CN117624809A - Heat-conducting high-temperature-resistant deformation-resistant fluororubber and preparation method thereof - Google Patents
Heat-conducting high-temperature-resistant deformation-resistant fluororubber and preparation method thereof Download PDFInfo
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000011258 core-shell material Substances 0.000 claims abstract description 27
- 239000002077 nanosphere Substances 0.000 claims abstract description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000006082 mold release agent Substances 0.000 claims abstract description 9
- 239000006096 absorbing agent Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- 229920001971 elastomer Polymers 0.000 claims description 29
- 239000005060 rubber Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000004073 vulcanization Methods 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 18
- 238000007906 compression Methods 0.000 abstract description 18
- 239000000945 filler Substances 0.000 abstract description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
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- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- 125000003821 2-(trimethylsilyl)ethoxymethyl group Chemical group [H]C([H])([H])[Si](C([H])([H])[H])(C([H])([H])[H])C([H])([H])C(OC([H])([H])[*])([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000899639 Reinhardtia Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- NRCSJPUCBTUPDG-UHFFFAOYSA-N benzyl-chloro-triphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(Cl)(C=1C=CC=CC=1)CC1=CC=CC=C1 NRCSJPUCBTUPDG-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 238000007542 hardness measurement Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a heat-conducting high-temperature-resistant deformation-resistant fluororubber and a preparation method thereof, wherein the fluororubber composite material comprises ternary fluororubber, triallyl isocyanurate (TAIC), a vulcanizing agent, a dispersing agent, an internal mold release agent, an acid absorber, a nano auxiliary agent and SiO 2 @TiO 2 A core-shell structure nanosphere; the fluororubber prepared in the preferred embodiment of the invention has the temperature resistance of 422 ℃ and the heat conductivity coefficient, the tensile strength, the electrical conductivity and the compression set percentage0.2209W/(m.K), 14.47MPa, 7.02E-13S/cm, 22.07%, 29.8%, 143.6%, 2600% and 40% respectively higher than the fluororubber without filler.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to heat-conducting high-temperature-resistant deformation-resistant fluororubber and a preparation method thereof.
Background
Fluororubber is a synthetic polymer elastomer containing fluorine atoms on carbon atoms of a main chain or a side chain, has excellent oxidation resistance, oil resistance, corrosion resistance and atmospheric aging resistance, and is widely applied to the fields of automobiles, machinery, aviation, aerospace, chemical industry and the like at present. However, the rubber has poor high-temperature wear resistance and large compression set, so that the rubber with high-temperature resistance, good heat conduction performance and compression set resistance needs to be invented. The invention can obviously improve the characteristics of high temperature resistance, heat conduction, deformation resistance and the like of the fluororubber, well improve the performance short plate, enhance the use quality of the fluororubber and ensure that the fluororubber has good popularization value.
Patent CN101875750A discloses a fluororubber compound with low compression set and a preparation method thereof, binary fluororubber, ternary fluororubber, active magnesium oxide, superfine calcium hydroxide, benzyl triphenyl phosphorus chloride, a reinforcing agent, an inorganic filler, a release agent, a vulcanizing agent and a plasticizer are mixed and added into an open mill for mixing, and the roller temperature is controlled at 45-50 ℃ and the roller spacing is 0.5-2 mm. After 230 ℃ for 24 hours of vulcanization, fluororubber compound is prepared. The prepared fluororubber has excellent compression set, but the preparation process is too complex during rubber mixing, and the mixing cost of the two rubbers is high, so that the fluororubber is not suitable for general application.
Patent CN102229748A discloses an organized rectorite modified silicone fluororubber sealing member and a preparation method thereof, and the special rubber sealing member has excellent low-temperature mechanical properties, excellent compression set resistance, high mechanical strength, oil resistance, environmental corrosion resistance and no skinning. However, the rubber is difficult to prepare, the process is quite complex, and meanwhile, the cost of synthesizing the rubber by adopting the silicone-fluorine rubber is too high, so that the rubber is not easy to produce.
Patent CN108017746a discloses a peroxide-vulcanized fluororubber with low compression set and a preparation method thereof, wherein the peroxide-vulcanized fluororubber is prepared by an intermittent emulsion method, a fluorine-containing composite emulsifier is selected, a bromine-containing vulcanization point monomer is selected, an iodine-containing chain transfer agent is selected, the adding time of the transfer agent is controlled, the compression set of the fluororubber is reduced, and the tensile strength of the fluororubber is enhanced. However, the preparation method is too complicated, and is difficult to process, and mass production is impossible.
Patent CN106496397a discloses an extremely low temperature resistant fluoroelastomer and a composition thereof, wherein the surface of a filler is modified to increase the compatibility with the extremely low temperature resistant fluoroelastomer so as to increase the crosslinking density, and the obtained rubber has the characteristics of low temperature resistance and low compression set, but the tensile strength is not improved well.
Patent CN1079336422a discloses a fluororubber composition with heat conduction and wear resistance, fluororubber and polyurethane raw rubber are plasticated in an internal mixer for 3 minutes, other fillers are added, banburying is carried out at 80-120 ℃, then thin passing is carried out in an open mill, sheet discharging is carried out, standing is carried out for 24 hours, and the composite composition is prepared by vulcanizing.
Patent CN110818825a discloses a peroxide-curable fluoroelastomer and a preparation method thereof, the fluoroelastomer has excellent flowability, and can be processed by extrusion and injection molding processes, and the vulcanized product has high strength, low compression set, excellent heat-resistant air aging and other properties. But the processing process is very complex and the economic benefit is not high.
In summary, although the prior art has improved part of the properties of the fluororubber composite material, the prior art cannot integrate heat conduction, high temperature resistance, low compression deformation and excellent mechanical properties. Fluororubber is mainly applied to the military industry such as sealing and has extremely high requirements. Accordingly, the applicant desires to develop a high performance fluororubber nanocomposite material that is thermally conductive, resistant to high temperatures, has low compression set, and is excellent in mechanical properties.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provide heat-conducting high-temperature-resistant deformation-resistant fluororubber and a preparation method thereof, and the technical scheme adopted by the invention is as follows:
in the first aspect, the fluororubber with heat conduction, high temperature resistance and deformation resistance is provided, and is prepared from the following raw materials in parts by weight:
90-100 parts by mass of ternary fluororubber;
1-3 parts by mass of triallyl isocyanurate;
1-2 parts of vulcanizing agent;
1-2 parts of dispersing agent;
1-2 parts by mass of an internal mold release agent;
1-3 parts of acid absorbent;
5-10 parts by mass of nano auxiliary agent;
SiO 2 @TiO 2 10-30 parts of core-shell structure nanospheres.
In a second aspect, a method for preparing the heat-conducting, high-temperature-resistant and deformation-resistant fluororubber is provided, wherein the SiO 2 @TiO 2 The preparation method of the core-shell structure nanosphere comprises the following steps:
adding the phosphoric acid solution into the sodium silicate solution, uniformly stirring, and adjusting the pH value of the solution to be 1-2; adding titanium dioxide into the mixed solution, stirring, adding sodium hydroxide solution to adjust pH to neutral, standing to solidify the solutionGel-like and freeze-dried to obtain titanium dioxide powder with core-shell structure, namely SiO 2 @TiO 2 Core-shell structured nanospheres.
Further, the preparation method of the heat-conducting high-temperature-resistant deformation-resistant fluororubber comprises the following steps of:
s1, weighing ternary fluororubber, triallyl isocyanurate, a vulcanizing agent, a dispersing agent, an internal mold release agent, an acid absorber, a nano auxiliary agent and SiO according to the formula dosage 2 @TiO 2 The nanospheres with the core-shell structure are subjected to open mill in an open mill at the temperature of 40-50 ℃ and uniformly mixed to prepare a mixed rubber;
s2, vulcanizing the mixed rubber prepared in the step S1 in a vulcanizing machine for one stage, wherein the vulcanizing temperature is 150-200 ℃;
s3, putting the product prepared in the step S2 into a baking oven for secondary vulcanization, wherein the vulcanization temperature is 200-250 ℃.
Specifically, in S1, the mixing conditions include: the temperature is 40-50 ℃, and the rotating speed of the open mill is 20-30rpm; in S2, the one-stage vulcanization is carried out for 5-15 min at 150-200 ℃; in S3, the condition of the two-stage vulcanization is 200-250 ℃, and the two-stage vulcanization is carried out for 8-24 hours.
The beneficial effects of the invention are as follows:
1. the thermal conductivity, tensile strength, electrical conductivity and compression set of the preferable fluororubber material prepared by the invention are 0.2209W/(m.K), 14.47MPa, 7.02E-13S/cm and 22.08%, respectively, which are increased by 29.8%, 143.6%, 2600% and 40% compared with fluororubber without filler;
2. the temperature resistance of the fluororubber material prepared by the invention can reach 422 ℃.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
Tensile strength test chart for the composite of fig. 1;
the thermal conductivity test chart of the composite of fig. 2;
FIG. 3 is a graph of hardness testing of the composite material;
FIG. 4 is a conductivity test chart for the composite;
FIG. 5 is a graph of compression set test of the composite material;
thermal Gravimetric (TG) test patterns for the composites of fig. 6;
FIG. 7 is a thermogravimetric analysis (DTG) test plot of the composite;
FIG. 8 is a Scanning Electron Microscope (SEM) test chart of the composite material;
fig. 9 is a fourier infrared (FTIR) spectrum test chart of the composite.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings; the following examples are preferred embodiments of the present application by comparing test examples with control examples and performing experimental tests.
The present invention will be described in detail with reference to the following examples, and the materials described in the following specific examples are only for the purpose of explaining the present invention, but the materials claimed in the present invention are not limited to the types of materials described below.
The materials used are as follows: ternary fluororubber with 67% fluorine content and Solvay Sorpe. The accelerator was triallyl isocyanurate (TAIC), a company of the chemical of reinhardtia (peninsula). The vulcanizing agent is supplied by Bispenta, arlema. The dispersing agent is one of saturated fatty acid and polymethyl methacrylate, and is available from Jingzhou bioengineering Co. The internal mold release agent is one of HT290 and WS280, and is Srtuktol in Germany. The acid absorbing agent is one of zinc oxide and magnesium oxide, and is used in Hengfeng chemical industry. The nanometer auxiliary agent is calcium carbonate, huzhou gold source chemical industry Co. The different modified titanium dioxide is nano titanium dioxide, rutile type nano titanium dioxide, hydrophilic rutile type nano titanium dioxide, hydrophobic rutile type nano titanium dioxide, oleophilic rutile type nano titanium dioxide, suzhou excellent zirconium nano material Co., ltd., siO 2 @TiO 2 And (3) modifying and self-synthesizing the nanospheres with the core-shell structures.
SiO 2 @TiO 2 The synthesis method of the core-shell structure nanosphere is as follows:
firstly, preparing a sodium silicate solution with a certain concentration, and uniformly stirring for 30 minutes. Then adding phosphoric acid solution with a certain concentration, and adjusting the pH value of the solution to be 1-2.
Then, a certain amount of titanium dioxide was added to the above mixed solution, and thoroughly stirred for 1 hour. Then adding sodium hydroxide solution with a certain concentration, and adjusting the pH value to 7. After standing for 24 hours, the solution was coagulated into a gel shape and lyophilized in a lyophilizer for 48 hours.
Finally, the titanium dioxide powder with a core-shell structure is obtained and marked as SiO 2 @TiO 2 Core-shell structured nanospheres.
The preparation of the heat-conducting high-temperature-resistant deformation-resistant fluororubber nanocomposite is carried out below, and the steps are as follows:
s1, weighing fluororubber, an accelerator, a vulcanizing agent, a dispersing agent, an internal mold release agent, an acid absorber, a nano auxiliary agent, different modified titanium dioxide or SiO according to the formula dosage 2 @TiO 2 Core-shell structured nanospheres.
S2, mixing the rubber weighed in S1 with an accelerator, a vulcanizing agent, a dispersing agent, an internal mold release agent, an acid absorber, a nano auxiliary agent, different modified titanium dioxide or SiO 2 @TiO 2 The core-shell structure nanospheres are subjected to open mill in an open mill at 40-50 ℃, preferably 45 ℃ and uniformly mixed to prepare the rubber compound.
S3, vulcanizing the mixed rubber prepared in the step S2 in a vulcanizing machine, wherein the vulcanization temperature is 150-200 ℃, and preferably 170 ℃.
S4, placing the rubber sheet prepared in the step S3 into a baking oven for secondary vulcanization, wherein the vulcanization temperature is 200-250 ℃, and preferably 200 ℃.
S5, performing performance test on the prepared nanocomposite, wherein: the tensile strength was tested according to the method in GB/T528-2009, the vulcanized rubber sheet was cut into a dumbbell shape, and then the cut rubber sheet was placed on a universal tester for stretching. The Shore hardness is tested according to the method in GB/T6031-2017, the vulcanized rubber ring is placed on a Shore hardness meter to measure hardness, five readings are read, and an average value is obtained; the thermal conductivity was tested according to the method in GB/T11205-2009, the vulcanized rubber sheet was cut to 40mm and placed in a thermal conductivity meter for measurement. Compression set was tested according to the method in ASTM D395, under the following conditions: 200 ℃ for 70h. Volume resistivity was tested according to the method in ASTM D2739.
Example 1
100 parts of fluororubber, 3 parts of TAIC, 2 parts of vulcanizing agent, 2 parts of dispersing agent, 1 part of internal mold release agent, 3 parts of acid absorber and 5 parts of nano auxiliary agent are added into an open mill. The feeding sequence is as follows: mixing fluororubber for 3min, uniformly mixing a dispersing agent and an internal release agent, adding the mixture for 3-4 times, uniformly mixing an acid absorbing agent and a nano auxiliary agent, adding the mixture for 8-10 times, finally adding TAIC and a vulcanizing agent, mixing for 5min after adding, and uniformly mixing the composite material. And taking out the mixed rubber after the open mill is finished, placing for 24 hours, then recycling, vulcanizing on a flat vulcanizing machine, preparing samples, and testing the rubber performance, wherein the prepared composite material is marked as M1.
Examples 2 to 7
In examples 2 to 7, the present invention adopts a similar method, and the preparation process is the same as that of example 1, except that the modified titanium dioxide is different in kind. As shown in table 1: respectively adopting 10 parts of nano titanium dioxide, 10 parts of rutile type nano titanium dioxide, 10 parts of hydrophilic rutile type nano titanium dioxide, 10 parts of hydrophobic rutile type nano titanium dioxide, 10 parts of oleophilic rutile type nano titanium dioxide and SiO 2 @TiO 2 10 parts of core-shell structure nanospheres are prepared into composite materials named M2, M3, M4, M5, M6 and M7 respectively.
As can be seen from Table 2, when SiO is used 2 @TiO 2 When the nanospheres with the core-shell structure are used, the heat conductivity, the compression set, the tensile strength, the hardness and the electric conductivity of the composite material are optimal.
As can be seen from FIG. 1, in the composite material, the tensile strengths of M1, M2, M3, M4, M5, M6 and M7 were 5.94MPa, 8.9MPa, 11.95MPa, 13.18MPa, 13.12MPa, 13.56MPa and 14.47MPa, respectively. Compared with M7, the tensile strength of M7 is improved by 143.6%, and the addition of titanium dioxide can improve the tensile strength of the composite material, so that the titanium dioxide and fluororubber are well crosslinked. The 7 groups of data are analyzed, and the tensile strength of the composite material is improved by the modified titanium dioxide, probably because the titanium dioxide is fully crosslinked in the rubber matrix, so that the crosslinking density of the composite material is greatly improved. It follows that the composite material is formed by adding SiO 2 @TiO 2 When the nanospheres with the core-shell structure are used, the nanospheres can show good tensile properties.
As can be seen from FIG. 2, in the composite materials, the thermal conductivities of M1, M2, M3, M4, M5, M6 and M7 are 0.1702W/(mK), 0.1874W/(mK), 0.1882W/(mK), 0.2122W/(mK), 0.1785W/(mK), 0.1750W/(mK) and 0.2209W/(mK), respectively. Compared with M1, the heat conductivity of M7 is improved by 29.8%, and the heat conductivity is good. Due to addition of SiO 2 @TiO 2 The core-shell structure nanospheres enable the composite material to open a good heat conduction channel, so that the heat conduction coefficient in M7 is improved.
As can be seen from fig. 3, M1, M2, M3, M4, M5, M6 and M7 have hardness of 50.2 HA, 55.4 HA, 56.7 HA, 54.8 HA, 54.2 HA, 53.6 HA and 58.1 HA, respectively, in the composite material. It can be seen that the hardness of the composite material is increased by adding different modified titanium dioxide, but the titanium dioxide can not obviously improve the hardness of the fluororubber, and other inorganic fillers are needed for crosslinking, so that the hardness of the fluororubber is well improved, but the addition of SiO can be seen 2 @TiO 2 When the nanospheres are of core-shell structure, the hardness is best.
As can be seen from FIG. 4, in the composite material, the conductivities of M1, M2, M3, M4, M5, M6 and M7 were 2.60E-14S/cm, 3.88E-14S/cm, respectively,3.73E-14S/cm, 1.45E-14S/cm, 2.71E-14S/cm, 3.95E-14S/cm and 7.02E-13S/cm. It follows that the electrical conductivity of the composite material changes as the addition of different modified titanium dioxide increases. The reason is that the modified titanium dioxide is uniformly dispersed in the rubber, so that the conductivity of the composite material is increased, while the SiO 2 @TiO 2 The core-shell structure nanospheres are added, so that the crosslinking density of the composite material is greatly improved, the mutual transfer speed between electrons is increased, the conductivity is greatly increased, and the conductivity is optimal.
As can be seen from fig. 5, the compression deformation rates of M1, M2, M3, M4, M5, M6 and M7 in the composite material were 36.8%, 23.7%, 29.8%, 21.31%, 35.59%, 29.06% and 22.07%, respectively. It can be seen that the compression set of fluororubber can be reduced by adding different modified titanium dioxide, and hydrophilic rutile type nano titanium dioxide and SiO are added 2 @TiO 2 When the nanospheres with the core-shell structure are used, the nanospheres have good deformation resistance.
FIG. 6 is a thermal weight (TG) curve of this fluororubber composite, and Table 3 shows the weight loss ratio and the corresponding temperature of the modified fluororubber. It can be seen that the initial decomposition temperature was varied to varying degrees by adding different modified titanium dioxide, but at 5%, 10% and 50% weight loss, the temperature of M7 was the highest, indicating that the temperature resistance of M7 was optimal. Meanwhile, as can be seen from fig. 7, the first peak is rapidly reduced, the second peak gradually moves forward along with the increase of the content of titanium dioxide, and the heat conduction performance of the rubber is excellent, so that the heat can be well absorbed, the heat is gathered, the loss of weight is slightly rapidly reduced, the thermal stability is excellent, and the initial degradation temperature is greatly improved.
As can be seen from fig. 8, the fracture surface SEMs corresponding to M1, M2, M3, M4, M5, M6 and M7 are (a), (b), (c), (d), (e), (f) and (g), respectively. The tensile fracture surface of M1 is relatively flatThroughout, but with increasing amounts of differently modified titanium dioxide, the fracture surface of the rubber became progressively coarser, and a pronounced fold-like structure was clearly seen in M7, due to SiO 2 @TiO 2 The core-shell structure nanospheres play a certain role in transferring stress in the process of stretching the composite material, so that the tensile force between the rubbers is enhanced, the crosslinking degree between the rubbers is improved to a certain extent, and the physical and mechanical properties of the rubbers are enhanced, so that SiO is added into the composite material 2 @TiO 2 The composite material of the nanospheres with the core-shell structure has the highest tensile strength, so that the SiO is added 2 @TiO 2 When the nanospheres with the core-shell structure are used for modifying titanium dioxide, the titanium dioxide has better physical and mechanical properties.
As can be seen from fig. 9, 1150 and 1150 cm -1 The peak with extremely strong position is the characteristic absorption peak of C-F, 1428 and 1428 cm -1 Is C-H in-plane bending vibration of olefin, 1396 cm -1 The peak at is CH 2 =CF 2 Is characterized by an absorption peak of 1694 cm -1 The peak at this point is the characteristic absorption peak of the amide. With the addition of different modified titanium dioxide, the baseline is tilted to different extents. The characteristic absorption peaks of the composite materials are basically consistent after different modified titanium dioxide is added, which shows that the chemical bonds are basically the same, new functional groups are not appeared, chemical reactions possibly occur, but the newly formed chemical bonds are the same as the types of the previous chemical bonds.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. The fluororubber with heat conduction, high temperature resistance and deformation resistance is characterized in that: the composite material is prepared from the following raw materials in parts by weight:
90-100 parts by mass of ternary fluororubber;
1-3 parts by mass of triallyl isocyanurate;
1-2 parts of vulcanizing agent;
1-2 parts of dispersing agent;
1-2 parts by mass of an internal mold release agent;
1-3 parts of acid absorbent;
5-10 parts by mass of nano auxiliary agent;
SiO 2 @TiO 2 10-30 parts of core-shell structure nanospheres.
2. The method for preparing a heat-conducting, high-temperature-resistant and deformation-resistant fluororubber according to claim 1, wherein the SiO 2 @TiO 2 The preparation method of the core-shell structure nanosphere comprises the following steps:
adding the phosphoric acid solution into the sodium silicate solution, uniformly stirring, and adjusting the pH value of the solution to be 1-2; adding titanium dioxide into the mixed solution, stirring, adding sodium hydroxide solution to adjust pH to neutrality, standing to solidify the solution into gel, and lyophilizing to obtain titanium dioxide powder with core-shell structure, namely SiO 2 @TiO 2 Core-shell structured nanospheres.
3. The method for preparing the heat-conducting, high-temperature-resistant and deformation-resistant fluororubber according to claim 2, comprising the following steps:
s1, weighing ternary fluororubber, triallyl isocyanurate, a vulcanizing agent, a dispersing agent, an internal mold release agent, an acid absorber, a nano auxiliary agent and SiO according to the formula dosage 2 @TiO 2 The nanospheres with the core-shell structure are subjected to open mill in an open mill at the temperature of 40-50 ℃ and uniformly mixed to prepare a mixed rubber;
s2, vulcanizing the mixed rubber prepared in the step S1 in a vulcanizing machine for one stage, wherein the vulcanizing temperature is 150-200 ℃;
s3, putting the product prepared in the step S2 into a baking oven for secondary vulcanization, wherein the vulcanization temperature is 200-250 ℃.
4. A method for preparing a heat-conducting, high-temperature-resistant and deformation-resistant fluororubber according to claim 3, characterized in that: in S1, the mixing conditions include: the temperature is 40-50 ℃, and the revolving speed of the open mill is 20-30rpm.
5. A method for preparing a heat-conducting, high-temperature-resistant and deformation-resistant fluororubber according to claim 3, characterized in that: in S2, the one-stage vulcanization is carried out for 5-15 min at 150-200 ℃.
6. A method for preparing a heat-conducting, high-temperature-resistant and deformation-resistant fluororubber according to claim 3, characterized in that: in S3, the condition of the two-stage vulcanization is 200-250 ℃, and the two-stage vulcanization is carried out for 8-24 hours.
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