CN114181434A - High-viscosity environment-friendly reinforcing filler for rubber and preparation method thereof - Google Patents
High-viscosity environment-friendly reinforcing filler for rubber and preparation method thereof Download PDFInfo
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- 239000012763 reinforcing filler Substances 0.000 title claims abstract description 106
- 229920001971 elastomer Polymers 0.000 title claims abstract description 77
- 239000005060 rubber Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 49
- 239000001913 cellulose Substances 0.000 claims abstract description 35
- 229920002678 cellulose Polymers 0.000 claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 32
- 239000004964 aerogel Substances 0.000 claims abstract description 32
- 239000004917 carbon fiber Substances 0.000 claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 42
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002134 carbon nanofiber Substances 0.000 claims description 30
- 150000001721 carbon Chemical class 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 229920005575 poly(amic acid) Polymers 0.000 claims description 25
- 229960003638 dopamine Drugs 0.000 claims description 20
- 239000000017 hydrogel Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004021 humic acid Substances 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- MCHZKGNHFPNZDP-UHFFFAOYSA-N 2-aminoethane-1,1,1-triol;hydrochloride Chemical compound Cl.NCC(O)(O)O MCHZKGNHFPNZDP-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000004642 Polyimide Substances 0.000 abstract description 5
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K7/06—Elements
-
- 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
- C08K7/26—Silicon- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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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 high-viscosity environment-friendly reinforcing filler for rubber and a preparation method thereof, and relates to the technical field of new materials. When the rubber is used as a high-viscosity environment-friendly reinforcing filler, the diatomite aerogel is connected to the modified carbon fiber and then coated with the polyimide and the polydopamine to prepare a two-phase reinforcing filler; the modified carbon fiber is prepared by connecting sodium humate on the spiral nano carbon fiber, and the diatomite aerogel is prepared by compounding, freezing and drying diatomite and cellulose, so that the surface of the diatomite is organized, and the compatibility with rubber is enhanced. The reinforcing filler is added into the rubber for mixing, so that the adhesion of the reinforcing filler and the rubber is enhanced, and the impact resistance of the rubber is improved.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a high-viscosity environment-friendly reinforcing filler for rubber and a preparation method thereof.
Background
Except for a few self-reinforcing rubber varieties such as natural rubber, chloroprene rubber and the like, most of synthetic rubber has poor performance under the condition of not filling reinforcing fillers, and has low independent use value. Reinforcing fillers have an important and unique role in rubber processing. The rubber can improve the mechanical property of rubber, and is indispensable to non-self-reinforcing rubber such as styrene butadiene rubber, nitrile butadiene rubber and the like; the rubber material processing technology requirement can be met, the shrinkage rate of the rubber material is reduced, the molding is facilitated, and the shape and the size of the vulcanized rubber material can be kept stable; some varieties also have other functions, such as flame retardance, electric conduction, heat resistance and the like; the sizing material cost can be reduced.
The existing dual-phase rubber reinforcing filler is usually prepared by mixing and adding two phases into rubber for mixing, which often cannot achieve the dual-phase effect, but can reduce the effect of the reinforcing filler; therefore, the application tries to connect two reinforcing fillers together to form an integral dual-phase reinforcing filler, so as to obtain better reinforcing effect.
Disclosure of Invention
The invention aims to provide a high-viscosity environment-friendly reinforcing filler for rubber and a preparation method thereof, so as to solve the problems in the background technology.
A high-viscosity environment-friendly reinforcing filler for rubber mainly comprises the following raw material components in parts by weight: 12-30 parts of diatomite aerogel, 10-20 parts of modified carbon fiber, 110-250 parts of polyetherimide membrane liquid and 220-500 parts of dopamine solution.
Preferably, the diatomite aerogel is prepared by composite freeze drying of diatomite and cellulose.
Preferably, the modified carbon fiber is prepared by connecting sodium humate to the spiral carbon nanofiber; the grain diameter of the spiral carbon nanofiber is 100 nm.
Preferably, the preparation method of the high-viscosity environment-friendly reinforcing filler for rubber comprises the following steps: the preparation method comprises the steps of diatomite aerogel preparation, modified carbon fiber preparation, reinforcing filler blank preparation and high-viscosity environment-friendly reinforcing filler preparation for rubber.
Preferably, the preparation method of the high-viscosity environment-friendly reinforcing filler for rubber comprises the following specific steps:
(1) dispersing the cleaned cellulose in deionized water with the mass 30-50 times of that of the cellulose, freezing for 0.5-1 h at the temperature of-20 to-30 ℃, adding sodium hydroxide solution with the same mass, dissolving, adding kieselguhr with the mass 3.5-4.2 times of that of the cellulose at room temperature, ultrasonically stirring for 3-5 min at the speed of 800-1200 rpm and the frequency of 20-30 kHz, standing for 1-2 h to prepare hydrogel, dropwise adding acetic acid solution with the mass fraction of 20% 20-30 times of that of the cellulose at the speed of 2-3 ml/min to the surface of the hydrogel, ultrasonically stirring for 20-30 min at the frequency of 20-30 kHz after dropwise adding is completed, standing for 1h, removing the surface solution of the hydrogel, dropwise adding deionized water with the mass of the acetic acid solution and the like at the speed of 2-3 ml/min to the surface of the hydrogel, ultrasonically stirring for 20-30 min at the frequency of 20-30 kHz after dropwise adding is completed, standing for 1h, and finally transferring to a freeze dryer, drying at-50 ℃ under 10Pa for 8h, and grinding the particles to a particle size range of 50-100 nm to obtain the diatomite aerogel;
(2) dispersing spiral carbon nanofibers in tetrahydrofuran which is 50-80 times of the mass of the spiral carbon nanofibers, uniformly stirring, adding dicyclohexylcarbodiimide which is 2 times of the mass of the spiral carbon nanofibers and 4-dimethylaminopyridine which is 0.1 time of the mass of the spiral carbon nanofibers, heating in a water bath to 60-70 ℃, dropwise adding a sodium humate solution which is 5-8 times of the mass of the spiral carbon nanofibers at a rate of 2-3 ml/min, stirring at a heat preservation speed of 400-600 rpm for 3-4 h, filtering, placing in a drying oven, and drying at a temperature of 80-100 ℃ for 2-4 h to obtain modified carbon fibers;
(3) dispersing modified carbon fibers in deionized water 15-20 times of the mass of the modified carbon fibers, heating the mixture in a water bath to 90-100 ℃, adding diatomite aerogel 1.2-1.5 times of the mass of the modified carbon fibers, dropwise adding 98% concentrated sulfuric acid 0.1-0.15 times of the mass of the modified carbon fibers at a rate of 1-2 ml/min, stirring the mixture at a speed of 600-800 rpm for reaction for 24 hours, cooling the mixture to room temperature, centrifuging the mixture, and drying the mixture in a drying box at a temperature of 100-120 ℃ for 30 minutes to prepare a reinforcing filler blank;
(4) dispersing a reinforcing filler blank in a dopamine solution which is 5-10 times of the mass of the reinforcing filler blank, stirring at 200-400 rpm for 10-15 min, standing for 10-15 min, and centrifuging to obtain a reinforcing filler solid; dispersing reinforcing filler solid in polyimide film liquid with the mass of the reinforcing filler solid being 5-10 times, stirring at 200-400 rpm for 10-15 min, centrifuging and transferring to a vacuum oven, drying at 230 ℃ for 12h, finally placing in dopamine solution with the mass of the reinforcing filler solid being 5-10 times, stirring at 200-400 rpm for 10-15 min, standing for 10-15 min, centrifuging, and drying in a drying oven at 80-90 ℃ for 2-3 h to obtain the high-viscosity environment-friendly reinforcing filler for rubber.
Preferably, in the step (1): the process of cleaning cellulose is as follows: washing the mixture for 5 to 8 times by using deionized water and absolute ethyl alcohol in sequence, and drying the mixture for 2 to 3 hours in a drying box at the temperature of 80 to 90 ℃; the sodium hydroxide solution is frozen at-20 to-30 ℃ for 1.5h, and the mass fraction of the sodium hydroxide solution is 7-10%.
Preferably, in the step (2): the preparation method of the sodium humate solution comprises the following steps: dispersing humic acid in deionized water with the mass of 25-30 times that of the humic acid, and adjusting the pH to 7.5-8.5 by using sodium hydroxide to obtain a sodium humate solution.
Preferably, in the step (4): the preparation method of the dopamine solution comprises the following steps: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH of the dopamine-hydrochloric acid solution to 8.5 by using a trihydroxymethyl aminomethane hydrochloride solution to prepare the dopamine solution.
Preferably, in the step (4): the preparation method of the polyimide film liquid comprises the following steps: dispersing polyamic acid in cyclohexane of which the mass is 3-5 times that of the polyamic acid, uniformly stirring, adding N-methyl pyrrolidone of which the mass is 0.3-0.4 time that of the polyamic acid and deionized water of which the mass is 20-30 times that of the polyamic acid, and finally dropwise adding glycol of which the mass is 0.2-0.25 time that of the polyamic acid at a rate of 3-5 ml/min to obtain the polyimide film liquid.
Compared with the prior art, the invention has the following beneficial effects:
when the rubber is used as a high-viscosity environment-friendly reinforcing filler, the diatomite aerogel is connected to the modified carbon fiber and then coated with polyimide and polydopamine to prepare a two-phase reinforcing filler; the modified carbon fiber is prepared by connecting sodium humate on spiral nano carbon fiber, and the diatomite aerogel is prepared by performing composite freeze drying on diatomite and cellulose;
the sodium humate is connected to the surface of the spiral carbon nanofibers through hydrogen bonds, and the surface of the sodium humate is charged, so that electrostatic repulsion exists among the modified carbon fibers, and the aggregation in rubber is avoided; cellulose is crosslinked with diatomite to prepare diatomite aerogel with higher porosity, so that the surface of the diatomite is organized, and the compatibility with rubber is enhanced; hydroxyl on the surface of the diatomite aerogel reacts with active groups of the modified carbon fibers, so that the hydrophilicity of the modified carbon fibers is reduced, and the diatomite aerogel is connected to the surface of the modified carbon fibers to prepare a reinforcing filler blank;
coating the reinforcing filler blank with polyimide and polydopamine to prepare a reinforcing filler; coating a reinforcing filler blank with polydopamine, then coating a layer of polyimide film, and finally coating a layer of polydopamine; the polyimide film is a breathable film, the polydopamine layer is weaker in mechanical property, the three layers of wrapped reinforcing fillers are added into rubber for mixing, rubber molecules are changed into polymer small molecules and are extruded into large holes of the reinforcing fillers, the film on the surface of the reinforcing fillers is sunken and tightly attached to modified diatomite, gas in the large holes escapes from the three layers of films, meanwhile, the gas escapes to form pores, the pores firmly adsorb the rubber small molecules along with continuous shearing, the adhesion with the rubber is enhanced, the polydopamine layer contacting the reinforcing fillers is adsorbed and deformed, and the polydopamine layer tightly attached to the diatomite aerogel reacts with the diatomite at the gaps to enable the rubber and the reinforcing fillers to be tightly connected; after vulcanization, the polymer micromolecules and the reinforcing filler are crosslinked again to form a net-shaped three-dimensional structure, and after external force is applied, the net-shaped three-dimensional structure disperses stress, so that the impact resistance of the rubber is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
To more clearly illustrate the method of the present invention, the following examples are given, and the methods for testing the indexes of the high-viscosity environmentally friendly reinforcing filler for rubber prepared in the examples and comparative examples are as follows:
mechanical properties: rubber materials were prepared using the high-viscosity, environmentally friendly reinforcing fillers for rubber obtained in examples 1 and 2 and comparative examples 1 to 5 in equal amounts, respectively, and the mechanical properties were measured according to GB/T528.
Example 1
A high-viscosity environment-friendly reinforcing filler for rubber mainly comprises the following components in parts by weight:
12 parts of diatomite aerogel, 10 parts of modified carbon fibers, 110 parts of polyetherimide membrane liquid and 220 parts of dopamine solution.
A preparation method of a high-viscosity environment-friendly reinforcing filler for rubber comprises the following steps:
(1) sequentially washing cellulose with deionized water and absolute ethyl alcohol for 5 times, and drying in a drying oven at 80 ℃ for 2 hours; the sodium hydroxide solution is a 7% sodium hydroxide solution which is frozen for 1.5h at the temperature of-20 ℃ to obtain cleaned cellulose; dispersing the cleaned cellulose in deionized water 30 times of the mass of the cellulose, freezing at-20 ℃ for 0.5h, adding sodium hydroxide solution with equal mass, dissolving, adding diatomite 3.5 times of the mass of the cellulose at room temperature, ultrasonically stirring at 800rpm and 20kHz for 5min, standing for 1h to obtain hydrogel, dripping 20 times of 20% acetic acid solution of cellulose by mass at 2ml/min on the surface of hydrogel, performing ultrasonic treatment at 20kHz for 30min, standing for 1h, removing the solution on the surface of the hydrogel, dripping deionized water with the same mass as that of the acetic acid solution onto the surface of the hydrogel at a rate of 2ml/min, performing ultrasonic treatment at 20kHz for 30min after the dripping is finished, standing for 1h, transferring to a freeze dryer, drying at-50 ℃ under 10Pa for 8h, and grinding to a particle size range of 50-100 nm to obtain diatomite aerogel;
(2) dispersing humic acid in deionized water with the mass of 25 times that of the humic acid, and adjusting the pH to 7.8 by using sodium hydroxide to obtain a sodium humate solution; dispersing spiral carbon nanofibers in tetrahydrofuran 50 times of the mass of the spiral carbon nanofibers, uniformly stirring, adding dicyclohexylcarbodiimide 2 times of the mass of the spiral carbon nanofibers and 4-dimethylaminopyridine 0.1 times of the mass of the spiral carbon nanofibers, heating in a water bath to 60 ℃, dropwise adding a sodium humate solution 5 times of the mass of the spiral carbon nanofibers at a rate of 2ml/min, stirring at a temperature of 400rpm for 4 hours, filtering, and drying in a drying oven at 80 ℃ for 4 hours to obtain modified carbon fibers;
(3) dispersing modified carbon fibers in deionized water 15 times the mass of the modified carbon fibers, heating the mixture in a water bath to 90 ℃, adding diatomite aerogel 1.2 times the mass of the modified carbon fibers, dropwise adding concentrated sulfuric acid with the mass fraction of 98 percent, 0.1 time the mass of the modified carbon fibers, 1ml/min, stirring the mixture at 600rpm for reaction for 24 hours, cooling the mixture to room temperature, centrifuging the mixture, and drying the mixture in a drying oven at 100 ℃ for 30 minutes to prepare a reinforcing filler blank;
(4) dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a trihydroxymethyl aminomethane hydrochloride solution to prepare a dopamine solution; dispersing polyamic acid in cyclohexane with the mass of 3 times that of the polyamic acid, uniformly stirring, adding N-methyl pyrrolidone with the mass of 0.3 time that of the polyamic acid and deionized water with the mass of 20 times that of the polyamic acid, and finally dropwise adding glycol with the mass of 0.2 time that of the polyamic acid at 3ml/min to prepare a polyimide film liquid; dispersing a reinforcing filler blank in a dopamine solution which is 5 times of the mass of the reinforcing filler blank, stirring at 200rpm for 15min, standing for 10min, and centrifuging to obtain a reinforcing filler solid; dispersing the reinforcing filler solid in a polyimide film liquid with the mass of the reinforcing filler being 5 times that of the reinforcing filler solid, stirring for 15min at 200rpm, centrifuging, transferring to a vacuum oven, drying for 12h at 230 ℃, finally placing in a dopamine solution with the mass of the reinforcing filler being 5 times that of the reinforcing filler solid, stirring for 10min at 200rpm, standing for 10min, centrifuging, and drying for 2h in a drying oven with the temperature of 80 ℃ to obtain the high-viscosity environment-friendly reinforcing filler for rubber.
Example 2
A high-viscosity environment-friendly reinforcing filler for rubber mainly comprises the following components in parts by weight:
30 parts of diatomite aerogel, 20 parts of modified carbon fibers, 250 parts of polyetherimide membrane liquid and 500 parts of dopamine solution.
A preparation method of a high-viscosity environment-friendly reinforcing filler for rubber comprises the following steps:
(1) sequentially washing cellulose with deionized water and absolute ethyl alcohol for 8 times, and drying in a drying oven at 90 ℃ for 3 hours; the sodium hydroxide solution is a 10% sodium hydroxide solution which is frozen for 1.5h at the temperature of minus 30 ℃ to obtain cleaned cellulose; dispersing the cleaned cellulose in deionized water 50 times of the mass of the cellulose, freezing at-30 ℃ for 1h, adding sodium hydroxide solution with equal mass, dissolving, adding diatomite 4.2 times of the mass of the cellulose at room temperature, ultrasonically stirring at 1200rpm and 30kHz for 3min, standing for 2h to obtain hydrogel, dripping 20% acetic acid solution 30 times of cellulose mass at 3ml/min onto hydrogel surface, performing ultrasonic treatment at 30kHz for 20min, standing for 2h, removing the solution on the surface of the hydrogel, dripping deionized water with the same mass as that of the acetic acid solution onto the surface of the hydrogel at a rate of 2ml/min, performing ultrasonic treatment at 30kHz for 20min after the dripping is finished, standing for 1h, transferring to a freeze dryer, drying at-50 ℃ under 10Pa for 8h, and grinding to a particle size range of 50-100 nm to obtain diatomite aerogel;
(2) dispersing humic acid in deionized water with the mass of 30 times that of the humic acid, and adjusting the pH to 8.2 by using sodium hydroxide to obtain a sodium humate solution; dispersing spiral carbon nanofibers in tetrahydrofuran with the mass of 80 times that of the spiral carbon nanofibers, uniformly stirring, adding dicyclohexylcarbodiimide with the mass of 2 times that of the spiral carbon nanofibers and 4-dimethylaminopyridine with the mass of 0.1 time that of the spiral carbon nanofibers, heating in a water bath to 70 ℃, dropwise adding a sodium humate solution with the mass of 8 times that of the spiral carbon nanofibers at a rate of 3ml/min, keeping the temperature and stirring at 600rpm for 3 hours, filtering, and placing in a drying oven for amide drying at 100 ℃ for 2 hours to obtain modified carbon fibers;
(3) dispersing modified carbon fibers in deionized water with the mass of 20 times that of the modified carbon fibers, heating the mixture in a water bath to 100 ℃, adding diatomite aerogel with the mass of 1.5 times that of the modified carbon fibers, dropwise adding concentrated sulfuric acid with the mass fraction of 98 percent, which is 0.15 time that of the modified carbon fibers, at the speed of 2ml/min, stirring the mixture at 800rpm for reaction for 24 hours, cooling the mixture to room temperature, centrifuging the mixture, and drying the mixture in a drying oven with the temperature of 120 ℃ for 30 minutes to prepare a reinforcing filler blank;
(4) dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a trihydroxymethyl aminomethane hydrochloride solution to prepare a dopamine solution; dispersing polyamic acid in cyclohexane with the mass of 5 times that of the polyamic acid, uniformly stirring, adding N-methyl pyrrolidone with the mass of 0.3 time that of the polyamic acid and deionized water with the mass of 30 times that of the polyamic acid, and finally dropwise adding glycol with the mass of 0.25 time that of the polyamic acid at 5ml/min to prepare a polyimide film liquid; dispersing a reinforcing filler blank in a dopamine solution which is 10 times of the mass of the reinforcing filler blank, stirring at 400rpm for 10min, standing for 15min, and centrifuging to obtain a reinforcing filler solid; dispersing the reinforcing filler solid in a polyimide film liquid with the mass of the reinforcing filler being 10 times that of the reinforcing filler solid, stirring at 400rpm for 10min, centrifuging, transferring to a vacuum oven, drying at 230 ℃ for 12h, finally placing in a dopamine solution with the mass of the reinforcing filler being 5 times that of the reinforcing filler solid, stirring at 400rpm for 10min, standing for 10min, centrifuging, and drying in a drying oven at 90 ℃ for 3h to obtain the high-viscosity environment-friendly reinforcing filler for rubber.
Comparative example 1
The formulation of comparative example 1 was the same as example 1. The preparation method of the high-viscosity environment-friendly reinforcing filler for rubber is different from that of the example 1 only in that the treatment of the step (2) is not carried out, and the step (3) uses carbon fiber to prepare a reinforcing filler blank.
Comparative example 2
Comparative example 2 was formulated as in example 1. The preparation method of the high-viscosity environment-friendly reinforcing filler for rubber is different from that of the example 1 only in that the treatment of the step (1) is not carried out, and the step (3) is carried out by using diatomite to prepare a reinforcing filler blank.
Comparative example 3
The formulation of comparative example 3 was the same as example 1. The preparation method of the high-viscosity environment-friendly reinforcing filler for the rubber is different from that of the example 1 only in the difference of the step (4), and the step (4) is modified as follows: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a trihydroxymethyl aminomethane hydrochloride solution to prepare a dopamine solution; dispersing polyamic acid in cyclohexane with the mass of 3 times that of the polyamic acid, uniformly stirring, adding N-methyl pyrrolidone with the mass of 0.3 time that of the polyamic acid and deionized water with the mass of 20 times that of the polyamic acid, and finally dropwise adding glycol with the mass of 0.2 time that of the polyamic acid at 3ml/min to prepare a polyimide film liquid; dispersing a reinforcing filler blank in a polyimide film liquid with the mass 5 times of the solid mass of the reinforcing filler, stirring at 200rpm for 15min, centrifuging, transferring to a vacuum oven, drying at 230 ℃ for 12h, finally placing in a dopamine solution with the mass 5 times of the solid mass of the reinforcing filler, stirring at 200rpm for 10min, standing for 10min, centrifuging, and drying in a drying oven at 80 ℃ for 2h to obtain the high-viscosity environment-friendly reinforcing filler for rubber.
Comparative example 4
Comparative example 4 was formulated as in example 1. The preparation method of the high-viscosity environment-friendly reinforcing filler for rubber is different from that of the example 1 only in that the step (3) is carried out without the treatment of the step (4) to prepare the high-viscosity environment-friendly reinforcing filler for rubber.
Comparative example 5
A high-viscosity environment-friendly reinforcing filler for rubber mainly comprises the following components in parts by weight:
12 parts of diatomite aerogel and 10 parts of modified carbon fiber.
A preparation method of a high-viscosity environment-friendly reinforcing filler for rubber comprises the following steps:
(1) sequentially washing cellulose with deionized water and absolute ethyl alcohol for 5 times, and drying in a drying oven at 80 ℃ for 2 hours; the sodium hydroxide solution is a 7% sodium hydroxide solution which is frozen for 1.5h at the temperature of-20 ℃ to obtain cleaned cellulose; dispersing the cleaned cellulose in deionized water 30 times of the mass of the cellulose, freezing at-20 ℃ for 0.5h, adding sodium hydroxide solution with equal mass, dissolving, adding diatomite 3.5 times of the mass of the cellulose at room temperature, ultrasonically stirring at 800rpm and 20kHz for 5min, standing for 1h to obtain hydrogel, dripping 20 times of 20% acetic acid solution of cellulose by mass at 2ml/min on the surface of hydrogel, performing ultrasonic treatment at 20kHz for 30min, standing for 1h, removing the solution on the surface of the hydrogel, dripping deionized water with the same mass as that of the acetic acid solution onto the surface of the hydrogel at a rate of 2ml/min, performing ultrasonic treatment at 20kHz for 30min after the dripping is finished, standing for 1h, transferring to a freeze dryer, drying at-50 ℃ under 10Pa for 8h, and grinding to a particle size range of 50-100 nm to obtain diatomite aerogel;
(2) dispersing humic acid in deionized water with the mass of 25 times that of the humic acid, and adjusting the pH to 7.8 by using sodium hydroxide to obtain a sodium humate solution; dispersing spiral carbon nanofibers in tetrahydrofuran 50 times of the mass of the spiral carbon nanofibers, uniformly stirring, adding dicyclohexylcarbodiimide 2 times of the mass of the spiral carbon nanofibers and 4-dimethylaminopyridine 0.1 times of the mass of the spiral carbon nanofibers, heating in a water bath to 60 ℃, dropwise adding a sodium humate solution 5 times of the mass of the spiral carbon nanofibers at a rate of 2ml/min, stirring at a temperature of 400rpm for 4 hours, filtering, and drying in a drying oven at 80 ℃ for 4 hours to obtain modified carbon fibers;
(3) mixing modified carbon fiber and diatomite aerogel according to the mass ratio of 1: 1.2, mixing to obtain the high-viscosity environment-friendly reinforcing filler for rubber.
Examples of effects
The following table 1 shows the results of performance analysis of rubber materials prepared by using the high-viscosity environmentally-friendly reinforcing fillers for rubber of examples 1 and 2 of the present invention and comparative examples 1, 2, 3 and 4.
TABLE 1
| Hardness of | Tensile strength | Elongation at Break (%) | Tear strength | |
| Example 1 | 75 | 33.9 | 655 | 131 |
| Example 2 | 74 | 34.5 | 643 | 139 |
| Comparative example 1 | 65 | 27.6 | 584 | 117 |
| Comparative example 2 | 70 | 30.0 | 607 | 121 |
| Comparative example 3 | 64 | 28.4 | 572 | 113 |
| Comparative example 4 | 72 | 31.2 | 632 | 105 |
| Comparative example 5 | 70 | 28.5 | 543 | 93 |
Compared with the experimental data of the embodiment and the comparative example in the table 1, the rubber material prepared by the high-viscosity environment-friendly reinforcing filler for the rubber prepared in the embodiments 1 and 2 has better mechanical property;
from the comparison of experimental data of examples 1 and 2 and experimental data of comparative examples 1 and 2, it can be found that the mechanical property of rubber can be enhanced by using the humic acid modified spiral nano carbon fiber to prepare the reinforcing filler, which indicates that electrostatic repulsion exists among the modified carbon fibers and agglomeration in the rubber is avoided; the diatomite aerogel of the diatomite and cellulose vegetation is connected to the surface of the modified carbon fiber, so that the hydrophilicity of the modified carbon fiber is reduced, and the compatibility with rubber is enhanced, thereby enhancing the mechanical property of the rubber; and cellulose is not used for preparing the aerogel, and diatomite is directly used, so that the porosity is low, the combination with rubber is not tight during mixing, and the mechanical property is poor.
From the comparison of experimental data of the embodiment 1 and the embodiment 2 and the comparative examples 3 and 4, it can be found that the reinforcing filler blank is coated with three layers of polydopamine, polyimide and polydopamine, gas in the filler escapes from the three-layer film, rubber micromolecules are firmly adsorbed by pores, the adhesiveness with rubber is enhanced, meanwhile, the polydopamine layer contacting with the reinforcing filler is adsorbed and deformed, and reacts with diatomite close to the gaps of the diatomite aerogel, so that the rubber and the reinforcing filler are tightly connected, and the mechanical property of the rubber is enhanced; the prepared rubber has poor mechanical property only by using two layers of polyimide and polydopamine for coating or not coating;
from the comparison of the experimental data of example 1, example 2 and comparative example 5, it can be found that the reinforcing effect of the dual-phase reinforcing filler formed by combining the modified carbon fiber and the diatomite aerogel is better for the rubber than the reinforcing effect of the blend of the modified carbon fiber and the diatomite aerogel and the reinforcing effect of the retrograde rubber.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The high-viscosity environment-friendly reinforcing filler for rubber is characterized by mainly comprising the following raw material components in parts by weight: 12-30 parts of diatomite aerogel, 10-20 parts of modified carbon fiber, 110-250 parts of polyetherimide membrane liquid and 220-500 parts of dopamine solution.
2. The high-viscosity environment-friendly reinforcing filler for rubber as claimed in claim 1, wherein the diatomite aerogel is prepared by freeze-drying diatomite and cellulose in a compounding manner.
3. The high-viscosity environment-friendly reinforcing filler for rubber as claimed in claim 2, wherein the modified carbon fiber is prepared by connecting sodium humate to a spiral carbon nanofiber; the grain diameter of the spiral carbon nanofiber is 100 nm.
4. A preparation method of a high-viscosity environment-friendly reinforcing filler for rubber is characterized by comprising the following steps: the preparation method comprises the steps of diatomite aerogel preparation, modified carbon fiber preparation, reinforcing filler blank preparation and high-viscosity environment-friendly reinforcing filler preparation for rubber.
5. The preparation method of the high-viscosity environment-friendly reinforcing filler for rubber according to claim 4, characterized by comprising the following specific steps:
(1) dispersing the cleaned cellulose in deionized water with the mass 30-50 times of that of the cellulose, freezing for 0.5-1 h at the temperature of-20 to-30 ℃, adding sodium hydroxide solution with the same mass, dissolving, adding kieselguhr with the mass 3.5-4.2 times of that of the cellulose at room temperature, ultrasonically stirring for 3-5 min at the speed of 800-1200 rpm and the frequency of 20-30 kHz, standing for 1-2 h to prepare hydrogel, dropwise adding acetic acid solution with the mass fraction of 20% 20-30 times of that of the cellulose at the speed of 2-3 ml/min to the surface of the hydrogel, ultrasonically stirring for 20-30 min at the frequency of 20-30 kHz after dropwise adding is completed, standing for 1h, removing the surface solution of the hydrogel, dropwise adding deionized water with the mass of the acetic acid solution and the like at the speed of 2-3 ml/min to the surface of the hydrogel, ultrasonically stirring for 20-30 min at the frequency of 20-30 kHz after dropwise adding is completed, standing for 1h, and finally transferring to a freeze dryer, drying at-50 ℃ under 10Pa for 8h, and grinding the particles to a particle size range of 50-100 nm to obtain the diatomite aerogel;
(2) dispersing spiral carbon nanofibers in tetrahydrofuran which is 50-80 times of the mass of the spiral carbon nanofibers, uniformly stirring, adding dicyclohexylcarbodiimide which is 2 times of the mass of the spiral carbon nanofibers and 4-dimethylaminopyridine which is 0.1 time of the mass of the spiral carbon nanofibers, heating in a water bath to 60-70 ℃, dropwise adding a sodium humate solution which is 5-8 times of the mass of the spiral carbon nanofibers at a rate of 2-3 ml/min, stirring at a heat preservation speed of 400-600 rpm for 3-4 h, filtering, placing in a drying oven, and drying at a temperature of 80-100 ℃ for 2-4 h to obtain modified carbon fibers;
(3) dispersing modified carbon fibers in deionized water 15-20 times of the mass of the modified carbon fibers, heating the mixture in a water bath to 90-100 ℃, adding diatomite aerogel 1.2-1.5 times of the mass of the modified carbon fibers, dropwise adding 98% concentrated sulfuric acid 0.1-0.15 times of the mass of the modified carbon fibers at a rate of 1-2 ml/min, stirring the mixture at a speed of 600-800 rpm for reaction for 24 hours, cooling the mixture to room temperature, centrifuging the mixture, and drying the mixture in a drying box at a temperature of 100-120 ℃ for 30 minutes to prepare a reinforcing filler blank;
(4) dispersing a reinforcing filler blank in a dopamine solution which is 5-10 times of the mass of the reinforcing filler blank, stirring at 200-400 rpm for 10-15 min, standing for 10-15 min, and centrifuging to obtain a reinforcing filler solid; dispersing reinforcing filler solid in polyimide film liquid with the mass of the reinforcing filler solid being 5-10 times, stirring at 200-400 rpm for 10-15 min, centrifuging and transferring to a vacuum oven, drying at 230 ℃ for 12h, finally placing in dopamine solution with the mass of the reinforcing filler solid being 5-10 times, stirring at 200-400 rpm for 10-15 min, standing for 10-15 min, centrifuging, and drying in a drying oven at 80-90 ℃ for 2-3 h to obtain the high-viscosity environment-friendly reinforcing filler for rubber.
6. The method for preparing a high-viscosity environment-friendly reinforcing filler for rubber according to claim 5, wherein in the step (1): the process of cleaning cellulose is as follows: washing the mixture for 5 to 8 times by using deionized water and absolute ethyl alcohol in sequence, and drying the mixture for 2 to 3 hours in a drying box at the temperature of 80 to 90 ℃; the sodium hydroxide solution is frozen at-20 to-30 ℃ for 1.5h, and the mass fraction of the sodium hydroxide solution is 7-10%.
7. The method for preparing a high-viscosity environment-friendly reinforcing filler for rubber according to claim 5, wherein in the step (2): the preparation method of the sodium humate solution comprises the following steps: dispersing humic acid in deionized water with the mass of 25-30 times that of the humic acid, and adjusting the pH to 7.5-8.5 by using sodium hydroxide to obtain a sodium humate solution.
8. The method for preparing a high-viscosity environment-friendly reinforcing filler for rubber according to claim 5, wherein in the step (4): the preparation method of the dopamine solution comprises the following steps: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH of the dopamine-hydrochloric acid solution to 8.5 by using a trihydroxymethyl aminomethane hydrochloride solution to prepare the dopamine solution.
9. The method for preparing a high-viscosity environment-friendly reinforcing filler for rubber according to claim 5, wherein in the step (4): the preparation method of the polyimide film liquid comprises the following steps: dispersing polyamic acid in cyclohexane of which the mass is 3-5 times that of the polyamic acid, uniformly stirring, adding N-methyl pyrrolidone of which the mass is 0.3-0.4 time that of the polyamic acid and deionized water of which the mass is 20-30 times that of the polyamic acid, and finally dropwise adding glycol of which the mass is 0.2-0.25 time that of the polyamic acid at a rate of 3-5 ml/min to obtain the polyimide film liquid.
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