CN117509614B - Preparation method of carbon material for rubber engineering equipment - Google Patents
Preparation method of carbon material for rubber engineering equipment Download PDFInfo
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- CN117509614B CN117509614B CN202410008788.4A CN202410008788A CN117509614B CN 117509614 B CN117509614 B CN 117509614B CN 202410008788 A CN202410008788 A CN 202410008788A CN 117509614 B CN117509614 B CN 117509614B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 49
- 229920001971 elastomer Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 104
- -1 tetrafluoroborate phosphine Chemical compound 0.000 claims abstract description 36
- 238000010000 carbonizing Methods 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 35
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 33
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 33
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004108 freeze drying Methods 0.000 claims abstract description 18
- 229920002678 cellulose Polymers 0.000 claims abstract description 12
- 239000001913 cellulose Substances 0.000 claims abstract description 12
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008213 purified water Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 230000001681 protective effect Effects 0.000 claims description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 239000003738 black carbon Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229920002284 Cellulose triacetate Polymers 0.000 abstract description 7
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 31
- 238000009826 distribution Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 16
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 15
- 239000000945 filler Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000005696 Diammonium phosphate Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- CJGAKQLHXBFASW-UHFFFAOYSA-N P.OBO Chemical compound P.OBO CJGAKQLHXBFASW-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
Abstract
The invention relates to a preparation method of a carbon material for rubber engineering equipment, which comprises the steps of ball milling cellulose, a component A, a component B and purified water, freeze-drying the formed suspension, and finally carbonizing to prepare the carbon material, wherein the cellulose is one or a combination of two of cellulose acetate and cellulose triacetate; the component A is one or two selected from diammonium hydrogen phosphate and diammonium hydrogen citrate; the component B is selected from one or more than two of tetrabutyl tetrafluoroborate phosphine, di-tert-butyl neopentyl tetrafluoroborate phosphine or tricyclohexyl phosphine fluoroborate. The carbon material obtained by the method is uniformly doped with nitrogen, phosphorus and boron, has excellent performance and ideal reinforcing performance, and experiments prove that the carbon material obtained by the method can be used as an additive of rubber products, can improve the performance of rubber, and has good market application prospect.
Description
Technical Field
The invention relates to a preparation method of a carbon material for rubber engineering equipment, and belongs to the technical field of carbon materials.
Background
Carbon is one of the most common elements in natural distribution, and its atoms form single bonds by sp3 hybridization, and also sp 3 And sp hybridization to form stable double and triple bonds, thus allowing the formation of homoisosteres of widely different structure and natureFeatures such as zero-dimensional carbon black and fullerenes, one-dimensional carbon nanotubes and carbon nanofibers, two-dimensional graphene, and the like. The carbon material can be used as a filler to be added into rubber, can enhance the physical, thermal, electrical and gas/liquid barrier properties of the rubber, and can reduce the production cost of rubber products.
In order to find excellent carbon material filler for rubber, the applicant and the energy resource institute of the national academy of sciences of Hebei have developed a deep cooperation to form a series of research results: CN115583647A, CN115611266A, CN115709983A, CN116332157A, CN116812915A, CN116986584a, the present application is also a new technical solution explored in the same research and development context, in order to form a patent pool of rubber carbon filler.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a carbon material for rubber engineering equipment.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: adding cellulose and purified water into a ball milling tank of a high-energy ball mill, ball milling, adding the component A in batches, adding the component B at one time after the addition, and ball milling to obtain a suspension;
s2: freeze-drying the suspension obtained in the step S1 at the temperature of-70 to-80 ℃ for 20-25 hours;
s3: carbonizing the product dried in the step S2 under the vacuumizing condition, and slowly cooling to room temperature to obtain the black carbon material.
As some preferred embodiments of the present invention, the mass ratio of the cellulose, the component a and the component B in the step S1 is 5.5 to 6.5:4.0 to 5.0: 3.5-4.5; the adding amount of the purified water is 2-3 times of the total mass of the materials;
the cellulose is selected from one or two of cellulose acetate or cellulose triacetate;
the component A is selected from one or two of diammonium hydrogen phosphate or diammonium hydrogen citrate;
the component B is selected from one or more than two of tetrabutyl tetrafluoroborate phosphine, di-tert-butyl neopentyl tetrafluoroborate phosphine or tricyclohexyl phosphine fluoroborate.
As some preferred embodiments of the present invention, the mass ratio of cellulose, component a and component B in step S1 is 6.0:4.5:4.0.
as some preferred embodiments of the present invention, the cellulose in the step S1 is cellulose acetate.
As some preferred embodiments of the present invention, component A in step S1 is diammonium phosphate.
As some preferred embodiments of the present invention, component B in step S1 is tetrabutyl phosphonium tetrafluoroborate.
As some preferred embodiments of the invention, the ball milling speed in the step S1 is 600-700 rpm, the component A is added in three times, ball milling is carried out for 25-35 min after each time of adding, the component B is added, the ball milling is stopped for 5-10 min after each 25-35 min of rotating, and the process is repeated for 2-4 times.
As some preferred embodiments of the present invention, the standing time in the step S1 is 50 to 70 minutes.
As some preferred embodiments of the invention, in the step S3, protective gas is continuously introduced at a rate of 15-25 mL/min in the carbonization process, the temperature is firstly raised to 420+/-10 ℃ from room temperature at a rate of 4.0-6.0 ℃/min, the temperature is kept for 1-1.2 h, then the temperature is raised to 850+/-10 ℃ at a rate of 1.5-2.5 ℃/min, the temperature is kept for 1-1.2 h, and the temperature is naturally lowered to the room temperature, thus obtaining the carbonized material.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in:
the method provided by the invention takes cellulose, the component A and the component B as raw materials, and the component A is added for ball milling and mixing for multiple times, so that hydroxyl and carboxyl on the cellulose are promoted to be fully combined with amino in the component A, hydrogen bonding is generated, the yield is improved, nitrogen fixation and nitrogen dispersion are realized, the intermittent ball milling is further realized after the component B is added, the uniform doping of nitrogen, phosphorus and boron is further realized, the obtained carbon material has excellent performance and ideal reinforcing performance, and the carbon material obtained by the method is used as an additive of a rubber product, so that the performance of rubber can be improved, and the method has good market application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an SEM image of a carbon material of example 1;
FIG. 2 is a graph showing the particle size distribution of the carbon material of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be clearly and completely described in connection with the following specific embodiments.
Acetyl 39.8, wt% and hydroxyl 3.5, wt% of the cellulose acetate in this example. In this example, cellulose triacetate acetyl was 43 to 44% and the esterification value was 60.5 to 61.5%.
Example 1
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 36mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 1572m 2 Per gram, the particle size distribution is 3.2-6.8 nm, and the pore volume is 1.20cm 3 /g。
Example 2
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 6.0g of cellulose triacetate, 4.5g of diammonium hydrogen citrate and 4.0g of di-tert-butyl neopentyl tetrafluoroborate are put into a ball milling tank of a high-energy ball mill for use, the cellulose triacetate and 36mL of distilled water are put into the ball milling tank for ball milling, the ball milling speed is 650 revolutions per minute, the diammonium hydrogen citrate is added in three batches in average, the ball milling is carried out for 30 minutes after each addition is carried out sequentially, after each addition, the di-tert-butyl neopentyl tetrafluoroborate phosphine is added for ball milling for three times, the ball milling speed is 650 revolutions per minute, the rotation is stopped for 8 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 1375m 2 Per gram, the particle size distribution is 4.0-15.3 nm, and the pore volume is 1.07cm 3 /g。
Example 3
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 6.0g of cellulose triacetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tricyclohexylphosphine fluoroborate are weighed for later use, the cellulose triacetate and 36mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at a ball milling speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and successively, ball milling is carried out for 30 minutes after each addition, tricyclohexylphosphine fluoroborate is added for three times for ball milling, the ball milling speed is 650 revolutions per minute for each time, the rotation is carried out for 30 minutes for 8 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 1189m 2 Per gram, the particle size distribution is 5.1-16.6 nm, and the pore volume is 0.93cm 3 /g。
Example 4
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 5.5g of cellulose acetate, 4g of diammonium hydrogen phosphate and 3.5g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 33mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling, the ball milling speed is 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, the ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate is added for ball milling for three times at a ball milling speed of 650 revolutions per minute, the rotation is carried out for 30 minutes for 8 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 1234m 2 Per gram, the particle size distribution is 5.7-17.7 nm, and the pore volume is 1.0cm 3 /g。
Example 5
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 6.5g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 38mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 1397m 2 Per gram, the particle size distribution is 5.5-18.1 nm, and the pore volume is 1.08cm 3 /g。
Comparative example 1
A method for preparing a carbon material, comprising the steps of:
s1: 6.0g of ethyl cellulose, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the ethyl cellulose and 36mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 932m 2 Per gram, the particle size distribution is 4.3-20.9 nm, and the pore volume is 0.84cm 3 /g。
Comparative example 2
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 6.0g of cellulose acetate, 4.5g of disodium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 36mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling, the ball milling speed is 650 revolutions per minute, three batches of disodium hydrogen phosphate are added successively in average, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for three times for ball milling, the ball milling speed is 650 revolutions per minute for each time, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 811m 2 Per gram, the particle size distribution is 2.5-16.2 nm, and the pore volume is 0.75cm 3 /g。
Comparative example 3
A method for preparing a carbon material, comprising the steps of:
s1: weighing 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0gTetraethylammonium tetrafluoroboratePlacing cellulose acetate and 36mL of distilled water into a ball milling tank of a high-energy ball mill for ball milling at a ball milling rotation speed of 650 revolutions per minute, adding three batches of diammonium phosphate in sequence, and ball milling after each addition in sequence30 minutes, after the addition is finished, add at a timeTetraethyltetrafluoroboric acid Ammonium ball millAnd (3) carrying out ball milling for three times, wherein the ball milling rotating speed is 650 revolutions per minute, the ball milling is stopped for 8 minutes after 30 minutes of rotation, and finally, the ball milling is kept stand for 1 hour to obtain a suspension.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 946m 2 Per gram, the particle size distribution is 6.8-24.0 nm, and the pore volume is 0.81cm 3 /g。
Comparative example 4
A method for preparing a carbon material, comprising the steps of:
s1: weighing 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0gTetrabutyl tetraphenyl phosphine boratePlacing cellulose acetate and 36mL of distilled water into a ball milling tank of a high-energy ball mill for ball milling at a ball milling speed of 650 revolutions per minute, adding three batches of diammonium phosphate in average, ball milling for 30 minutes after each addition, and adding at one time after the additionTetrabutyl tetraphenyl boronic acid Phosphine (P)Ball milling is carried out for three times, the ball milling rotating speed is 650 revolutions per minute each time, the ball milling is stopped for 8 minutes after 30 minutes of rotation, and finally, the ball milling is kept stand for 1 hour to obtain suspension.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 900m 2 And/g, wherein the particle size distribution is 10.1-33.0 nm, and the pore volume is 0.79cm 3 /g。
Comparative example 5
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: weighing 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of ammonium borate for later use, putting the cellulose acetate and 20mL of distilled water into a ball milling tank of a high-energy ball mill for ball milling at a ball milling speed of 650 revolutions per minute, adding three batches of diammonium hydrogen phosphate in average, ball milling for 30 minutes after each addition, ball milling for three times by adding ammonium borate once after each addition, stopping for 8 minutes after each ball milling at a speed of 650 revolutions per minute for 30 minutes, and finally standing for 1 hour to obtain a suspension.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 925m 2 Per gram, the particle size distribution is 8.6-35.4 nm, and the pore volume is 0.72cm 3 /g。
Comparative example 6
S1: 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroboric acid phosphine are weighed for standby, the cellulose acetate is put into a ball milling tank of a high-energy ball mill for ball milling, the ball milling speed is 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average, the ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroboric acid phosphine is added for ball milling for three times after each addition, the ball milling speed is 650 revolutions per minute, the rotation is carried out for 30 minutes for 8 minutes, and finally the standing is carried out for 1 hour.
S2: carbonizing the mixture obtained in the step S1 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic composite material.
The prepared carbon material has the following properties: specific surface area 615m 2 Per gram, the particle size distribution is 14.1-54.7 nm, and the pore volume is 0.43cm 3 /g。
Comparative example 7
S1: 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 36mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling, the ball milling speed is 650 revolutions per minute, diammonium hydrogen phosphate is added, the ball milling is performed three times, ball milling is performed for 30 minutes after each time of adding, the ball milling is performed for 5 minutes again, the tetrabutyl tetrafluoroborate is added again for three times, the ball milling speed is 650 revolutions per minute, the ball milling is performed for 30 minutes, the ball milling is performed for 8 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 721m 2 Per gram, particle size distribution of 21.1-46.7 nm, pore volume of 0.69cm 3 /g。
Comparative example 8
S1: 6.0g of cellulose acetate, 3.0g of diammonium hydrogen phosphate and 2.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 28mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and successively, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 803m 2 Per gram, the particle size distribution is 19.4-36.5 nm, and the pore volume is 0.74cm 3 /g。
Comparative example 9
S1: 6.5g of cellulose acetate, 3.5g of diammonium hydrogen phosphate and 5.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 38mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 947m 2 Per gram, the particle size distribution is 12.4-29.6 nm, and the pore volume is 0.80cm 3 /g。
Comparative example 10
S1: 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 36mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, heating to 850+/-2 ℃ from room temperature at the speed of 2 ℃/min, maintaining for 1 hour, and naturally cooling to the room temperature to obtain the product.
The prepared carbon material has the following properties: specific surface area 686m 2 Per gram, the particle size distribution is 8.8-41.0 nm, and the pore volume is 0.45cm 3 /g。
Comparative example 11
A preparation method of a carbon material for rubber engineering equipment comprises the following steps:
s1: 6.0g of cellulose acetate, 4.5g of diammonium hydrogen phosphate and 4.0g of tetrabutyl tetrafluoroborate are weighed for standby, the cellulose acetate and 50mL of distilled water are put into a ball milling tank of a high-energy ball mill for ball milling at the speed of 650 revolutions per minute, the diammonium hydrogen phosphate is added in three batches in average and sequentially, ball milling is carried out for 30 minutes after each addition, the tetrabutyl tetrafluoroborate phosphine is added for ball milling for three times at the speed of 650 revolutions per minute, the rotation is suspended for 30 minutes, and finally, the suspension is obtained after standing for 1 hour.
S2: and (3) freeze-drying the suspension obtained in the step (S1) at 75+/-2 ℃ for 24 hours.
S3: carbonizing the product dried in the step S2 under the vacuumizing condition, continuously introducing protective gas at the speed of 20mL/min in the carbonizing process, firstly heating to 420+/-2 ℃ from room temperature at the speed of 5.0 ℃/min, preserving heat for 1h, then heating to 850+/-2 ℃ at the speed of 2 ℃/min, then preserving heat for 1 hour, and naturally cooling to the room temperature to obtain the modified carbon fiber reinforced plastic material.
The prepared carbon material has the following properties: specific surface area 831m 2 Per gram, particle size distribution of 7.8-19.2 nm, pore volume of 0.83cm 3 /g。
Effect example
The carbon materials prepared in examples 1 to 5 and comparative examples 1 to 11 were used to prepare rubber water stop samples 1 to 5 and comparative samples 1 to 11 by the following methods:
the preparation method of the rubber water stop belt comprises the following steps:
100 parts of natural rubber;
30 parts of reinforcing agent (the materials prepared in examples 1-5 and comparative examples 1-11, and the control sample is carbon black N330);
6 parts of zinc oxide;
1 part of stearic acid;
17 parts of petroleum resin;
3 parts of an anti-aging agent (DM);
2 parts of accelerator (CZ);
170 parts of filler FD;
step one: plasticating
Setting the initial temperature of the internal mixer to 70 ℃, cutting the natural rubber into small pieces, adding the small pieces into the internal mixer, plasticating for 6 minutes, and discharging when the internal mixer temperature reaches 100 ℃. And (5) carrying out thin pass on an open mill, opening a triangular bag for 4 times, and standing for at least 8 hours for later use.
Step two: one-stage mixing
Setting the initial temperature of an internal mixer at 85 ℃, rotating at 35 revolutions per minute, adding the plasticated natural rubber into the internal mixer, lifting an upper top bolt, adding a reinforcing agent, a filling agent, an active agent, stearic acid, a softening agent and an anti-aging agent after about 45 seconds, pressing the upper top bolt, mixing for 160 seconds, lifting the middle bolt once, and discharging the rubber at 110 ℃. After the first section of rubber compound falls into an open mill, the roll spacing is adjusted to 5mm, the rubber compound is automatically poured for 4 times, and the roll temperature of the open mill is not higher than 60 ℃. And (5) after the pouring of the adhesive is completed, discharging the adhesive, and standing for at least 8 hours for later use.
Step three: two-stage mixing
Setting the initial temperature of the internal mixer at 85 ℃ and the rotating speed of 35 revolutions per minute, filling a section of mixed rubber material into the internal mixer, pressurizing for 45 seconds, lifting an upper top bolt, and adding a vulcanizing agent and an accelerator. The upper bolt is pressed down, the mixture is mixed for 80 seconds, the mixing temperature is 110 ℃, and the rubber is discharged. After the two-stage rubber compound falls into an open mill, the roll gap is adjusted to 5mm, the rubber compound is automatically poured for 4 times, and the roll temperature of the open mill is not higher than 60 ℃. And (5) after the pouring of the adhesive is completed, discharging the adhesive, and standing for at least 8 hours for later use.
According to Q/CR 562.2-2017 section 2 of railway Tunnel waterproof and drainage Material: water stops the performance test was performed on rubber water stops, the results of which are shown in Table 1 below:
table 1 Properties of the rubber Water stop samples prepared in examples 1 to 5
Table 1 properties of samples prepared in examples 1-5
Table 2 Properties of the samples prepared in comparative examples 1 to 11
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. The preparation method of the carbon material for the rubber engineering equipment is characterized by comprising the following steps of:
s1: adding cellulose and purified water into a ball milling tank of a high-energy ball mill, ball milling, adding the component A in batches, adding the component B at one time after the addition, and ball milling to obtain a suspension;
s2: freeze-drying the suspension obtained in the step S1 at the temperature of-70 to-80 ℃ for 20-25 hours;
s3: carbonizing the product dried in the step S2 under the vacuumizing condition, and slowly cooling to room temperature to obtain a black carbon material;
the mass ratio of the cellulose to the components A and B in the step S1 is 6.0:4.5:4, a step of; the adding amount of the purified water is 2-3 times of the total mass of the materials;
the cellulose is cellulose acetate;
the component A is selected from one or two of diammonium hydrogen phosphate or diammonium hydrogen citrate;
the component B is selected from one or more than two of tetrabutyl tetrafluoroborate phosphine, di-tert-butyl neopentyl tetrafluoroborate phosphine or tricyclohexyl phosphine fluoroborate;
the ball milling speed in the step S1 is 600-700 revolutions per minute, the component A is added in three times, ball milling is carried out for 25-35 min after adding once, the component B is suspended for 5-10 min after rotating for 25-35 min, and the steps are repeated for 2-4 times.
2. The method for preparing a carbon material for rubber engineering equipment according to claim 1, wherein the component A in the step S1 is diammonium hydrogen phosphate.
3. The method for preparing a carbon material for rubber engineering equipment according to claim 1, wherein the component B in the step S1 is tetrabutyl tetrafluoroboric acid phosphine.
4. The method for preparing a carbon material for rubber engineering equipment according to claim 1, wherein in the step S3, a protective gas is continuously introduced at a rate of 15-25 ml/min in the carbonization process, the temperature is raised to 420+ -10 ℃ from room temperature at a rate of 4.0-6.0 ℃/min, the temperature is kept for 1-1.2 h, the temperature is raised to 850+ -10 ℃ at a rate of 1.5-2.5 ℃/min, the temperature is kept for 1-1.2 h, and the temperature is naturally lowered to room temperature, thereby obtaining the carbon material.
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| CN103725014A (en) * | 2013-12-16 | 2014-04-16 | 芜湖万润机械有限责任公司 | Silicone rubber for railway vehicle |
| CN104159865A (en) * | 2012-03-09 | 2014-11-19 | 帕雷克斯集团有限公司 | Use of at least one superabsorbent polymer (psa) (b), in a dry composition based on a mineral binder and used for preparing a hardenable moist formulation for the building industry |
| JP2015118911A (en) * | 2013-12-19 | 2015-06-25 | 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 | Silicon-based composite negative electrode material for lithium ion secondary batteries, manufacturing method, and battery |
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| LU62830A1 (en) * | 1970-03-23 | 1971-03-24 | ||
| CA2668580A1 (en) * | 2009-04-30 | 2010-10-30 | Barbara Brooke Jennings | Compounds, methods, and treatments for abnormal signaling pathways for prenatal and postnatal development |
| CN104159865A (en) * | 2012-03-09 | 2014-11-19 | 帕雷克斯集团有限公司 | Use of at least one superabsorbent polymer (psa) (b), in a dry composition based on a mineral binder and used for preparing a hardenable moist formulation for the building industry |
| CN103725014A (en) * | 2013-12-16 | 2014-04-16 | 芜湖万润机械有限责任公司 | Silicone rubber for railway vehicle |
| JP2015118911A (en) * | 2013-12-19 | 2015-06-25 | 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 | Silicon-based composite negative electrode material for lithium ion secondary batteries, manufacturing method, and battery |
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