CN112029284A - Graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber and preparation method thereof - Google Patents
Graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber and preparation method thereof Download PDFInfo
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 108
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 13
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber and a preparation method thereof, wherein graphene oxide dispersion-assisted montmorillonite (rich functional groups on the surface of graphene oxide are utilized to form good fixation with montmorillonite through mutual immobilization effect to realize synergistic dispersion) is added into polysulfide rubber for improving the mechanical and thermal properties of the polysulfide rubber. According to the invention, the polysulfide rubber is modified by graphene oxide-assisted dispersion of montmorillonite, and graphene oxide and the montmorillonite modified by cetyl trimethyl ammonium bromide are combined through electrostatic interaction, so that a graphene oxide/montmorillonite assembly is formed, the agglomeration of nano-filler is prevented, the interaction between the assembly and a polymer matrix is enhanced, and the mechanical and thermal properties of the polysulfide rubber are obviously improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber and a preparation method thereof.
Background
Polysulfide rubber (PSR) is a polysulfide oligomer, is mainly used in the fields of sealants, adhesives and the like at present, and is receiving attention due to its excellent adhesion to different surfaces, corrosion resistance to fuels and solvents, and high tolerance to ozone and ultraviolet rays. But the mechanical property and the thermal property of the polysulfide rubber are very low, so that the exploration of a proper modification method for improving the property of the polysulfide rubber is the key for expanding the application of the polysulfide rubber.
The nano material has the characteristics of small particle size, large specific surface area and the like, so that the nano material has a larger contact area with a matrix when a polymer is modified, the improvement of interface bonding strength is facilitated, and the polymer can be effectively enhanced. However, since the surface energy of the nanomaterial is large and is usually in a thermodynamically unstable state, modification of a polymer with the nanomaterial tends to have the following problems. First, the nanomaterial is prone to agglomeration after incorporation into the polymer, resulting in a loss of the small size advantage. When the composite material is stressed, the positions of the agglomerates are usually firstly broken due to stress concentration, so that the reinforcing effect of the filler is not obvious, and the strength of the composite material is even lower than that before modification when the agglomerates are serious. Second, the nanomaterial interacts poorly with the polymer interface. The existence of the interface can prevent the crack from expanding and slow down the stress concentration, so that the filler and the matrix form a whole and transfer the stress. If the wettability between the matrix and the filler is poor, the interface bonding strength is low, and the performance of the polymer composite material is directly influenced. At present, the main method for improving the dispersibility of the nano material in the polymer and improving the interaction force of the interface is surface chemical modification. Through modification, the functional groups on the surface of the nano material increase the moving resistance of the nano material in the polymer, and the nano material is prevented from being agglomerated. However, the means for improving compatibility by chemical modification has the following problems: 1) a large amount of organic solvent is generally consumed in the chemical modification process, so that the cost is high and the environment is not protected; 2) modified molecules are difficult to uniformly cover the surface of the nano material, the interaction between the nano material which is not covered by the modified groups and the interface of the polymer matrix is weak, and the defects usually appear firstly when the nano material is stressed; 3) the introduction of organic functional groups can weaken the properties of the nano material and reduce the due modification effect of the nano material. For example, Wang et al added silanized graphene oxide to an epoxy matrix and found that modified graphene oxide was covered by a flexible interfacial layer, which reduced the stress transfer efficiency at the filler-polymer interface. Therefore, the method for exploring a brand-new method for promoting the uniform dispersion of the nano-components in the polymer, improving the interface combination and simultaneously not sacrificing the intrinsic performance of the nano-material has important research value.
The graphene is formed by the SP of carbon atoms2The layered material formed by hybrid connection is the material with the highest known mechanical strength at present. Graphene oxide is an oxide of graphene, and the surface of graphene oxide prepared by a chemical method contains abundant carboxyl, hydroxyl and epoxy groups, so that the graphene oxide can be dispersed in various polymer matrixes at a nanometer level and can form strong interaction with other nanometer materials. Therefore, the graphene is used as a carrier, and after a proper nano material is screened and compounded, the composite material has great research value when being used for modifying the polysulfide rubber material.
Disclosure of Invention
The invention discloses graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber and a preparation method thereof, and aims to solve the problem of agglomeration of a nano filler in a polymer matrix through synergistic dispersion of graphene oxide and montmorillonite so as to improve the mechanical and thermal properties of the polysulfide rubber to the greatest extent.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention firstly discloses graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber which is characterized in that: the modified polysulfide rubber is prepared by adding modified filler graphene oxide to polysulfide rubber to help disperse montmorillonite, and is used for improving the mechanical and thermal properties of the polysulfide rubber; the graphene oxide dispersion-assisted montmorillonite is a graphene oxide/montmorillonite assembly formed by combining graphene oxide and montmorillonite nano-materials through electrostatic interaction. The graphene oxide is well fixed with montmorillonite by utilizing the mutual immobilization of rich functional groups on the surface of the graphene oxide, so that the synergistic dispersion is realized.
Further, the montmorillonite nano material is a Cetyl Trimethyl Ammonium Bromide (CTAB) modified montmorillonite nano material.
Further, the graphene oxide-assisted dispersion montmorillonite is obtained by uniformly mixing graphene oxide and montmorillonite nano-materials in the form of water dispersion, washing with water and freeze-drying, wherein the mass ratio of the graphene oxide to the montmorillonite nano-materials is 1: 1-5, and most preferably 1: 5.
furthermore, the addition amount of the graphene oxide dispersion-assisting montmorillonite accounts for 0.1-2% of the mass of the polysulfide rubber.
The invention also discloses a preparation method of the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber, which comprises the following steps:
weighing 10g of peeled montmorillonite, and dispersing the montmorillonite in a proper amount of deionized water to obtain montmorillonite suspension; weighing 5g of hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in a proper amount of ethanol, then adding the solution into the montmorillonite suspension, and heating and stirring the mixture for 24 hours; then centrifugally washing and drying to obtain modified montmorillonite which is marked as OMMT;
step 2, respectively dispersing graphene oxide and OMMT in deionized water, then ultrasonically mixing water dispersions of the graphene oxide and the OMMT according to the mass ratio of 1: 1-5, standing for 15-24 h, washing and freeze-drying the obtained precipitate to obtain graphene oxide-assisted dispersion montmorillonite, which is marked as GO-OMMT;
Further, in the step 3, the raw materials comprise the following components in parts by weight: 100 parts of polysulfide rubber, 0.1-2 parts of GO-OMMT and MnO210 parts.
The invention has the beneficial effects that:
according to the preparation method, the polysulfide rubber is modified by the graphene oxide-assisted dispersion of the montmorillonite, and the graphene oxide and the montmorillonite modified by Cetyl Trimethyl Ammonium Bromide (CTAB) are combined through electrostatic interaction, so that a graphene oxide/montmorillonite (GO-OMMT) assembly is formed, the agglomeration of a nano filler is prevented, the interaction between the assembly and a polymer matrix is enhanced, and the mechanical and thermal properties of the polysulfide rubber are obviously improved.
Drawings
Fig. 1 is an infrared spectrum of a lamellar Graphene Oxide (GO), montmorillonite (MMT), CTAB-modified montmorillonite nanomaterial (OMMT), and each graphene oxide-loaded montmorillonite sample in example 1 of the present invention;
FIGS. 2(a) - (c) are TEM images of montmorillonite (MMT), CTAB modified montmorillonite nanomaterial (OMMT) and graphene oxide assisted dispersion montmorillonite sample in the example 1 of the present invention;
FIG. 3 is a Raman spectrum of a sample of lamellar Graphene Oxide (GO) and each graphene oxide-assisted montmorillonite in example 1 of the present invention;
fig. 4 is a drawing (fig. 4(a)) of tensile properties and young's modulus of each graphene oxide-assisted montmorillonite modified polysulfide rubber prepared in example 2 of the present invention (fig. 4 (b)).
Detailed Description
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The montmorillonite nanomaterials used in the examples below are commercially available.
The preparation method of graphene oxide used in the following examples is as follows: 2g of graphite powder and 1g of NaNO3Adding the powder into a three-neck flask, and adding 50mL of concentrated H with the mass concentration of 98%2SO4Magnetic stirring in ice-water bath, adding 6g KMnO4Adding the solid particles into a three-neck flask in batches at the temperature of 5 ℃, heating to 35 ℃ after adding, and stirring for reacting for 24 hours; after the reaction is finished, adding 100mL of deionized water into the reaction solution, stirring and mixing uniformly, then adding 250mL of deionized water, then dropwise adding 15mL of 30 wt% hydrogen peroxide into the reaction solution, stirring and mixing uniformly, then centrifuging at the rotating speed of 4500r/min, removing supernatant, washing with water and centrifuging the precipitate until the pH is close to neutral; and transferring the centrifuged precipitate to a 500mL big beaker, adding 300mL deionized water, performing ultrasonic treatment for more than 2h, centrifuging the solution for 20min at the rotating speed of 4500r/min, collecting the liquid on the upper part of the centrifuge tube, namely the brown graphene oxide solution, dialyzing for one week by a dialysis bag with the molecular weight cutoff of 12000-14000, and performing freeze drying at-50 ℃ for 24h to obtain the graphene oxide.
According to the method, a high-temperature oxidation stage at 95 ℃ is omitted, and the reaction time at a medium-temperature reaction stage at 35 ℃ is increased, so that the oxidation of graphite is more sufficient, the oxidation degree of graphene oxide is higher, and the structural damage degree of graphene oxide is smaller.
Example 1 preparation of graphene oxide-assisted montmorillonite
weighing 10g of peeled montmorillonite, and dispersing the montmorillonite in a proper amount of deionized water to obtain montmorillonite suspension; weighing 5g of hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in a proper amount of ethanol, then adding the solution into the montmorillonite suspension, and heating and stirring the mixture for 24 hours; and then centrifugally washing and drying at 80 ℃ for 24h to obtain the CTAB modified montmorillonite nano material which is marked as OMMT.
Step 2, dispersing graphene oxide and OMMT in water respectively, then ultrasonically mixing water dispersions of the graphene oxide and the OMMT uniformly according to the mass ratios of 1:1, 1:3 and 1:5, standing for 20 hours, washing and freeze-drying the obtained precipitate to obtain graphene oxide dispersion-assisted montmorillonite which is marked as GO-OMMT (1:1), GO-OMMT (1:3) and GO-OMMT (1:5) respectively;
fig. 1 is an infrared spectrum of a sample of lamellar Graphene Oxide (GO), montmorillonite (MMT), CTAB-modified montmorillonite nanomaterial (OMMT), and each graphene oxide-loaded montmorillonite in this embodiment. As can be seen from FIG. 1, the main infrared absorption peak of MMT is 3622cm-1And 1026cm-1Corresponding to the hydroxyl group stretching vibration peak and Si-O stretching vibration peak of MMT, respectively. Modified MMT at 3016cm-1At position 1472cm-1A new peak appears, corresponding to-CH respectively3、-N-CH3The absorption peak of (a), indicating successful modification of MMT by CTAB. At 1533cm-1The peak appeared at position is C ═ C vibration peak of GO, 1390cm-1The peak is C-H bending vibration. GO and GO-OMMT with three different ratios at 1797cm-1The infrared peak is obvious, which is the stretching vibration peak of the C ═ O bond on the surface of GO, which shows that the graphene oxide and montmorillonite assembly has the characteristic peak of graphene oxide and montmorillonite at the same time.
Fig. 2(a) - (c) are TEM images of montmorillonite (MMT), CTAB modified montmorillonite nanomaterial (OMMT), and graphene oxide co-dispersed montmorillonite sample (GO-OMMT (1:5)) in this example in this order. From FIG. 2(b) it can be seen that the modified montmorillonite interlamellar spacing is enlarged, indicating that CTAB modification was successful, thereby enlarging the interlamellar spacing. In fig. 2(c), it is observed that a small number of MMT sheets show the characteristics of the two-dimensional nanomaterial, the graphene oxide is in a large sheet corrugated shape, the black part is MMT sheets, and the MMT sheets are laid on the surface of the graphene oxide, indicating that a relatively stable assembly structure is formed between GO and MMT.
Fig. 3 is a raman spectrum of the sample of the Graphene Oxide (GO) sheet and each of the graphene oxide-assisted montmorillonite in this example. As can be seen from the figure: at 1350cm-1And 1590cm-1There are two distinct characteristic peaks, D and G. The carbon material has a wave number of 1000-2000cm-1In the range, the G peak is a carbon atomsp2Characteristic peaks of hybridization, indicating the carbon atom sp2High degree of hybridization, D peak characterizing sp of carbon atom3Hybridization is carried out, and the disorder degree of the carbon material structure is represented. Ratio of D peak to G peak ID/IGFor assessing structural defect degree of the carbon material as a whole, I of GOD/IGThe value was 0.84. I of GO-OMMT (1:1) when GO and OMMT are compoundedD/IGI with a value of 0.81, GO-OMMT (1:3)D/IGI with a value of 0.82, GO-OMMT (1:5)D/IGThe value was 0.83. GO-OMMT (1:5) with I of GOD/IGThe closest value is likely to be that the OMMT sheets are inserted into the GO sheet layer during sonication causing delamination. It can be seen that GO and OMMT assemble successfully.
Example 2 modification of polysulfide rubber by graphene oxide-assisted montmorillonite
In the embodiment, graphene oxide-assisted dispersion montmorillonite modified polysulfide rubber samples with different addition amounts are firstly prepared according to the following steps:
1. 100 parts of polysulfide rubber and 10 parts of curing agent MnO2Adding into a plastic container, stirring for 65s by a stirrer, blending, and standing at room temperature for 24h to obtain the unmodified polysulfide rubber (GO-OMMT content is 0 phr).
2. 100 parts of polysulfide rubber, 0.1 part of GO-OMMT (1:5) and 10 parts of MnO2Adding the mixture into a plastic container, stirring the mixture for 65 seconds by a stirrer, and standing the mixture at room temperature for 24 hours to obtain the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber (GO-OMMT content is 0.1 phr).
3. 100 parts of polysulfide rubber, 0.5 part of GO-OMMT (1:5) and 10 parts of MnO2Adding the mixture into a plastic container, stirring the mixture for 65 seconds by a stirrer, and standing the mixture at room temperature for 24 hours to obtain the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber (GO-OMMT content is 0.5 phr).
4. 100 parts of polysulfide rubber, 1 part of GO-OMMT (1:5) and 10 parts of MnO2Adding the mixture into a plastic container, stirring the mixture for 65 seconds by a stirrer, and standing the mixture at room temperature for 24 hours to obtain the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber (GO-OMMT content is 1 phr).
5. 100 parts of polysulfide rubber, 2 parts of GO-OMMT (1:5) and 10 parts of MnO2Adding the mixture into a plastic container, stirring the mixture for 65 seconds by a stirrer, and standing the mixture at room temperature for 24 hours to obtain the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber (GO-OMMT content is 2 phr).
6. 100 parts of polysulfide rubber, 0.5 part of OMMT and 10 parts of MnO2Adding the mixture into a plastic container, stirring the mixture for 65 seconds by a stirrer, and standing the mixture at room temperature for 24 hours to obtain the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber (the OMMT content is 0.5 phr).
FIG. 4(a) is a graph of tensile properties of each sample prepared in this example. For unfilled polysulfide rubber, the tensile strength is 0.706 MPa. When 0.5phr OMMT was added, the tensile strength of the PSR composite was 0.88MPa, an improvement of 24.6%. When 0.5phr GO-OMMT is added, the tensile strength of the PSR composite material is 0.976MPa, and the tensile strength is improved by 38.2 percent, which is attributed to the uniform dispersion of GO-OMMT and the improved interface interaction between the filler and the PSR, so that the mechanical property of the PSR composite material is improved.
FIG. 4(b) is a graph showing Young's modulus of each sample prepared in this example. The Young's modulus of pure PSR is 1.2MPa, and when 0.5phr OMMT and 0.5phr GO-OMMT are respectively added, the Young's modulus is respectively improved to 2.41MPa and 1.89MPa, and is respectively improved to 57.2 percent and 100.8 percent.
Table 1 is a thermogravimetric plot of the various samples prepared in this example, and it can be seen that: initial degradation temperature (T) of pure PSR5％) 247.93 ℃ was obtained, with a residual content of 5.99%. Addition of OMMT and GO-OMMT promotes T of PSR composite material5％And residual amounts, indicating an improved thermal stability of the PSR composite. Under the same filler content, the thermal stability of the PSR of 0.5phr GO-OMMT added is better than that of 0.5phr OMMT/PSR composite material, which shows that the thermal degradation of the PSR composite material in the air is effectively delayed by the proper amount of GO-OMMT, the oxygen molecule penetration is prevented, and the release of decomposition products is slowed down.
TABLE 1
The results in fig. 4 and table 1 show that compared with pure polysulfide rubber, the mechanical and thermal properties of the graphene oxide-assisted montmorillonite modified polysulfide rubber are significantly improved.
Claims (6)
1. The graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber is characterized in that: the modified polysulfide rubber is prepared by adding modified filler graphene oxide to polysulfide rubber to help disperse montmorillonite, and is used for improving the mechanical and thermal properties of the polysulfide rubber;
the graphene oxide dispersion-assisted montmorillonite is a graphene oxide/montmorillonite assembly formed by combining graphene oxide and montmorillonite nano-materials through electrostatic interaction.
2. The graphene oxide-assisted dispersion montmorillonite modified polysulfide rubber of claim 1, wherein: the montmorillonite nano material is a cetyl trimethyl ammonium bromide modified montmorillonite nano material.
3. The graphene oxide-assisted dispersion montmorillonite modified polysulfide rubber of claim 1 or 2, wherein: the graphene oxide-assisted dispersion montmorillonite is obtained by uniformly mixing graphene oxide and montmorillonite nano materials in the form of water dispersion, washing with water and freeze-drying, wherein the mass ratio of the graphene oxide to the montmorillonite nano materials is 1: 1-5.
4. The graphene oxide-assisted dispersion montmorillonite modified polysulfide rubber of claim 1 or 2, wherein: the addition amount of the graphene oxide dispersion-assisting montmorillonite accounts for 0.1-2% of the mass of the polysulfide rubber.
5. A preparation method of the graphene oxide-assisted dispersion montmorillonite modified polysulfide rubber as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
step 1, firstly, dispersing a proper amount of montmorillonite in deionized water, carrying out ultrasonic treatment for 1-2 hours, and then continuously stirring for 3-5 days to ensure that the montmorillonite is fully dissolved and effectively stripped; then centrifugally separating and drying to obtain peeled montmorillonite;
weighing 10g of peeled montmorillonite, and dispersing the montmorillonite in a proper amount of deionized water to obtain montmorillonite suspension; weighing 5g of hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in a proper amount of ethanol, then adding the solution into the montmorillonite suspension, and heating and stirring the mixture for 24 hours; then centrifugally washing and drying to obtain modified montmorillonite which is marked as OMMT;
step 2, respectively dispersing graphene oxide and OMMT in deionized water, then ultrasonically mixing water dispersions of the graphene oxide and the OMMT according to the mass ratio of 1: 1-5, standing for 15-24 h, washing and freeze-drying the obtained precipitate to obtain graphene oxide-assisted dispersion montmorillonite, which is marked as GO-OMMT;
step 3, mixing polysulfide rubber with GO-OMMT and curing agent MnO2And (3) placing the mixture into a plastic container, stirring and mixing the mixture uniformly by a stirrer, and placing the mixture at room temperature for 24 hours to obtain the graphene oxide dispersion-assisted montmorillonite modified polysulfide rubber.
6. The preparation method of the graphene oxide-assisted dispersion montmorillonite modified polysulfide rubber according to claim 5, wherein in step 3, the raw materials comprise, by weight: 100 parts of polysulfide rubber, 0.1-2 parts of GO-OMMT and MnO210 parts.
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