CN112500619A - Aramid fiber reinforced nitrile rubber composite material and preparation method thereof - Google Patents
Aramid fiber reinforced nitrile rubber composite material and preparation method thereof Download PDFInfo
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004816 latex Substances 0.000 claims abstract description 63
- 229920000126 latex Polymers 0.000 claims abstract description 63
- 229920001971 elastomer Polymers 0.000 claims abstract description 33
- 239000005060 rubber Substances 0.000 claims abstract description 33
- 239000002562 thickening agent Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 9
- GDESEHSRICGNDP-UHFFFAOYSA-L [Cl-].[Cl-].[Ca+2].CCO Chemical compound [Cl-].[Cl-].[Ca+2].CCO GDESEHSRICGNDP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 150000002825 nitriles Chemical class 0.000 claims abstract description 5
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 52
- 229960003638 dopamine Drugs 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004760 aramid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000000679 carrageenan Substances 0.000 claims description 2
- 235000010418 carrageenan Nutrition 0.000 claims description 2
- 229920001525 carrageenan Polymers 0.000 claims description 2
- 229940113118 carrageenan Drugs 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 229940080313 sodium starch Drugs 0.000 claims description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000005987 sulfurization reaction Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 16
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 8
- 230000008719 thickening Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010074 rubber mixing Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920003008 liquid latex Polymers 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- AHLIATSKXNSERY-UHFFFAOYSA-N N-(1,3-benzoxazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCC(CC1)NSc1nc2ccccc2o1 AHLIATSKXNSERY-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides an aramid fiber reinforced nitrile rubber composite material and a preparation method thereof, wherein the aramid fiber reinforced nitrile rubber composite material comprises 100 parts of nitrile latex, 0.2-20 parts of modified aramid fiber, 0.1-5 parts of thickening agent and 5-14 parts of auxiliary material by mass. The preparation method comprises 1) mixing the thickening agent with the butyronitrile latex, adding the modified aramid fiber, and uniformly stirring and mixing to obtain pre-mixed latex; 2) dropwise adding a calcium chloride-ethanol solution into the premixed latex, performing flocculation and sedimentation on the modified aramid fiber to obtain premixed rubber, and drying the premixed rubber to obtain masterbatch; 3) mixing the master batch on an open mill, sequentially adding auxiliary materials after rubber plasticating and roll coating, turning over, thinly passing and discharging to obtain a rubber compound; 4) and (4) standing the rubber compound, and vulcanizing to obtain a final product. The aramid fiber in the invention has good dispersibility in the butyronitrile latex matrix, stronger bonding with the rubber matrix interface, and obviously improved performance of the composite material.
Description
Technical Field
The invention relates to the technical field of fiber reinforced composite materials, in particular to an aramid fiber reinforced nitrile rubber composite material and a preparation method thereof.
Background
Aramid fibers have the characteristics of high specific strength, large modulus, fatigue resistance, wear resistance and the like, and are widely applied to various fields of aerospace, machinery, military, electronics and electricity and the like. The nitrile rubber is a non-crystalline synthetic rubber, has polar cyano groups in the molecular structure, and has good oil resistance, wear resistance, air tightness, antistatic property and the like. The unreinforced nitrile rubber has lower strength, and the Short Fiber Reinforced Polymer (SFRP) composite material prepared by blending the aramid fiber and the nitrile rubber can greatly improve the mechanical property of the composite material while the characteristics of rubber collagen are kept. It is well known that the mechanical properties of fiber reinforced polymer composites depend not only on the mechanical properties of the fibers and the matrix itself, but also on the fiber surface properties and the load transfer mechanism at the interface of the fibers and the matrix in the composite. However, a large number of benzene rings which are not easy to freely rotate and move exist in the molecular structure of the aramid fiber, and the hydrogen bonding action or chemical reaction of an amide group and other groups in molecules or among molecules is limited, so that the surface of the aramid fiber is smooth and chemically inert, and the interfacial adhesion between the aramid fiber and a matrix is small. In addition, due to the large length-diameter ratio and soft texture of the aramid fiber, the aramid fiber is difficult to be uniformly dispersed when blended with a polymer matrix, which limits the application of the aramid fiber in high-performance composite materials. Therefore, the dispersion of the aramid fiber in the matrix and the interface bonding capability of the aramid fiber and the polymer matrix are improved, the excellent performance of the aramid fiber is better exerted, the application of the aramid fiber in a high-performance composite material is expanded, and the problem which is mainly solved in the existing aramid fiber reinforced composite material is solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides the aramid fiber reinforced nitrile rubber composite material and the preparation method thereof, the preparation process is simple, the aramid fiber has good dispersibility in the nitrile latex matrix, the interface bonding with the rubber matrix is stronger, and the performance of the composite material is obviously improved.
The aramid fiber reinforced nitrile rubber composite material comprises, by mass, 100 parts of nitrile latex, 0.2-20 parts of modified aramid fiber, 0.1-5 parts of a thickening agent and 5-14 parts of an auxiliary material.
The invention relates to a preparation method of an aramid fiber reinforced nitrile rubber composite material, which comprises the following steps: 1) mixing a thickening agent and butyronitrile latex to obtain thickened latex, adding modified aramid fiber into the thickened latex, and uniformly stirring and mixing to obtain pre-mixed latex; 2) gradually dropwise adding a calcium chloride-ethanol solution into the premixed latex to flocculate and settle the modified aramid fibers in the premixed latex to obtain premixed rubber, and drying the premixed rubber to obtain masterbatch; 3) mixing the master batch on an open mill, sequentially adding auxiliary materials after rubber plasticating and roll coating, turning over, thinly passing and discharging to obtain a rubber compound; 4) and (3) standing the rubber compound, and vulcanizing to obtain a final product.
Compared with the prior art, the invention has the advantages and positive effects that: according to the invention, firstly, the pretreatment of the modified aramid fiber and the thickening pretreatment of the liquid latex are carried out, and the modified aramid fiber and the thickening latex are fully mixed in a liquid state by a wet rubber mixing technology, so that the dispersibility of the aramid fiber in a latex matrix and the associativity of the aramid fiber with the matrix are improved, and the performance of the composite material is obviously improved.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following embodiments.
The aramid fiber reinforced nitrile rubber composite material in the embodiment comprises, by mass, 100 parts of nitrile latex, 0.2-20 parts of modified aramid fiber, 0.1-5 parts of a thickening agent and 5-14 parts of an auxiliary material. The nitrile-butadiene latex is suspension latex obtained by emulsifying rubber, and is liquid latex.
Wherein the auxiliary materials comprise 1-3 parts of stearic acid, 2-5 parts of zinc oxide, 1-3 parts of accelerator CZ (sulfenamide accelerator, N-cyclohexyl-2-benzoxazole sulfenamide) and 1-3 parts of sulfur by mass.
The modified aramid fiber is obtained by treating aramid fiber with dopamine aqueous solution, and the mass concentration of the dopamine aqueous solution is 0.5-3 g/L. The specific method comprises the following steps: soaking aramid fiber into dopamine aqueous solution for 10-30h under mechanical stirring, washing with deionized water, filtering, and drying in an oven at 40-100 deg.C. The dopamine molecules can undergo self-polymerization reaction under the oxidation condition to form poly-dopamine molecules which are deposited on the surface of the material. The aramid fiber is soaked in the dopamine alkaline buffer solution to realize the surface modification, and a polydopamine film is spontaneously deposited on the fiber surface, so that the interfacial adhesion performance with a nitrile rubber matrix is effectively improved.
The thickener is one or more of polyacrylic acid, polyoxyethylene, cellulose, sodium alginate, carrageenan, polyvinylpyrrolidone and sodium starch phosphate.
The preparation method of the aramid fiber reinforced nitrile rubber composite material in the embodiment comprises the following steps:
1) mixing a thickening agent and butyronitrile latex to obtain thickened latex, adding modified aramid fiber into the thickened latex, stirring and mixing uniformly to obtain premixed latex, wherein the stirring speed is 200-1500rpm;
2) gradually dropwise adding a calcium chloride-ethanol solution with the mass concentration of 0.5-5% into the premixed latex to flocculate and settle the modified aramid fibers in the premixed latex to obtain premixed rubber, and drying the premixed rubber in a drying oven at the temperature of 30-80 ℃ for 72 hours to obtain master batch;
3) blending the master batch on an open mill, wherein the initial roll temperature is 35-90 ℃, the rotation speed is 20-60rpm, and the auxiliary materials are sequentially added after the rubber plasticating and roll wrapping, are turned over, thinned and are discharged to obtain the rubber compound;
4) and standing the mixed rubber for 12 hours, and vulcanizing by using a flat vulcanizing machine at the vulcanization temperature of 100-180 ℃ to obtain a final product.
According to the embodiment, a thickening agent is added into the butyronitrile latex in advance through a wet rubber mixing technology, the modified aramid fiber is pre-dispersed in the thickened latex to prepare the masterbatch, the dispersion of the aramid fiber in a latex matrix is improved, the interaction force between the aramid fiber and the rubber matrix is increased, and the performance of the composite material is obviously improved.
In industrial production, a rubber mixing mill is usually directly used for mixing rubber and a filler in a solid phase to obtain uniform mixing of two phases or multiple phases, while in solid phase mixing, a satisfactory dispersion effect of the filler phase is often difficult to obtain, and in wet rubber mixing technology, the filler can obtain better matrix dispersibility due to solvation, so that the limitation of poor dispersibility of the filler directly used in solid phase mixing can be improved by a wet pre-dispersion process. In the wet pre-dispersion process, the density of the aramid fiber is higher than that of a water solvent in latex, so that the improvement effect of the dispersibility of the filler fiber is limited due to the gravity settling effect. In order to solve the technical problem, a proper high-molecular thickening agent is selected to improve the viscosity of latex, and fibers can form a kinetically stable metastable state in emulsion under higher solution viscosity, so that the aggregation phenomenon of the fibers under the gravity settling action or higher filling degree condition is overcome.
Example one
(1) Preparing the following raw materials in parts by mass: 100 parts of butyronitrile latex, 0.5 part of aramid fiber, 0.25% of thickening agent by mass, dopamine solution, 1 part of stearic acid, 2 parts of zinc oxide, 1 part of accelerator CZ and 1 part of sulfur;
the method for treating the aramid fiber by using the dopamine comprises the following steps: preparing a dopamine impregnation solution with the concentration of 0.5g/L, immersing aramid fibers into the dopamine mixed solution for 12 hours under mechanical stirring, washing with deionized water, performing suction filtration, and fully drying in a 60-DEG C drying oven;
thickening the latex by using a thickening agent, adding the modified aramid fiber into the thickened latex, and stirring and mixing uniformly by using a cantilever stirrer at the rotating speed of 500rpm;
gradually dropwise adding 0.5% calcium chloride ethanol solution to flocculate and settle the modified aramid fiber pre-mixed latex, and drying the obtained pre-mixed latex in a 60 ℃ oven for three days;
and (3) blending the master batch on an open mill, wherein the initial roller temperature is 45 ℃, the rotation speed is 60rpm, sequentially adding auxiliary materials after rubber plasticating and roll-coating, turning over, thinly passing, discharging, standing the mixed rubber for one night, and vulcanizing by using a flat vulcanizing machine at 120 ℃ to obtain a final product.
Example two
(1) Preparing the following raw materials in parts by mass: 100 parts of butyronitrile latex, 3 parts of aramid fiber, 0.5% of thickening agent by mass, a dopamine solution, 2 parts of stearic acid, 2 parts of zinc oxide, 1 parts of accelerator CZ and 1 part of sulfur;
treating aramid fibers with dopamine;
thickening the latex by using a thickening agent, adding the modified aramid fiber into the thickened latex, and uniformly stirring and mixing at the rotating speed of 750rpm by using a cantilever stirrer, wherein the specific method comprises the following steps: preparing a dopamine impregnation solution with the concentration of 1.5g/L, immersing aramid fibers into the dopamine mixed solution for 16 hours under mechanical stirring, washing with deionized water, performing suction filtration, and fully drying in a 60-DEG C drying oven;
gradually dropwise adding 1% calcium chloride-ethanol solution to flocculate and settle the modified aramid fiber pre-mixed latex, and drying the obtained pre-mixed latex in a 50 ℃ oven for three days.
And (3) blending the master batch on an open mill, wherein the initial roller temperature is 50 ℃, the rotation speed is 40rpm, the rubber plasticating and roll wrapping are sequentially added with auxiliary materials, the auxiliary materials are turned over, thinned and discharged, and the master batch is vulcanized at 140 ℃ by a flat plate vulcanizing machine after being placed for one night to obtain the final product.
EXAMPLE III
(1) Preparing the following raw materials in parts by mass: 100 parts of butyronitrile latex, 5 parts of aramid fiber, 0.75% of thickening agent by mass, dopamine solution, 1 part of stearic acid, 3 parts of zinc oxide, 2 parts of accelerator CZ and 1 part of sulfur;
the method for treating the aramid fiber by using the dopamine comprises the following steps: preparing a dopamine impregnation solution with the concentration of 2g/L, immersing aramid fibers into the dopamine mixed solution for 18 hours under mechanical stirring, washing with deionized water, carrying out suction filtration, and fully drying in a 70 ℃ drying oven;
thickening the latex by using a thickening agent, adding the modified aramid fiber into the thickened latex, and stirring and mixing uniformly by using a cantilever stirrer at the rotating speed of 1000 rpm;
gradually dropwise adding an ethanol solution of 2% calcium chloride to flocculate and settle the modified aramid fiber pre-mixed latex, and drying the obtained pre-mixed latex in an oven at 70 ℃ for three days.
And (3) blending the master batch on an open mill, wherein the initial roller temperature is 80 ℃, the rotation speed is 60rpm, the auxiliary materials are sequentially added after the rubber is plasticated and coated, turned over, thinned and chipped, and the master batch is vulcanized by a flat plate vulcanizing machine at 150 ℃ after being placed for one night to obtain the final product.
Example four
Preparing the following raw materials in parts by mass: 100 parts of butyronitrile latex, 8 parts of aramid fiber, 1% of thickening agent by mass, a dopamine solution, 2 parts of stearic acid, 5 parts of zinc oxide, 1 parts of accelerator CZ and 2 parts of sulfur;
the method for treating the aramid fiber by using the dopamine comprises the following steps: preparing a dopamine impregnation solution with the concentration of 3g/L, immersing aramid fibers into the dopamine mixed solution for 20 hours under mechanical stirring, washing with deionized water, carrying out suction filtration, and fully drying in an oven at 80 ℃;
thickening the latex by using a thickening agent, adding the modified aramid fiber into the thickened latex, and stirring and mixing uniformly by using a cantilever stirrer at the rotating speed of 800 rpm;
gradually dropwise adding an ethanol solution of 5% calcium chloride to flocculate and settle the modified aramid fiber pre-mixed latex, and drying the obtained pre-mixed latex in an oven at 80 ℃ for three days.
And (3) blending the master batch on an open mill, wherein the initial roller temperature is 90 ℃, the rotation speed is 60rpm, the auxiliary materials are sequentially added after the rubber is plasticated and coated, turned over, thinned and chipped, and the master batch is vulcanized at 180 ℃ by using a flat plate vulcanizing machine after being placed for one night to obtain the final product.
EXAMPLE five
(1) Preparing the following raw materials in parts by mass: 100 parts of butyronitrile latex, 10 parts of aramid fiber, 2% of thickening agent by mass, a dopamine solution, 2 parts of stearic acid, 3 parts of zinc oxide, 1 parts of accelerator CZ and 1.5 parts of sulfur;
the method for treating the aramid fiber by using the dopamine comprises the following steps: preparing a dopamine impregnation solution with the concentration of 2.5g/L, immersing aramid fibers into the dopamine mixed solution for 15 hours under mechanical stirring, washing with deionized water, performing suction filtration, and fully drying in an oven at 80 ℃;
(3) thickening the latex by using a thickening agent, adding the modified aramid fiber into the thickened latex, and stirring and mixing uniformly by using a cantilever stirrer at the rotating speed of 900 rpm;
gradually dropwise adding an ethanol solution of 4% calcium chloride to flocculate and settle the modified aramid fiber pre-mixed latex, and drying the obtained pre-mixed latex in an oven at 60 ℃ for three days.
And (3) blending the master batch on an open mill, wherein the initial roller temperature is 70 ℃, the rotation speed is 50rpm, sequentially adding auxiliary materials after rubber plasticating and roll-coating, turning over, thinly passing and discharging, standing the mixed rubber for one night, and vulcanizing by using a flat vulcanizing machine at 150 ℃ to obtain a final product.
The influence of the addition of thickeners with different mass concentrations on the mechanical properties of the composite material: the concentration of the thickener greatly affects the mechanical properties of the composite. If the concentration of the thickener is too low, the viscosity of the butyronitrile latex is not high enough, and the aramid fiber cannot reach a dynamic equilibrium state to form a suspension with good distribution in the wet pre-dispersion process of the butyronitrile latex, so that the aramid fiber cannot be well dispersed in the masterbatch, and the mechanical properties of the masterbatch are greatly reduced by local fiber enrichment and aggregates; if the concentration of the thickener is too high, energy consumption in production increases, and the mechanical properties of the masterbatch are affected by the large amount of the remaining thickener. From the experimental results, it can be seen that when the mass concentration of the thickener is 0.75%, the mechanical properties of the produced aramid reinforced nitrile rubber composite material are optimal, and the mechanical properties of the composite material are reduced by too low and too high concentrations of the thickener.
The above examples are only a few of the several preferred embodiments of the present invention, and it should be noted that the present invention is not limited to the above examples; for a person skilled in the art, modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (10)
1. The aramid fiber reinforced nitrile rubber composite material is characterized by comprising 100 parts of nitrile latex, 0.2-20 parts of modified aramid fiber, 0.1-5 parts of thickening agent and 5-14 parts of auxiliary material by mass.
2. The aramid fiber reinforced nitrile butadiene rubber composite material as claimed in claim 1, wherein the preparation method of the modified aramid fiber comprises the following steps: and (3) soaking the aramid fiber into the dopamine aqueous solution under stirring, then washing with water, carrying out suction filtration, and fully drying.
3. The aramid fiber reinforced nitrile rubber composite material as claimed in claim 1, wherein the auxiliary materials comprise 1-3 parts by mass of stearic acid, 2-5 parts by mass of zinc oxide, 1-3 parts by mass of accelerator CZ and 1-3 parts by mass of sulfur.
4. The aramid fiber reinforced nitrile rubber composite material as claimed in claim 1, wherein the thickener is one or a mixture of more than two of polyacrylic acid, polyethylene oxide, cellulose, sodium alginate, carrageenan, polyvinylpyrrolidone and sodium starch phosphate.
5. The preparation method of the aramid fiber reinforced nitrile rubber composite material is characterized by comprising the following steps of:
1) mixing a thickening agent and butyronitrile latex to obtain thickened latex, adding modified aramid fiber into the thickened latex, and uniformly stirring and mixing to obtain pre-mixed latex;
2) gradually dropwise adding a calcium chloride-ethanol solution into the premixed latex to flocculate and settle the modified aramid fibers in the premixed latex to obtain premixed rubber, and drying the premixed rubber to obtain masterbatch;
3) mixing the master batch on an open mill, sequentially adding auxiliary materials after rubber plasticating and roll coating, turning over, thinly passing and discharging to obtain a rubber compound;
4) and (3) standing the rubber compound, and vulcanizing to obtain a final product.
6. The method as claimed in claim 5, wherein the stirring speed in step 1) is 200-1500 rpm.
7. The preparation method according to claim 5, wherein the mass concentration of the calcium chloride-ethanol solution in the step 2) is 0.5 to 5%.
8. The preparation method according to claim 5, wherein the drying temperature in the step 2) is 30-80 ℃ and the drying time is 70-75 h.
9. The preparation method of claim 5, wherein the blending in the step 3) is performed at an initial roll temperature of 35 ℃ to 90 ℃ and a rotation speed of 20 rpm to 60 rpm.
10. The method according to claim 5, wherein the temperature of the sulfuration in the step 4) is 100 ℃ to 180 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087983A (en) * | 2021-05-25 | 2021-07-09 | 黄河三角洲京博化工研究院有限公司 | Enhanced HNBR material, preparation method and application thereof |
| CN113321857A (en) * | 2021-04-30 | 2021-08-31 | 宁波市大器密封科技有限公司 | Aramid fiber pressing ring and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417996A (en) * | 2017-09-25 | 2017-12-01 | 安徽依采妮纤维材料科技有限公司 | A kind of preparation method of aramid fiber enhancing rubber composite |
| CN108951140A (en) * | 2017-05-18 | 2018-12-07 | 北京化工大学 | A kind of surface modification method of fiber |
| CN110204806A (en) * | 2019-07-05 | 2019-09-06 | 黄河三角洲京博化工研究院有限公司 | A kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and preparation method thereof |
| WO2019172538A1 (en) * | 2018-03-06 | 2019-09-12 | 김덕수 | Synthetic rubber latex resin composition and method for manufacturing polymer fabric including microcell foam by using same |
-
2020
- 2020-10-22 CN CN202011134144.8A patent/CN112500619A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108951140A (en) * | 2017-05-18 | 2018-12-07 | 北京化工大学 | A kind of surface modification method of fiber |
| CN107417996A (en) * | 2017-09-25 | 2017-12-01 | 安徽依采妮纤维材料科技有限公司 | A kind of preparation method of aramid fiber enhancing rubber composite |
| WO2019172538A1 (en) * | 2018-03-06 | 2019-09-12 | 김덕수 | Synthetic rubber latex resin composition and method for manufacturing polymer fabric including microcell foam by using same |
| CN110204806A (en) * | 2019-07-05 | 2019-09-06 | 黄河三角洲京博化工研究院有限公司 | A kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 郭大双等: ""湿法混炼芳纶短纤维/丁腈橡胶复合材料的性能研究"", 《橡胶工业》 * |
| 郭大双等: ""湿法混炼芳纶短纤维/丁腈橡胶复合材料的性能研究"", 《橡胶工业》, no. 9, 25 September 2020 (2020-09-25), pages 683 - 683 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321857A (en) * | 2021-04-30 | 2021-08-31 | 宁波市大器密封科技有限公司 | Aramid fiber pressing ring and preparation method thereof |
| CN113087983A (en) * | 2021-05-25 | 2021-07-09 | 黄河三角洲京博化工研究院有限公司 | Enhanced HNBR material, preparation method and application thereof |
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