying out ultrasonic treatment for 60min to obtain a MXene/THF solution;
c) Dropwise adding the MXene/THF solution into the stirred acrylic rubber/THF solution, stirring for 6h, and carrying out ultrasonic treatment for 2h;
d) Adding 5phr of ethyl orthosilicate and 2phr of dibutyl tin dilaurate into the mixed solution in the step c), stirring for 10min, performing ultrasonic treatment for 10min, defoaming, and curing at room temperature to obtain the acrylic rubber with the modified MXene-loaded metal oxide composite material as the heat-resistant filler.
Test example 1
The silicon rubber and the blank silicon rubber added with the modified MXene-loaded metal oxide composite material prepared in the example 1 as heat-resistant filler are subjected to thermogravimetric analysis, and a Mettler Toledo thermogravimetric analyzer in Switzerland is used for thermogravimetric analysis under a nitrogen atmosphere, so that the mass change rate is recorded. The temperature rising rate is 10 ℃/min, the temperature rising interval is 30-800 ℃, and the sample dosage is 3-5mg.
As in fig. 1, the 5% weight loss temperature of the blank silicone rubber was 323 ℃, the 5% weight loss temperature of the example 1 silicone rubber was 353 ℃, and was 30 ℃ higher than the 5% weight loss temperature of the blank silicone rubber; the 50% weight loss temperature of the blank silicone rubber was 370 ℃, the 50% weight loss temperature of the example 1 silicone rubber was 515 ℃, 145 ℃ higher than the 50% weight loss temperature of the blank silicone rubber; the final decomposition temperature of the blank silicone rubber was 546 c, the final decomposition temperature of the example 1 silicone rubber was 613 c, and 67 c higher than the final decomposition temperature of the blank silicone rubber.
Test example 1 shows that the modified MXene loaded metal oxide composite material provided by the invention can be used for enhancing the heat resistance of the silicon rubber, and the heat resistance of the silicon rubber added with the composite material is greatly improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (5)

1. The preparation method of the modified MXene-loaded metal oxide composite material used as the heat-resistant filler of the rubber is characterized by comprising the following steps:
s1: etching Ti with etchant 3 AlC 2 Etching to obtain an MXene material and preparing an MXene solution;
the etching includes the steps of:
(1) Ti is mixed with 3 AlC 2 Slowly adding the mixture into the etchant, and uniformly stirring to obtain dispersion;
(2) The dispersion liquid in the step (1) is subjected to constant temperature water bath for T3 time at the temperature of T1 to prepare reaction liquid;
(3) Washing and centrifuging the reaction liquid in the step (2), and freeze-drying the precipitate to obtain an MXene material;
wherein the temperature of T1 in the step (2) is 35-45 ℃;
the t3 time in the step (2) is 24-48h;
the washing agent in the step (3) is deionized water, and the washing agent is washed until the PH value of the solution is 6; the freezing temperature is-50 to-70 ℃; the drying temperature is 50-60 ℃;
s2: adding a modifier into the MXene solution in the step S1, and freeze-drying after full reaction to obtain modified MXene powder;
s3: preparing an ethanol solution of metal salt, adding the modified MXene powder in the step S2, and stirring for ultrasonic treatment for t1 time to obtain a precursor solution;
s4: adding an active agent into the precursor solution in the step S3, stirring for t2 time, washing, vacuum drying and calcining to obtain the modified MXene loaded metal oxide composite material;
the etchant is a mixture of hydrochloric acid and lithium fluoride;
the Ti is 3 AlC 2 The molar mass ratio of the lithium fluoride to the hydrochloric acid is 1:20-40:1-3;
the modifier comprises chloroacetic acid and/or sodium hydroxide;
the active agent comprises sodium dodecyl benzene sulfonate and ammonia water.
2. The method according to claim 1, wherein the Ti is 3 AlC 2 The molar mass ratio of lithium fluoride to hydrochloric acid is 1:20:1.6.
3. The method of claim 1, wherein step S2 satisfies one or more of the following conditions:
a. 30-50 parts by mass of an MXene material in the MXene solution, and 60-80 parts by mass of a modifier;
b. the freezing temperature is-50 to-70 ℃;
c. the drying temperature is 50-60 ℃.
4. The method of claim 1, wherein step S3 satisfies one or more of the following conditions:
d. the metal salts comprise transition metal salts and/or rare earth metal salts;
e. the transition metal salt comprises an iron salt and/or a copper salt;
f. the iron salt comprises ferric nitrate, ferric oxalate and/or ferric chloride;
g. the copper salt comprises copper nitrate, copper oxalate and/or copper chloride;
h. the rare earth metal salt comprises cerium nitrate, cerium oxalate and/or cerium chloride;
i. 30-50 parts by mass of modified MXene powder, 50-100 parts by mass of ethanol solution of metal salt, and 3-20mmol/L of metal ions in the ethanol solution of metal salt;
j. the time t1 is 5-9h;
k. the t1 time is 6-6.5h.
5. The method of claim 1, wherein step S4 satisfies one or more of the following conditions:
30-50 parts by mass of modified MXene powder in the precursor solution, and 30-50 parts by mass of active agent;
m. the t2 time is 6-10h;
n, the t2 time is 7-8h;
the washed detergent is deionized water;
and p, the calcining temperature is 500-700 ℃ and the calcining time is 6-8h.
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