CN115746416B - Composite film loaded silicon dioxide reinforced natural rubber roller material and preparation method thereof - Google Patents
Composite film loaded silicon dioxide reinforced natural rubber roller material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 118
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 36
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 36
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 71
- 239000012528 membrane Substances 0.000 claims abstract description 63
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 229920001971 elastomer Polymers 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 15
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008117 stearic acid Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000007865 diluting Methods 0.000 claims abstract description 13
- 235000019253 formic acid Nutrition 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000004073 vulcanization Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 81
- 238000010041 electrostatic spinning Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 27
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 18
- WCKIDCVWRJUPFY-UHFFFAOYSA-L zinc;oxalate;dihydrate Chemical compound O.O.[Zn+2].[O-]C(=O)C([O-])=O WCKIDCVWRJUPFY-UHFFFAOYSA-L 0.000 claims description 18
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000001523 electrospinning Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920006173 natural rubber latex Polymers 0.000 claims 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
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- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a composite film loaded silica reinforced natural rubber roller material and a preparation method thereof. The method comprises the following steps: taking SiO 2 particles loaded on a composite film, and adding water into the composite film to mechanically stir the composite film to obtain a dispersion; diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid; adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch; mixing the masterbatch with stearic acid, an anti-aging agent, a vulcanizing agent and a vulcanization aid, and mixing on an open mill to obtain a rubber compound; vulcanizing in a plate vulcanizing machine at the vulcanizing temperature to obtain the product. According to the invention, siO 2 is loaded on the composite film, so that the problem that the rubber performance is affected due to the fact that the surface of SiO 2 contains a large number of polar groups and particles are easy to agglomerate is solved. Meanwhile, carbon-carbon double bonds are generated in the calcining process of the composite membrane, and more reactive sites are provided for the crosslinking reaction during vulcanization, so that the mechanical properties of the composite natural rubber are improved.
Description
Technical Field
The invention relates to the technical field of functional rubber materials, in particular to a composite film loaded silica reinforced natural rubber roller material and a preparation method thereof.
Background
Rubber rollers are roller-shaped products which are manufactured by taking metal or other materials as cores and vulcanizing rubber covered on the cores, and are widely applied to various industries at present. The rubber covered on the rubber roller directly determines the performance of the rubber roller, and with the rapid development of the modern industry, the requirement on the rubber roller material is also higher and higher, wherein the rubber roller with good mechanical strength is one of research objects. The natural rubber is used as a renewable biological resource, has excellent performance and is widely applied. However, natural rubber has the defects of low mechanical properties, easy aging and the like, and SiO 2 is commonly used as a reinforcing agent to be added into the natural rubber by researchers to improve the mechanical properties. However, siO 2 contains a large amount of polar groups on the surface, and the particles are easy to agglomerate, so that the reinforcing effect on the rubber performance is affected. On the other hand, nanocarbon is also used as a reinforcing filler in general use, but there is also a problem of difficulty in dispersion. The ceramic fiber has large specific surface area and high surface activity, can also have the effect of enhancing mechanical properties, and has certain flame retardance, thus playing an important role in the application of the rubber roller. How to perfectly combine the three is a problem to be solved.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the technical problems, the invention aims to provide a composite film loaded silica reinforced natural rubber roller material and a preparation method thereof, and SiO 2 is loaded on a composite film, so that the problem that the surface of SiO 2 contains a large number of polar groups and particles are easy to agglomerate, thereby influencing the rubber performance is solved. Meanwhile, in the calcining process of the composite film, the carbon fiber part is converted from an amorphous carbon structure into a local graphitized structure, meanwhile, the surface of the carbon fiber contains rich oxygen-containing groups, carbon-carbon double bonds are also present besides carbon hydrogen bonds and alkyl groups after calcining, and the double bonds and oxygen-containing functional groups provide more reactive points for crosslinking reaction during vulcanization, so that SiO 2 particles loaded on the composite film are combined with a natural rubber interface more tightly, and the mechanical property of the composite natural rubber is improved.
The technical scheme is as follows: the composite film-loaded silica reinforced natural rubber roller material comprises the following components: the composite membrane loaded SiO 2 particles are used as a filler, natural rubber is used as a base material, sulfur is used as a vulcanizing agent, and zinc methacrylate is used as a vulcanization aid;
The composite membrane is a composite membrane of ceramic fibers and carbon nanofibers;
the size of SiO 2 particles loaded on the composite film is 0.1-0.2 mu m.
Preferably, stearic acid and an anti-aging agent are also included.
Preferably, the preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
s2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 13-15%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
S3: adopting a double spinneret electrospinning device to carry out electrostatic spinning;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting for 40min at 600 ℃, and crushing to obtain composite membrane loaded SiO 2 particles.
Preferably, the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is (5-8): 100.
Preferably, the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1 (2-3).
Preferably, the electrostatic spinning condition in S3 is: the distance between the two spinnerets is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm.
Preferably, the porosity of the composite membrane is 25-33%.
The preparation method of the composite film supported silica reinforced natural rubber roller material comprises the following steps:
step 1: taking SiO 2 particles loaded on a composite film, and adding water into the composite film to mechanically stir the composite film to obtain a dispersion;
step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 10-15min on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Preferably, the ratio of the solids content of the dispersion to the solids content of the natural latex is (20-30): 100.
The beneficial effects are that:
1. According to the invention, siO 2 is loaded on the composite film, so that the problem that the rubber performance is affected due to the fact that the surface of SiO 2 contains a large number of polar groups and particles are easy to agglomerate is solved.
2. In the invention, in the calcining process, the carbon fiber part is converted from an amorphous carbon structure into a local graphitized structure, meanwhile, the surface of the carbon fiber contains rich oxygen-containing groups, carbon-carbon double bonds are also present besides carbon hydrogen bonds and alkyl groups after calcining, and the double bonds and oxygen-containing functional groups provide more reactive points for crosslinking reaction during vulcanization, so that SiO 2 particles loaded on the composite film are combined with a natural rubber interface more tightly, thereby being beneficial to improving the mechanical property of the composite natural rubber.
3. Compared with the natural ceramic raw material, the composite membrane adopted by the invention has high controllability, large specific surface area and high surface activity, is more beneficial to the increase of the mechanical properties of the natural rubber, and has a certain flame retardant effect.
4. The composite film loaded silica reinforced natural rubber roller material has good mechanical strength and a certain flame retardant effect, and is suitable for preparing rubber rollers.
Detailed Description
The invention provides a composite film supported silica reinforced natural rubber roller material and a preparation method thereof, and the invention is further described in detail by the following matching examples in order to make the purposes, the technical scheme and the effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
S2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 13%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 7:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 32.8%.
Example 2
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
s2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 14%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 7:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 30.1%.
Example 3
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
s2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 15%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 7:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 26.4%.
Example 4
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
S2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 14%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 5:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 29.8%.
Example 5
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
S2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 14%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 6:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 30.0%.
Example 6
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
S2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 14%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 8:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 1:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 30.3%.
Example 7
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps in parts by weight:
S1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, and then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and the uniform electrostatic spinning solution A is obtained after stirring for 2 hours;
S2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 14%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, wherein the mass ratio of the zinc oxalate dihydrate to the polyacrylonitrile is 7:100, and the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 2:3, and stirring for 4 hours to obtain uniform electrostatic spinning solution B;
s3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is about 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0mL/h, and the receiving distance is 15cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into tetraethoxysilane, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring for 8 hours to prepare SiO 2 sol, and immersing the composite membrane in the SiO 2 sol for 2 hours;
S7: taking out, placing in a muffle furnace, roasting at 600 ℃ for 40min, crushing, and obtaining composite membrane loaded SiO 2 particles with the size of 0.1-0.2 mu m.
The porosity of the composite membrane was 27.6%.
Example 8
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 2, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 20:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 10 minutes on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 9
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 2, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
Step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 11 minutes on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 10
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 2, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 30:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
Step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 11 minutes on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 11
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 1, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 12 minutes on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 12
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking SiO 2 particles loaded on the composite membrane prepared in the embodiment 3, adding water, and mechanically stirring to obtain a dispersion liquid;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 12 minutes on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 13
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 4, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
Step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 13min on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 14
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 5, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
Step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 13min on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 15
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking composite membrane loaded SiO 2 particles prepared in example 6, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
Step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 14 minutes on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Example 16
The preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking SiO 2 particles loaded on the composite membrane prepared in the example 7, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 15min on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Comparative example 1
The comparative example differs from example 2 in that a composite film obtained without carrying SiO 2 particles and individual SiO 2 particles were used in exactly the same amounts as in example 2, in particular:
the preparation method of the composite film loaded silica reinforced natural rubber roller material comprises the following steps:
Step 1: taking the composite membrane particles without SiO 2 and SiO 2 prepared in example 2, adding water, and mechanically stirring to obtain a dispersion;
Step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid, wherein the ratio of the solid content of the dispersion liquid to the solid content of the natural latex is 25:100;
step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing for 10-15min on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
Mechanical properties of the example of the invention were tested with a universal tensile tester.
Table 1 mechanical properties of the examples
Claims (6)
1. The composite film-loaded silica reinforced natural rubber roller material is characterized by comprising the following components: the composite membrane loaded SiO 2 particles are used as a filler, natural rubber is used as a base material, sulfur is used as a vulcanizing agent, and zinc methacrylate is used as a vulcanization aid;
The composite membrane is a composite membrane of ceramic fibers and carbon nanofibers;
the size of SiO 2 particles loaded on the composite film is 0.1-0.2 mu m;
the porosity of the composite film is 25-33%;
The preparation method of the composite membrane loaded SiO 2 particles comprises the following steps of:
s1: 1.3 parts of aluminum nitrate nonahydrate and 0.5 part of magnesium nitrate hexahydrate are taken and dissolved in 20 parts of absolute ethyl alcohol, then 1.3 parts of polyvinylpyrrolidone and 3 parts of dimethylformamide are added, and uniform electrostatic spinning solution A is obtained after stirring 2 h;
S2: stirring and dissolving polyacrylonitrile in dimethylformamide to obtain a solution with the mass fraction of 13-15%, adding zinc oxalate dihydrate and polyvinylpyrrolidone, and stirring for 4 h to obtain uniform electrostatic spinning solution B;
S3: adopting a double spinneret electrospinning device to carry out electrostatic spinning, wherein the electrostatic spinning conditions are as follows: the distance between the two spinning nozzles is 15cm, the spinning voltage is 15kV, the spinning flow rate is 1.0 mL/h, and the receiving distance is 15 cm;
s4: drying the composite film at 80 ℃ for 24 hours;
s5: calcining, and heating to 290 ℃ for 1h, wherein the heating rate is 3 ℃/min; vacuumizing, heating to 900 ℃ and maintaining for 30min, wherein the heating rate is 6 ℃/min, and then cooling at the cooling rate of 3 ℃/min to obtain a composite membrane;
S6: slowly dripping absolute ethyl alcohol and distilled water into ethyl orthosilicate, continuously magnetically stirring, adjusting the pH value of the solution to 2-4, continuously stirring 8h to prepare SiO 2 sol, and immersing the composite membrane in the solution for 2h;
S7: taking out, placing in a muffle furnace, roasting for 40min at 600 ℃, and crushing to obtain composite membrane loaded SiO 2 particles.
2. The composite film-supported silica reinforced natural rubber roll material of claim 1 further comprising stearic acid and an anti-aging agent.
3. The composite film-supported silica reinforced natural rubber roll material according to claim 1, wherein the mass ratio of zinc oxalate dihydrate to polyacrylonitrile is (5-8): 100.
4. The composite film-supported silica reinforced natural rubber roller material according to claim 1, wherein the mass ratio of polyvinylpyrrolidone to dimethylformamide is 1 (2-3).
5. The method for preparing the composite membrane supported silica reinforced natural rubber roller material according to claim 2, which is characterized by comprising the following steps:
step 1: taking SiO 2 particles loaded on a composite film, and adding water into the composite film to mechanically stir the composite film to obtain a dispersion;
step 2: diluting the concentrated natural latex with water to a concentration of 10wt%, adding the dispersion liquid, and mechanically stirring and mixing to obtain a mixed liquid; step 3: adding formic acid solution for precipitation, washing the acid on the surface of the precipitation with deionized water, and drying to obtain master batch;
Step 4: mixing 100 parts of master batch with 2 parts of stearic acid, 0.5 part of anti-aging agent, 3 parts of vulcanizing agent and 0.8 part of auxiliary vulcanizing agent, and mixing 10-15min parts of the master batch on an open mill to obtain a mixed batch;
step 5: and (3) placing the rubber compound for 24 hours, and vulcanizing in a flat vulcanizing machine at a vulcanizing temperature to obtain the rubber compound.
6. The method for producing a composite film-supported silica-reinforced natural rubber roll material as claimed in claim 5, wherein the ratio of the solid content of the dispersion to the solid content of the natural rubber latex is (20-30): 100.
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