CN117004087A - Graphene oxide-glass fiber modified rubber composition and application thereof - Google Patents
Graphene oxide-glass fiber modified rubber composition and application thereof Download PDFInfo
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- CN117004087A CN117004087A CN202310977563.5A CN202310977563A CN117004087A CN 117004087 A CN117004087 A CN 117004087A CN 202310977563 A CN202310977563 A CN 202310977563A CN 117004087 A CN117004087 A CN 117004087A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 165
- 229920001971 elastomer Polymers 0.000 title claims abstract description 136
- 239000005060 rubber Substances 0.000 title claims abstract description 136
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 239000000835 fiber Substances 0.000 title claims abstract description 55
- 239000000075 oxide glass Substances 0.000 title claims abstract description 55
- 239000003607 modifier Substances 0.000 claims abstract description 77
- 239000003365 glass fiber Substances 0.000 claims abstract description 71
- 241001669679 Eleotris Species 0.000 claims abstract description 31
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000009210 therapy by ultrasound Methods 0.000 claims description 27
- 238000005576 amination reaction Methods 0.000 claims description 20
- 230000003712 anti-aging effect Effects 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 20
- 244000043261 Hevea brasiliensis Species 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 229920003052 natural elastomer Polymers 0.000 claims description 18
- 229920001194 natural rubber Polymers 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 17
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical group C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 claims description 17
- 239000005062 Polybutadiene Substances 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 229910052882 wollastonite Inorganic materials 0.000 claims description 15
- 239000010456 wollastonite Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- -1 saturated aliphatic diamine Chemical class 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000007514 turning Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- 150000004984 aromatic diamines Chemical class 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RHJXLYKEPZLABW-UHFFFAOYSA-N Sangol Natural products CC(C)=C1CC=C(C)C2=CC=C(CO)C2=C1 RHJXLYKEPZLABW-UHFFFAOYSA-N 0.000 description 3
- 241000532412 Vitex Species 0.000 description 3
- 235000009347 chasteberry Nutrition 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HPSILLNWMJOWNM-UJMOMDHXSA-N utilin Chemical compound C1([C@]2(C3(O)CC1(C)[C@H](CC(=O)OC)[C@@]3(C)[C@@]13OC4(C)OC5([C@]3([C@@H]2OC(C)=O)O4)CC(=O)O[C@H]([C@]5(C)C[C@H]1OC(=O)C(C)CC)C1=COC=C1)O)OC(=O)C1(C)OC1C HPSILLNWMJOWNM-UJMOMDHXSA-N 0.000 description 1
- 229930195056 utilin Natural products 0.000 description 1
Classifications
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene oxide-glass fiber modifier and a preparation method thereof. The modifier comprises the following raw materials: graphene oxide, bismuth chloride, polyamine and hollow glass fiber; wherein the mass ratio of the graphene oxide to the bismuth chloride is 10:1-20:1; based on the mass of graphene oxide, the mass ratio of the polyamine is 1-10%, and the mass ratio of the hollow glass fiber is 150-300%. The invention also provides a rubber composition comprising the modifier and a rubber backing plate for a railway track concrete sleeper prepared from the rubber composition.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a graphene oxide-glass fiber modifier for rubber reinforcement modification, a rubber composition containing the modifier and application of the rubber composition.
Background
Rubber tie plates are an important component in railway track construction, mounted between the rails and the concrete ties. The high-speed vibration and impact generated when the vehicle passes through the rail are buffered, the roadbed and the sleeper are protected, the abrasion between the wheel pair and the rail is reduced, and the railway signal system is electrically insulated. Therefore, the rubber pad plays an important role in damping and buffering the whole track structure. According to the TB/T3065-2020 elastic strip type II fastener, the performance of the rubber backing plate for the railway concrete sleeper must meet the index shown in Table 1.
Table 1 Performance of rubber shim plate for railway concrete sleeper specified by TB/T3065-2020
However, rubber pad plates conforming to the above performance indexes have disadvantages of large compression set, poor aging resistance, serious abrasion, short service life, etc. under the conditions of continuous acceleration of trains and continuous increase of freight traffic. Under actual working conditions, the rubber backing plate under the steel rail often has the phenomena of eccentric wear and cracking, even has the situation of wear-through, and causes the direct contact between the steel rail and the concrete sleeper, so that the train loses buffering and signal transmission faults, and the line safety is seriously threatened. In order to ensure the transportation safety, maintenance personnel in the working department need to check the service condition of the backing plate on line at random and replace the backing plate with serious damage. Because the number of the replaced backing plates is large, the replacement period is short, the maintenance cost is greatly increased, and the railway transportation cost is indirectly increased.
In order to solve the problems, the prior art has a technical proposal of adding a reinforcing agent and an antiwear agent to improve the rubber performance. The Chinese patent application No. CN113583314A (published day 2021, 11, 2) discloses a rubber composition taking one or more of MT novel carbon black, 774 carbon black, white carbon black, natural gas semi-reinforcing carbon black and fly ash type rubber reinforcing agent as reinforcing agent and taking one or more of high wear-resistant carbon black N300, N550 and N774 as wear-resistant agent. The rubber backing plate prepared from the rubber composition has excellent properties. But has a constant compression set of about 16%; after aging for 72 hours at 100 ℃, the tensile strength and the elongation at break are obviously reduced: the tensile strength is reduced from 17.7MPa to 12.8MPa, and the retention rate of the tensile strength is only 67.8%; the elongation at break is reduced from 338% to 225%, and the retention rate of the elongation at break is 66.5%.
Therefore, there is a need for developing a rubber composition for use as a rubber shim plate for railway track concrete ties which has a smaller constant compression set and better aging resistance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a graphene oxide-glass fiber modifier and a rubber composition comprising the same. The rubber composition modified by the modifier has the compression set of less than 9%, the tensile strength retention rate of more than 95% and the elongation at break retention rate of more than 90% after being aged for 72 hours at 100 ℃. In addition, the rubber composition of the invention has outstanding wear resistance, and the Aldrich abrasion is less than 0.2cm 3 /1.61kg。
In order to achieve the technical effects, the invention adopts the following technical scheme:
a graphene oxide-glass fiber modifier comprises the following raw materials: graphene oxide, bismuth chloride, polyamine and hollow glass fiber;
wherein the mass ratio of the graphene oxide to the bismuth chloride is 10:1-20:1; based on the mass of graphene oxide, the mass ratio of the polyamine is 1-10%, and the mass ratio of the hollow glass fiber is 150-300%.
Preferably, the mass ratio of the graphene oxide to the bismuth chloride is 13:1-17:1.
Preferably, the mass ratio of the polyamine is 4-8% based on the mass of the graphene oxide.
Preferably, the polyamine is selected from one or more of a C2-C6 saturated aliphatic diamine, a C3-C6 saturated aliphatic triamine, a C4-C6 saturated aliphatic tetramine and an aromatic diamine; more preferably a C2-C4 saturated aliphatic diamine, such as ethylenediamine.
Preferably, the hollow glass fiber has an outer diameter of 4 to 8 μm, an inner diameter of 1 to 3 μm, and an aspect ratio of 10 to 20.
More preferably, the hollow glass fiber is composed of a hollow glass fiber 1 having an outer diameter of 4 to 8 μm, an inner diameter of 1 to 3 μm and an aspect ratio of 15 to 20, and a hollow glass fiber 2 having an outer diameter of 4 to 8 μm, an inner diameter of 1 to 3 μm and an aspect ratio of 10 to 15, and the mass ratio of the hollow glass fiber 1 to the hollow glass fiber 2 is 1 to 3:1.
The invention also provides a preparation method of the graphene oxide-glass fiber modifier, which comprises the following steps:
I. preparing graphene oxide, bismuth chloride, polyamine and hollow glass fiber according to the proportion;
adding graphene oxide and bismuth chloride into anhydrous N, N-dimethylformamide, stirring for 15-20 min at room temperature, and then performing ultrasonic treatment for 5-10 min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1g:50 ml-1 g:100ml;
III, adding polyamine into the graphene oxide dispersion liquid obtained in the step II, stirring for 40-45 h at the temperature of 65-85 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3-5 times to obtain aminated graphene oxide;
IV, adding the amination graphene oxide obtained in the step III into absolute ethyl alcohol, and performing ultrasonic treatment for 1-1.5 h at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1 g:1.5L-1 g:3.0L;
and V, adding the hollow glass fiber into the amination graphene dispersion liquid obtained in the step IV, performing ultrasonic treatment at room temperature for 15-30 min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and performing vacuum drying at 90-100 ℃ and minus 0.1MPa for 10-12 h to obtain the graphene oxide-hollow glass fiber modifier.
Preferably, in the steps II, IV and V, the power of the ultrasound is 550-600 w.
It is still another object of the present invention to provide a rubber composition comprising the graphene oxide-glass fiber modifier.
Preferably, the rubber composition comprises the following components in parts by weight:
100 parts of rubber, 20-40 parts of graphene oxide-glass fiber modifier, 50-70 parts of filler, 2-4 parts of surface modifier, 0.5-1.5 parts of vulcanizing agent, 0.5-1.5 parts of accelerator and 1-3 parts of antioxidant RD.
Further preferably, the rubber composition comprises the following components in parts by weight:
100 parts of rubber, 25-35 parts of graphene oxide-glass fiber modifier, 53-62 parts of filler, 2.5-3.5 parts of surface modifier, 0.7-1.3 parts of vulcanizing agent, 0.7-1.3 parts of accelerator and 1.7-2.3 parts of anti-aging agent.
Preferably, the rubber is selected from one or more of natural rubber, ethylene propylene rubber and styrene butadiene rubber.
Further preferably, the rubber is a natural rubber and a styrene-butadiene rubber in a mass ratio of 1 to 3:1.
Preferably, the filler is carbon black and superfine wollastonite with the mass ratio of 1:1-2;
preferably, the surface modifier is liquid epoxy-terminated polybutadiene (ETPB).
Preferably, the vulcanizing agent is sulfur.
Preferably, the accelerator is tetrabenzyl thiuram disulfide.
Preferably, the anti-aging agent is an anti-aging agent RD.
The invention also provides an application of the rubber composition in preparing a rubber backing plate for a railway track concrete sleeper.
A rubber backing plate for a railway track concrete sleeper takes the rubber composition as a raw material.
The rubber backing plate for the railway track concrete sleeper can be prepared according to a conventional method in the field.
As a preferred embodiment, the rubber backing plate for the railway track concrete sleeper of the present invention can be prepared by the following steps:
A. placing rubber into an internal mixer, banburying for 8-10 min, then adding a surface modifier, a graphene oxide-glass fiber modifier, a filler and an anti-aging agent, banburying for 3-5 min, controlling the temperature of the internal mixer to be 90-110 ℃, discharging rubber, and standing at room temperature for 12-24 h to obtain a banburying rubber;
B. mixing the banburying glue in the step A in an open mill for 3-5 min, adding vulcanizing agent and accelerator, turning, packing, discharging sheets, cooling and standing to obtain a film;
C. and C, cutting the rubber sheet obtained in the step B according to the requirement, and putting the rubber sheet into a die for vulcanization to obtain the rubber backing plate.
The graphene has the characteristics of light weight, high strength, self-lubrication and the like, and can be used as nano filler to be added into a rubber composition, so that the performances of abrasion resistance, crushing resistance, mechanical strength and the like of a rubber product can be effectively improved, and the elastic advantage of rubber is maintained. However, graphene has a large specific surface area, is liable to cause irreversible agglomeration, so that the graphene has poor dispersibility in a rubber composition, and is difficult to play a role in improving rubber performance. The graphene oxide-glass fiber modifier provided by the invention can enable graphene to be uniformly distributed in rubber, and glass fiber plays a role in modifying and enhancing in cooperation with graphene, so that the performance of the rubber backing plate disclosed by the invention reaches the level shown in Table 2.
TABLE 2 Performance index of rubber backing plate of the invention
At present, the rubber backing plate for the concrete sleeper in the market has the compression set of 12-19 percent and the Aldrich abrasion value of 0.42-0.58 cm 3 And/1.61 kg, wherein after hot air aging, the tensile strength retention rate is 65-95%, and the elongation at break retention rate is 45-75%. The rubber backing plate provided by the invention has the above propertiesAll are significantly better than the commercial products.
Herein, the "parts by weight" is not a mass unit, and parts by weight of components represent a mass ratio relationship between the components. According to practical circumstances, 1 part by weight may be any mass number such as 1 ton, 10kg, 5kg, 1kg, 1.1kg, 1.5kg, 2.1kg, 100g, 250g or 1g, and the like.
Detailed Description
The invention is described below with reference to specific examples. It will be appreciated by those skilled in the art that these examples are for illustration of the invention only and are not intended to limit the scope of the invention in any way.
The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials, reagent materials and the like used in the examples described below are commercially available products unless otherwise specified. Wherein, the purchase conditions of partial reagents and raw materials are as follows: .
Graphene oxide: the Chinese academy of sciences contains 30.9wt% of oxygen, each of which has a diameter of 3-10 μm and a number of 3-5 layers;
bismuth chloride: nanjing chemical Agents Co Ltd;
ethylenediamine: nanjing chemical Agents Co Ltd;
hollow glass fiber 1 (outer diameter 5 μm, inner diameter 2 μm, aspect ratio 18): beijing Sangol's Vitex;
hollow glass fiber 2 (outer diameter 6 μm, inner diameter 2 μm, aspect ratio 12): beijing Sangol's Vitex;
hollow glass fiber 3 (outer diameter 20 μm, inner diameter 7 μm, aspect ratio 30): beijing Sangol's Vitex;
natural rubber: 3 # Tobacco flake glue, thailand product;
styrene-butadiene rubber: number 1502, china petrochemical Olympic company;
carbon black: brand N330, kaposi chemical (Shanghai) Co., ltd;
ultra-fine wollastonite: 1250 mesh, shanggao county Ming Zheng plasticizing Limited company;
epoxy-terminated liquid polybutadiene: astronomical aviation materials (barracks) science and technology share limited company;
tetrabenzyl thiuram disulfide (TBzTD): utilin New Material science and technology Co., ltd;
anti-aging agent RD: brand SY-100, UVLin New Material science and technology Co., ltd.
Example 1 graphene oxide-glass fiber modifier
The graphene oxide-glass fiber modifier of the present example was prepared by the following method:
1. adding graphene oxide and bismuth chloride in a mass ratio of 15:1 into anhydrous N, N-dimethylformamide, stirring for 15min at room temperature, and then performing ultrasonic treatment for 5min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1g to 50ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 40 hours at 67+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of ethylenediamine is 6% of that of graphene oxide;
3. adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1h at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 1.5L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 15min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 10h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 200% of that of the graphene oxide; the hollow glass fiber consists of a hollow glass fiber 1 and a hollow glass fiber 2 in a mass ratio of 2:1.
Example 2 graphene oxide-glass fiber modifier
The graphene oxide-glass fiber modifier of the present example was prepared by the following method:
1. adding graphene oxide and bismuth chloride with the mass ratio of 10:1 into anhydrous N, N-dimethylformamide, stirring for 15min at room temperature, and then performing ultrasonic treatment for 5min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1 g/60 ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 40 hours at 67+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of the ethylenediamine is 8 percent of that of the graphene oxide
3. Adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1h at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 2.0L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 15min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 10h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 150% of that of graphene oxide; the hollow glass fiber consists of a hollow glass fiber 1 and a hollow glass fiber 2 in a mass ratio of 2:1.
Example 3 graphene oxide-glass fiber modifier
The graphene oxide-glass fiber modifier of the present example was prepared by the following method:
1. adding graphene oxide and bismuth chloride with the mass ratio of 20:1 into anhydrous N, N-dimethylformamide, stirring for 20min at room temperature, and then performing ultrasonic treatment for 10min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1 g/70 ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 40 hours at 70+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of the ethylenediamine is 10 percent of that of the graphene oxide
3. Adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1.5 hours at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 2.5L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 20min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 12h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 200% of that of the graphene oxide; the hollow glass fiber consists of a hollow glass fiber 1 and a hollow glass fiber 2 in a mass ratio of 2:1.
Example 4 graphene oxide-glass fiber modifier
The graphene oxide-glass fiber modifier of the present example was prepared by the following method:
1. adding graphene oxide and bismuth chloride with the mass ratio of 13:1 into anhydrous N, N-dimethylformamide, stirring for 20min at room temperature, and then performing ultrasonic treatment for 10min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1 g/70 ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 45h at 75+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of the ethylenediamine is 6 percent of that of the graphene oxide
3. Adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1.5 hours at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 2.5L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 30min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 12h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 250% of that of graphene oxide; the hollow glass fiber consists of a hollow glass fiber 1 and a hollow glass fiber 2 in a mass ratio of 2:1.
Example 5 graphene oxide-glass fiber modifier
The graphene oxide-glass fiber modifier of the present example was prepared by the following method:
1. adding graphene oxide and bismuth chloride in a mass ratio of 17:1 into anhydrous N, N-dimethylformamide, stirring for 15min at room temperature, and then performing ultrasonic treatment for 10min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1 g/100 ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 45h at 67+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of the ethylenediamine is 1 percent of that of the graphene oxide
3. Adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1.5 hours at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 3.0L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 30min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 10h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 300% of that of the graphene oxide; the hollow glass fiber consists of a hollow glass fiber 1 and a hollow glass fiber 2 in a mass ratio of 2:1.
Example 6 rubber composition and rubber pad for railway track concrete sleeper prepared from the same
The composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 1.
The rubber backing plate for the railway track concrete sleeper is prepared by taking the composition as a raw material through the following method:
A. placing natural rubber and styrene-butadiene rubber into an internal mixer, carrying out internal mixing for 8-10 min, then adding epoxy-terminated liquid polybutadiene, graphene oxide-hollow glass fiber modifier and carbon black, carrying out internal mixing for 3-5 min, controlling the temperature of the internal mixer to be 90-110 ℃, discharging rubber, and standing at room temperature for 12-24 h to obtain an internal mixing rubber;
B. mixing the banburying glue in the step A in an open mill for 3-5 min, adding sulfur and tetrabenzyl thiuram disulfide, turning, packing, discharging sheets, cooling and standing to obtain a film;
C. and B, cutting the rubber sheet obtained in the step B according to the requirement, and placing the rubber sheet in a die for vulcanization to obtain the rubber backing plate for the railway track concrete sleeper.
Example 7 a rubber composition and a rubber pad for railway track concrete sleeper prepared therefrom the composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 40 parts of graphene oxide-glass fiber modifier, 20 parts of carbon black, 30 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.2 parts of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 2.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 8 a rubber composition and a rubber pad for railway track concrete sleeper prepared therefrom the composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 25 parts of graphene oxide-glass fiber modifier, 30 parts of carbon black, 32 parts of superfine wollastonite, 3.5 parts of epoxy-terminated liquid polybutadiene, 1.3 parts of sulfur, 1.5 parts of tetrabenzyl thiuram disulfide and 3 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 3.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 9 a rubber composition and a rubber pad for railway track concrete sleeper prepared therefrom the composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 20 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 25 parts of superfine wollastonite, 2.0 parts of epoxy-terminated liquid polybutadiene, 0.5 part of sulfur, 0.5 part of tetrabenzyl thiuram disulfide and 1.0 part of antioxidant RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 4.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 10 rubber composition and rubber pad for railway track concrete sleeper prepared from the same
The composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 40 parts of graphene oxide-glass fiber modifier, 30 parts of carbon black, 40 parts of superfine wollastonite, 4.0 parts of epoxy-terminated liquid polybutadiene, 1.5 parts of sulfur, 1.5 parts of tetrabenzyl thiuram disulfide and 3.0 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 5.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 11 rubber composition and rubber pad for railway track concrete sleeper prepared from the same
The composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 2.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 12 rubber composition and rubber pad for railway track concrete sleeper prepared from the same
The composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 3.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 13 rubber composition and rubber pad for railway track concrete sleeper prepared from the same
The composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 4.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Example 14 rubber composition and rubber pad for railway track concrete sleeper prepared from the same
The composition of the rubber composition of this example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
wherein the graphene oxide-glass fiber modifier was prepared as described in example 5.
The rubber backing plate for the railway track concrete sleeper was prepared by the same procedure and process as in example 6 using the above composition as a raw material.
Comparative example 1A rubber composition and a rubber gasket prepared therefrom
The composition of the rubber composition of this comparative example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 0 part of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
the rubber backing plate is prepared by taking the composition as a raw material according to the substantially same steps and processes of the embodiment 6, except that the graphene oxide-glass fiber modifier is not added during feeding in the step A.
Comparative example 2A rubber composition and a rubber gasket prepared therefrom
The composition of the rubber composition of this comparative example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
the rubber backing plate was prepared by the same procedure and process as in example 6, using the above composition as a raw material.
Wherein, the graphene oxide-glass fiber modifier is prepared by the following method:
1. adding graphene oxide and bismuth chloride in a mass ratio of 5:1 into anhydrous N, N-dimethylformamide, stirring for 15min at room temperature, and then performing ultrasonic treatment for 5min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1 g/60 ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 40 hours at 67+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of the ethylenediamine is 8 percent of that of the graphene oxide
3. Adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1h at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 2.0L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 15min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 10h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 150% of that of graphene oxide; the hollow glass fiber consists of a hollow glass fiber 1 and a hollow glass fiber 2 in a mass ratio of 2:1.
Comparative example 3A rubber composition and a rubber gasket prepared therefrom
The composition of the rubber composition of this comparative example was (1 part by weight=1 kg):
70 parts of natural rubber, 30 parts of styrene-butadiene rubber, 30 parts of graphene oxide-glass fiber modifier, 25 parts of carbon black, 35 parts of superfine wollastonite, 2.8 parts of epoxy-terminated liquid polybutadiene, 1.1 parts of sulfur, 1.0 part of tetrabenzyl thiuram disulfide and 2.1 parts of anti-aging agent RD;
the rubber backing plate was prepared by the same procedure and process as in example 6, using the above composition as a raw material.
Wherein, the graphene oxide-glass fiber modifier is prepared by the following method:
1. adding graphene oxide and bismuth chloride in a mass ratio of 15:1 into anhydrous N, N-dimethylformamide, stirring for 15min at room temperature, and then performing ultrasonic treatment for 5min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1 g/60 ml;
2. adding ethylenediamine into the graphene oxide dispersion liquid obtained in the step 1, stirring for 40 hours at 67+/-2 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3 times to obtain aminated graphene oxide; wherein the mass of the ethylenediamine is 8 percent of that of the graphene oxide
3. Adding the amination graphene oxide obtained in the step 2 into absolute ethyl alcohol, and performing ultrasonic treatment for 1h at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1g to 2.0L;
4. adding hollow glass fibers into the aminated graphene dispersion liquid obtained in the step 3, carrying out ultrasonic treatment at room temperature for 15min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and carrying out vacuum drying at-0.1 MPa for 10h at 90-100 ℃ to obtain the graphene oxide-hollow glass fiber modifier; wherein the mass of the hollow glass fiber is 150% of that of graphene oxide; the hollow glass fiber consists of a hollow glass fiber 3 and a hollow glass fiber 2 in a mass ratio of 2:1.
Test examples 6 to 14 and comparative examples 1 to 3 were prepared for measuring the properties of rubber pads
The properties of examples 6 to 14 and comparative examples 1 to 3 were measured according to the method of Q/CR564-2017, spring-strip type II fastener, and the measurement results are shown in Table 3 and Table 4.
TABLE 3 results of measurement of rubber backing plate Performance of examples 6 to 14
a : tensile strength retention = tensile strength after hot air aging at 100 ℃ for 72 h/tensile strength measured at normal temperature x 100%; the following is the same.
b : elongation at break retention = 100 ℃ x 72h elongation at break after hot air aging/elongation at break measured at normal temperature x 100%; the following is the same.
The data in Table 3 shows that the properties of the rubber compositions of the present invention are far beyond those specified in the current industry standard TB/T3065-2020 elastic strip type II fastener.
Table 4 results of measuring the properties of rubber mats of comparative examples 1 to 3
In summary, the invention provides a graphene oxide-glass fiber modifier, a rubber composition modified by the modifier and a rubber backing plate for a railway track concrete sleeper prepared from the rubber composition. The rubber composition (rubber backing plate) modified by the modifier has excellent performance, can meet the development trend of high-speed and heavy-load railway lines, and better ensures the running safety of railway trains.
Claims (10)
1. A graphene oxide-glass fiber modifier comprises the following raw materials: graphene oxide, bismuth chloride, polyamine and hollow glass fiber;
wherein the mass ratio of the graphene oxide to the bismuth chloride is 10:1-20:1; based on the mass of graphene oxide, the mass ratio of the polyamine is 1-10%, and the mass ratio of the hollow glass fiber is 150-300%.
2. The graphene oxide-glass fiber modifier according to claim 1, wherein the mass ratio of the graphene oxide to the bismuth chloride is 13:1-17:1;
preferably, the mass ratio of the polyamine is 4-8% based on the mass of the graphene oxide;
preferably, the polyamine is selected from one or more of a C2-C6 saturated aliphatic diamine, a C3-C6 saturated aliphatic triamine, a C4-C6 saturated aliphatic tetramine and an aromatic diamine; more preferably a C2-C4 saturated aliphatic diamine; most preferably ethylenediamine;
preferably, the outer diameter of the hollow glass fiber is 4-8 mu m, the inner diameter is 1-3 mu m, and the length-diameter ratio is 10-20;
more preferably, the hollow glass fiber is composed of a hollow glass fiber 1 having an outer diameter of 4 to 8 μm, an inner diameter of 1 to 3 μm and an aspect ratio of 15 to 20, and a hollow glass fiber 2 having an outer diameter of 4 to 8 μm, an inner diameter of 1 to 3 μm and an aspect ratio of 10 to 15, and the mass ratio of the hollow glass fiber 1 to the hollow glass fiber 2 is 1 to 3:1.
3. The preparation method of the graphene oxide-glass fiber modifier according to claim 1 or 2, comprising the following steps:
I. preparing graphene oxide, bismuth chloride, polyamine and hollow glass fiber according to the proportion;
adding graphene oxide and bismuth chloride into anhydrous N, N-dimethylformamide, stirring for 15-20 min at room temperature, and then performing ultrasonic treatment for 5-10 min to obtain graphene oxide dispersion liquid; wherein the ratio of the mass of the graphene oxide to the volume of the anhydrous N, N-dimethylformamide is 1g:50 ml-1 g:100ml;
III, adding polyamine into the graphene oxide dispersion liquid obtained in the step II, stirring for 40-45 h at the temperature of 65-85 ℃ in water bath, standing, filtering, and washing with absolute ethyl alcohol for 3-5 times to obtain aminated graphene oxide;
IV, adding the amination graphene oxide obtained in the step III into absolute ethyl alcohol, and performing ultrasonic treatment for 1-1.5 h at room temperature to obtain amination graphene oxide dispersion liquid; wherein the volume ratio of the mass of the graphene oxide to the absolute ethyl alcohol is 1 g:1.5L-1 g:3.0L;
adding hollow glass fibers into the amination graphene dispersion liquid obtained in the step IV, performing ultrasonic treatment at room temperature for 15-30 min, filtering, washing with absolute ethyl alcohol, transferring a filter cake into a vacuum oven, and performing vacuum drying at 90-100 ℃ and minus 0.1MPa for 10-12 h to obtain the graphene oxide-hollow glass fiber modifier;
preferably, in the steps II, IV and V, the power of the ultrasound is 550-600 w.
4. A rubber composition comprising the graphene oxide-glass fiber modifier according to claim 1 or 2 or a graphene oxide-glass fiber modifier directly obtained according to the production method of claim 3.
5. The rubber composition according to claim 4, wherein the rubber composition comprises the following components in parts by weight:
100 parts of rubber, 20-40 parts of graphene oxide-glass fiber modifier, 50-70 parts of filler, 2-4 parts of surface modifier, 0.5-1.5 parts of vulcanizing agent, 0.5-1.5 parts of accelerator and 1-3 parts of antioxidant RD;
preferably, the rubber composition comprises the following components in parts by weight:
100 parts of rubber, 25-35 parts of graphene oxide-glass fiber modifier, 53-62 parts of filler, 2.5-3.5 parts of surface modifier, 0.7-1.3 parts of vulcanizing agent, 0.7-1.3 parts of accelerator and 1.7-2.3 parts of anti-aging agent.
6. The rubber composition well according to claim 5, wherein said rubber is selected from one or more of natural rubber, ethylene propylene rubber and styrene butadiene rubber;
further preferably, the rubber is a natural rubber and a styrene-butadiene rubber in a mass ratio of 1 to 3:1.
7. The rubber composition according to claim 5, wherein the filler is carbon black and ultra-fine wollastonite in a mass ratio of 1:1-2;
preferably, the surface modifier is liquid epoxy-terminated polybutadiene;
preferably, the vulcanizing agent is sulfur;
preferably, the accelerator is tetrabenzyl thiuram disulfide;
preferably, the anti-aging agent is an anti-aging agent RD.
8. Use of the rubber composition according to any one of claims 4 to 7 for the preparation of rubber tie plates for railway track concrete ties.
9. A rubber backing plate for a railway track concrete sleeper, which is prepared from the rubber composition as claimed in any one of claims 4 to 7.
10. The method for preparing the rubber backing plate of claim 9, comprising the steps of:
A. placing rubber into an internal mixer, banburying for 8-10 min, then adding a surface modifier, a graphene oxide-glass fiber modifier, a filler and an anti-aging agent, banburying for 3-5 min, controlling the temperature of the internal mixer to be 90-110 ℃, discharging rubber, and standing at room temperature for 12-24 h to obtain a banburying rubber;
B. mixing the banburying glue in the step A in an open mill for 3-5 min, adding vulcanizing agent and accelerator, turning, packing, discharging sheets, cooling and standing to obtain a film;
C. and C, cutting the rubber sheet obtained in the step B according to the requirement, and putting the rubber sheet into a die for vulcanization to obtain the rubber backing plate.
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