CN117430877A - Antibacterial sealing rubber for water delivery pipeline of dish washer and production process - Google Patents
Antibacterial sealing rubber for water delivery pipeline of dish washer and production process Download PDFInfo
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- CN117430877A CN117430877A CN202311310267.6A CN202311310267A CN117430877A CN 117430877 A CN117430877 A CN 117430877A CN 202311310267 A CN202311310267 A CN 202311310267A CN 117430877 A CN117430877 A CN 117430877A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 113
- 239000005060 rubber Substances 0.000 title claims abstract description 113
- 238000007789 sealing Methods 0.000 title claims abstract description 50
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000006229 carbon black Substances 0.000 claims abstract description 53
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 43
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920001195 polyisoprene Polymers 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 11
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 229920002943 EPDM rubber Polymers 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000010074 rubber mixing Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 2
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003921 oil Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 3
- 150000002357 guanidines Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 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
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of pipeline rubber sealing, and discloses an antibacterial sealing rubber for a water pipeline of a dish washer and a production process, wherein the antibacterial sealing rubber for the water pipeline of the dish washer comprises the following raw materials in parts by weight: 25-40 parts of styrene-butadiene rubber, 15-30 parts of modified nitrile rubber, 5-8 parts of modified white carbon black, 1-3 parts of lignocellulose, 2-3 parts of nano zinc oxide, 2-4 parts of a modification accelerator M, 0.5-1 part of stearic acid, 1-3 parts of sulfur, 1-2 parts of a tri-guanidine organic antibacterial agent XT-11 and 1-2 parts of an anti-aging agent BHT.
Description
Technical Field
The invention belongs to the technical field of pipeline rubber sealing, and particularly relates to an antibacterial sealing rubber for a water pipeline of a dish washer and a production process thereof.
Background
Rubber is a polymer having elasticity. At present, the rubber products are widely applied to various fields of daily life, such as sealing of a dishwasher water pipeline, and the sealing rubber is one of important sealing elements for solving the phenomena of running, overflowing, dripping and leaking in the pipeline, and has wide application in production and life. In order to meet the requirements of production equipment, the pipeline seal is required to meet the requirements of the use conditions, besides necessary structural design and improvement, higher requirements are also provided for matched rubber sealing elements, and rubber used for the sealing elements is not only required to be excellent in physical and mechanical properties, but also required to be in accordance with the requirements of environmental protection.
The prior sealing rubber can adopt hydrogenated nitrile rubber, has excellent heat resistance, weather resistance and the like on the basis of keeping the excellent oil resistance of the nitrile rubber, but in the practical application process, the hydrogenated nitrile rubber is required to be modified due to the contradiction between low temperature property and oil resistance, and the hydrogenated nitrile rubber and ethylene propylene diene monomer rubber are blended in the prior art, but have poor compatibility due to different polarities. In addition, the prior sealing rubber uses white carbon black as a reinforcing filler, because the rubber matrix is usually nonpolar, a large number of hydroxyl groups are arranged on the surface of the white carbon black, the white carbon black has strong polarity, and the white carbon black is easy to gather due to the influence of hydrogen bonds, so that the contact surface between the filler and the rubber is reduced, the reinforcing effect of the filler is weakened, the prior art generally uses a silane coupling agent to modify the white carbon black, but the hydroxyl groups on the surface of the white carbon black acted by the silane coupling agent can release volatile organic matters, can cause harm to the environment and human bodies, does not meet the green environment-friendly requirement, and meanwhile, the dispersibility of the silane coupling agent on the white carbon black in the rubber matrix needs to be further enhanced so as to further improve the physical and mechanical properties of the rubber.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide the antibacterial sealing rubber for the water conveying pipeline of the dish washer and the production process, wherein the hydrogenated styrene-butadiene block copolymer serving as the third component is adopted to improve the compatibility of a blending system of the hydrogenated nitrile rubber and the ethylene propylene diene monomer, and the modified white carbon black and the modified accelerator M are added to enhance the dispersibility of the white carbon black in a rubber matrix, so that the physical and mechanical properties of the rubber are further improved, and volatile organic compounds are not generated in the reaction, so that the dish washer meets the requirements of green environmental protection.
The aim of the invention can be achieved by the following technical scheme:
an antibacterial sealing rubber for a water delivery pipeline of a dish washer comprises the following raw materials in parts by weight: 25-40 parts of styrene-butadiene rubber, 15-30 parts of modified nitrile rubber, 5-8 parts of modified white carbon black, 1-3 parts of lignocellulose, 2-3 parts of nano zinc oxide, 2-4 parts of a modification accelerator M, 0.5-1 part of stearic acid, 1-3 parts of sulfur, 1-2 parts of a trivet guanidine organic antibacterial agent XT-11 and 1-2 parts of an anti-aging agent BHT.
Preferably, the production process of the antibacterial sealing rubber of the water delivery pipeline of the dish-washing machine comprises the following steps:
s1: taking styrene-butadiene rubber and modified nitrile rubber, plasticating the styrene-butadiene rubber and the modified nitrile rubber on a rubber mixing mill with the temperature of 40-50 ℃ until the Wilson plasticity is 0.55-0.60, sequentially adding sulfur, a modification accelerator M, nano zinc oxide, stearic acid, lignocellulose and modified white carbon black, mixing at the temperature of 40-50 ℃ for 25-30 min, uniformly turning the rubber material under the roll gap of 5-7 mm, discharging the rubber material, naturally cooling to room temperature, and standing for 18-25 h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding a trivet guanidine organic antibacterial agent XT-11 and an anti-aging agent BHT, and heating and pressing for 3-5 min in a four-column oil press with the temperature of 150-166 ℃ and the pressure of 20-25 MPa to obtain the antibacterial sealing rubber.
Preferably, the preparation method of the modified nitrile rubber in the step S1 is as follows: under the protection of nitrogen, taking nitrile rubber, dissolving the nitrile rubber in acetone, adding a Pd/resin catalyst, carrying out three-time replacement by hydrogen, reacting for 6-8 hours at the temperature of 50-55 ℃ and the pressure of 5-7 MPa, carrying out suction filtration to recover the Pd/resin catalyst, carrying out vacuum drying for 6-8 hours at the temperature of 55-60 ℃ to obtain hydrogenated nitrile rubber, heating and melting the hydrogenated nitrile rubber and ethylene propylene diene monomer, adding a hydrogenated styrene-butadiene block copolymer, stirring, naturally cooling to 25-35 ℃, tabletting and granulating.
Preferably, the modified nitrile rubber is prepared from hydrogenated nitrile rubber, ethylene propylene diene monomer rubber and hydrogenated styrene-butadiene block copolymer according to the mass ratio of 8-10: 2-3: 1, and mixing.
Preferably, the Pd/resin catalyst is a heterogeneous catalyst with palladium supported on a resin, and the resin is a chelate resin.
Preferably, the preparation method of the modification accelerator M in the step S1 is as follows: dissolving the accelerator M and potassium hydroxide with ethanol, adding 1-ethyl-3-methylimidazole chloride, stirring for 40-60 min at room temperature by an electric stirrer, filtering inorganic solids, evaporating ethanol, extracting with anhydrous acetone, filtering potassium chloride, evaporating acetone, and drying in a vacuum drying oven at 85-95 ℃ for 9-10 h to obtain the modified accelerator M.
Preferably, the mass ratio of the accelerator M to the potassium hydroxide to the 1-ethyl-3-methylimidazole chloride is 3:1: 2-3.
Preferably, the preparation method of the modified white carbon black in the step S1 specifically comprises the following steps:
s101: weighing white carbon black and a silane coupling agent KH450, preparing a white carbon black/polyvinyl alcohol suspension by taking polyvinyl alcohol as a dispersing agent, and then mixing the white carbon black and the polyvinyl alcohol suspension according to a volume ratio of 3:6:50 preparing a mixed solution of a silane coupling agent KH450, water and absolute ethyl alcohol, mixing the two components, reacting for 4-5 hours at 85-90 ℃, centrifugally separating solids, washing the solids with absolute ethyl alcohol for multiple times, and drying the solids at 95-105 ℃ for 2-3 hours to obtain a component A;
s102: cleaning and drying a flask, sequentially adding loose particles of polyisoprene rubber, sodium bicarbonate and ethyl acetate into distilled water, magnetically stirring for 2-3 hours at a water bath temperature of 35-45 ℃, then cooling to 8-12 ℃, adding acetone, slowly dropwise adding ammonium persulfate solution into the flask by using a constant pressure dropping funnel, reacting for 6-8 hours, and performing suction filtration, washing for three times and drying to obtain epoxidized polyisoprene;
s103: and adding the epoxidized polyisoprene and the component A into a pulverizer, stirring for 3-5 minutes, fully and uniformly mixing the epoxidized polyisoprene and the component A, and placing the mixture into a baking oven at 140-160 ℃ for heat treatment for 20-30 minutes to obtain the modified white carbon black.
Preferably, in the step S101, the mass ratio of the white carbon black to the silane coupling agent KH450 is 5:1.
preferably, the mass ratio of the epoxidized polyisoprene to component a in step S103 is 1:10.
the invention has the beneficial effects that:
according to the invention, the hydrogenated styrene-butadiene block copolymer serving as a third component is introduced into a blending system of hydrogenated nitrile rubber and ethylene propylene diene monomer, so that the compatibility of the blending system is effectively improved, the silane coupling agent KH450 and the epoxidized polyisoprene are introduced to modify the white carbon black, the epoxy groups in the epoxidized polyisoprene react with the hydroxyl groups on the surface of the white carbon black, no volatile organic matters are generated in the reaction, the environment-friendly requirement is met, the polyisoprene is coated on the surface of the white carbon black to achieve the effect of isolating the white carbon black, the dispersibility of the white carbon black in a rubber matrix is enhanced, and the physical and mechanical properties of the rubber are improved. Meanwhile, the invention adds the organic antibacterial agent XT-11 of the trivet guanidine into the rubber to ensure that the rubber product has an antibacterial function.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of modified nitrile rubber
Under the protection of nitrogen, 100g of nitrile rubber is weighed and dissolved in 900g of acetone, 30g of Pd/chelating resin catalyst is added, three times of replacement are carried out by hydrogen, the Pd/resin catalyst is recovered by suction filtration under the conditions of 55 ℃ and 6MPa of pressure for 8 hours, the hydrogenated nitrile rubber is obtained by vacuum drying at 60 ℃ for 8 hours, 80.4g of hydrogenated nitrile rubber and 20.5g of ethylene propylene diene monomer rubber are weighed and melted by heating, 10.1g of hydrogenated styrene-butadiene block copolymer is added for stirring, and tabletting and granulating are carried out when the mixture is naturally cooled to 30 ℃.
2. Preparation of modification promoter M
30.6g of accelerator M and 10.2g of potassium hydroxide are weighed and dissolved by ethanol, 26.5g of 1-ethyl-3-methylimidazole chloride is added, the mixture is stirred by an electric stirrer at room temperature for 50min, inorganic solid is filtered, ethanol is evaporated, extraction is performed by anhydrous acetone, the acetone is evaporated after potassium chloride is filtered, and the mixture is dried in a vacuum drying oven at 90 ℃ for 10h, so that the modified accelerator M is obtained.
3. Preparation of modified white carbon black
S101: weighing 30.5g of white carbon black and 6.1g of silane coupling agent KH450, preparing white carbon black/polyvinyl alcohol suspension by taking polyvinyl alcohol as a dispersing agent, and then mixing the white carbon black/polyvinyl alcohol suspension with the polyvinyl alcohol according to the volume ratio of 3:6:50 preparing a silane coupling agent KH450, mixing water and absolute ethyl alcohol to obtain 118mL, mixing the two components, reacting at 90 ℃ for 5 hours, centrifuging to separate solid, washing with absolute ethyl alcohol for multiple times, and drying at 100 ℃ for 2 hours to obtain a component A;
s102: cleaning and drying 50mL two-neck flasks, sequentially adding 0.5g of polyisoprene rubber loose powder particles with the particle size of 40 meshes, 1.0g of sodium bicarbonate and 3.0mL of ethyl acetate into 2mL of distilled water by adopting a titanium-supported catalytic bulk precipitation polymerization method, magnetically stirring for 3h at the water bath temperature of 40 ℃, then cooling to 10 ℃, adding 1.5mL of acetone, slowly dropwise adding 5mL of ammonium persulfate solution with the mass fraction of 1% into the two-neck flasks by using a constant-pressure dropping funnel, reacting for 8h, filtering, washing for three times, and drying to obtain epoxidized polyisoprene;
s103: weighing 2g of epoxidized polyisoprene and 20g of component A, adding into a pulverizer, stirring for 5min, fully and uniformly mixing the two components, and placing into a baking oven at 150 ℃ for heat treatment for 30min to obtain the modified white carbon black.
4. Preparation of antibacterial sealing rubber
S1: taking 30 parts of styrene-butadiene rubber and 17 parts of modified nitrile-butadiene rubber, plasticating the styrene-butadiene rubber on a rubber mixing mill with the temperature of 45 ℃ until the Wildebrand plasticity is 0.55, sequentially adding 1 part of sulfur, 3 parts of a modification accelerator M, 2 parts of nano zinc oxide, 0.7 part of stearic acid, 2 parts of lignocellulose and 7 parts of modified white carbon black, mixing at the temperature of 45 ℃ for 30min, uniformly mixing the rubber material at the roll gap of 5mm, discharging the rubber material, naturally cooling to room temperature, and standing for 24h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding 2 parts of the organic antibacterial agent XT-11 and 2 parts of the antioxidant BHT, and heating and pressing for 5min in a four-column oil press with the temperature of 156 ℃ and the pressure of 20MPa to obtain the antibacterial sealing rubber.
Example 2
The preparation method of the modified nitrile rubber, the modified accelerator M and the modified white carbon black is the same as that of the example 1.
The preparation method of the antibacterial sealing rubber comprises the following steps:
s1: taking 32 parts of styrene-butadiene rubber and 22 parts of modified nitrile rubber, plasticating the styrene-butadiene rubber to have a Wildew plasticity of 0.58 on a rubber mixing machine with a temperature of 48 ℃, sequentially adding 2 parts of sulfur, 3 parts of a modification accelerator M, 2 parts of nano zinc oxide, 0.8 part of stearic acid, 3 parts of lignocellulose and 7 parts of modified white carbon black, mixing at the temperature of 48 ℃ for 28min, uniformly mixing the rubber material at a roll gap of 5mm, discharging the rubber material, naturally cooling to room temperature, and standing for 20h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding 2 parts of organic antibacterial agent XT-11 parts of trivet guanidine and 2 parts of anti-aging agent BHT, and heating and pressing for 4min in a four-column oil press with the temperature of 155 ℃ and the pressure of 22Mpa to obtain the antibacterial sealing rubber.
Example 3
The preparation method of the modified nitrile rubber, the modified accelerator M and the modified white carbon black is the same as that of the example 1.
The preparation method of the antibacterial sealing rubber comprises the following steps:
s1: taking 40 parts of styrene-butadiene rubber and 28 parts of modified nitrile-butadiene rubber, plasticating the 40 parts on a rubber mixing machine with the temperature of 44 ℃ until the Wildew plasticity is 0.60, sequentially adding 3 parts of sulfur, 4 parts of a modification accelerator M, 3 parts of nano zinc oxide, 0.9 part of stearic acid, 1 part of lignocellulose and 8 parts of modified white carbon black, mixing at the temperature of 44 ℃ for 30min, uniformly mixing the rubber material under the roll gap of 7mm, discharging the rubber material, naturally cooling to room temperature, and standing for 25h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding 1 part of the organic antibacterial agent XT-11 parts of the organic antibacterial agent XT and 1 part of the anti-aging agent BHT, and heating and pressing for 3min in a four-column oil press with the temperature of 160 ℃ and the pressure of 23Mpa to obtain the antibacterial sealing rubber.
Comparative example 1
The preparation methods of the modification accelerator M and the modified white carbon black are the same as in example 1.
The preparation method of the antibacterial sealing rubber comprises the following steps:
s1: taking 40 parts of styrene-butadiene rubber, 20 parts of hydrogenated nitrile rubber and 4 parts of ethylene propylene diene monomer rubber, plasticating on a rubber mixing machine at 46 ℃ until the Weissel plasticity is 0.56, sequentially adding 2 parts of sulfur, 3 parts of a modification accelerator M, 2 parts of nano zinc oxide, 0.7 part of stearic acid, 1 part of lignocellulose and 7 parts of modified white carbon black, mixing at 46 ℃ for 30min, uniformly mixing the rubber material at a roll gap of 6mm, discharging, naturally cooling to room temperature, and standing for 24h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding the organic antibacterial agent XT-11 parts of the trivet guanidine and the anti-aging agent BHT 1 parts, and heating and pressing for 5min in a four-column oil press with the temperature of 160 ℃ and the pressure of 25Mpa to obtain the antibacterial sealing rubber.
Comparative example 2
The preparation methods of the modified nitrile rubber and the modified white carbon black are the same as in example 1.
The preparation method of the antibacterial sealing rubber comprises the following steps:
s1: taking 38 parts of styrene-butadiene rubber and 23 parts of modified nitrile rubber, plasticating the styrene-butadiene rubber on a rubber mixing mill with the temperature of 48 ℃ until the Wilded plasticity is 0.58, sequentially adding 1 part of sulfur, 2 parts of accelerator M, 3 parts of nano zinc oxide, 1 part of stearic acid, 1 part of lignocellulose and 7 parts of modified white carbon black, mixing at the temperature of 48 ℃ for 25min, uniformly turning and smelting the rubber material under the roll gap of 6mm, blanking, naturally cooling to room temperature, and standing for 24h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding 2 parts of organic antibacterial agent XT-11 and 2 parts of antioxidant BHT, and heating and pressing for 4min in a four-column oil press with the temperature of 162 ℃ and the pressure of 20Mpa to obtain the antibacterial sealing rubber.
Comparative example 3
The preparation method of the modified nitrile rubber and the modified accelerator M is the same as that of example 1.
The preparation method of the antibacterial sealing rubber comprises the following steps:
s1: taking 35 parts of styrene-butadiene rubber and 26 parts of modified nitrile-butadiene rubber, plasticating the styrene-butadiene rubber on a rubber mixing mill with the temperature of 49 ℃ until the Wildebrand plasticity is 0.56, sequentially adding 3 parts of sulfur, 3 parts of a modification accelerator M, 3 parts of nano zinc oxide, 0.8 part of stearic acid, 2 parts of lignocellulose, 5 parts of white carbon black and 4501 parts of a silane coupling agent KH, mixing at the temperature of 49 ℃ for 30min, uniformly mixing the rubber material under the roll gap of 6mm, discharging the rubber material, naturally cooling to room temperature, and standing for 18h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding 1 part of the organic antibacterial agent XT-11 parts of the organic antibacterial agent XT and 1 part of the anti-aging agent BHT, and heating and pressing for 5min in a four-column oil press with the temperature of 165 ℃ and the pressure of 24Mpa to obtain the antibacterial sealing rubber.
Comparative example 4
The preparation method of the modified nitrile rubber, the modified accelerator M and the modified white carbon black is the same as that of the example 1.
The preparation method of the antibacterial sealing rubber comprises the following steps:
s1: taking 35 parts of styrene-butadiene rubber and 28 parts of modified nitrile rubber, plasticating the styrene-butadiene rubber on a rubber mixing mill with the temperature of 45 ℃ until the Wildebrand plasticity is 0.59, sequentially adding 2 parts of sulfur, 2 parts of a modification accelerator M, 3 parts of nano zinc oxide, 1 part of stearic acid, 2 parts of lignocellulose and 8 parts of modified white carbon black, mixing at the temperature of 45 ℃ for 30min, uniformly turning and refining a sizing material at a roll gap of 6mm, discharging the sizing material, naturally cooling to room temperature, and standing for 24h to obtain a mixed rubber;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding 2 parts of anti-aging agent BHT, and heating and pressing in a four-column oil press with the temperature of 163 ℃ and the pressure of 24Mpa for 5min to obtain the antibacterial sealing rubber.
Physical and mechanical property test
The seal rubbers prepared in examples 1 to 3 and comparative examples 1 to 4 were tested for tensile strength and elongation at break according to national standard GB/T528-2009, for tear strength according to national standard GB/T529-2008, and for Shore A hardness according to national standard GB/T531.1-2008.
TABLE 1 test results of physical and mechanical Properties of samples
As can be seen from the data of Table 1, the comparative example 1, in which the hydrogenated styrene-butadiene block copolymer was not added, shows that the tensile strength, elongation at break, tear strength and Shore A hardness of the prepared sealing rubber were all lower than those of examples 1 to 3 and comparative example 4, indicating that the addition of the hydrogenated styrene-butadiene block copolymer improved the tensile strength, elongation at break, tear strength and Shore A hardness of the rubber to some extent, with the tensile strength and elongation at break being improved more significantly; the tensile strength, the elongation at break and the tearing strength of the prepared sealing rubber measured by the comparative example 2 without adding 1-ethyl-3-methylimidazole chloride are slightly worse than those of the examples 1-3 and the comparative example 4, and the Shore A hardness is not obviously different from those of the examples 1-3 and the comparative example 4, so that the tensile strength, the elongation at break and the tearing strength of the rubber are improved to a certain extent by using the ionic liquid type accelerator, and the possible reasons are that the dispersibility of the white carbon black in the rubber is effectively improved by using the ionic liquid type rubber accelerator, and the interaction between the filler and the rubber matrix is enhanced; in comparative example 3, the tensile strength, elongation at break, tear strength and Shore A hardness of the prepared sealing rubber are slightly worse than those of examples 1-3 and comparative example 4, probably because the epoxy group reacts with the silicon ethoxy group on the surface of the white carbon black, the polyisoprene is combined with the surface of the white carbon black through a chemical bond, the polarity of the surface of the white carbon black is shielded, and the white carbon black is better dispersed in the rubber matrix through better compatibility with the rubber matrix.
Antibacterial property test
The sealing rubbers prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to antibacterial performance test according to national standard QB/T2881-2007 by a double-layer flat-plate punching method. Placing rubber particles into a perforated bacteria indicator bacteria flat plate, standing for 15-20 min, placing into an electrothermal constant temperature incubator at 37 ℃ for culturing for 12h, measuring the diameters of sponge sizing material antibacterial spots in an escherichia coli culture dish and a staphylococcus aureus culture dish by using an ultraviolet-visible spectrophotometer, measuring the diameter of each antibacterial spot for 3 times, and taking an average value. The test results obtained are shown in table 2 below.
Table 2 results of antibacterial property test
As can be seen from the data in Table 2, the sealing rubbers prepared in examples 1 to 3 and comparative examples 1 to 3 have good antibacterial performance, and the antibacterial effect of the organic guanidine antibacterial agent XT-11 on staphylococcus aureus is greater than that of escherichia coli, and the antibacterial performance measured by the sealing rubber prepared in comparative example 4 without adding the organic guanidine antibacterial agent XT-11 is slightly poorer than that of examples 1 to 3 and comparative examples 1 to 3, which means that the antibacterial performance of the sealing rubber is improved to a certain extent by adding the organic guanidine antibacterial agent XT-11, because the antibacterial agent mainly exists in the form of guanidine salt, the guanidine salt can be derived into guanidine derivatives with strong alkalinity, high stability and good biological activity, so that the good antibacterial performance is obtained, and in addition, the organic active functional group of the guanidine organic antibacterial agent carries positive charges, and the bacteria with negative charges on the surface can be adsorbed by virtue of coulombic force, so that the cell wall of the bacteria and the integrity of the whole cell structure are destroyed, and the death of the bacteria is finally caused.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The antibacterial sealing rubber for the water delivery pipeline of the dish washer is characterized by comprising the following raw materials in parts by weight: 25-40 parts of styrene-butadiene rubber, 15-30 parts of modified nitrile rubber, 5-8 parts of modified white carbon black, 1-3 parts of lignocellulose, 2-3 parts of nano zinc oxide, 2-4 parts of a modification accelerator M, 0.5-1 part of stearic acid, 1-3 parts of sulfur, 1-2 parts of a trivet guanidine organic antibacterial agent XT-11 and 1-2 parts of an anti-aging agent BHT.
2. The process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 1, which is characterized by comprising the following steps:
s1: taking styrene-butadiene rubber and modified nitrile rubber, plasticating the styrene-butadiene rubber and the modified nitrile rubber on a rubber mixing mill with the temperature of 40-50 ℃ until the Wilson plasticity is 0.55-0.60, sequentially adding sulfur, a modification accelerator M, nano zinc oxide, stearic acid, lignocellulose and modified white carbon black, mixing at the temperature of 40-50 ℃ for 25-30 min, uniformly turning the rubber material under the roll gap of 5-7 mm, discharging the rubber material, naturally cooling to room temperature, and standing for 18-25 h to obtain a rubber compound;
s2: cutting the prepared rubber compound into rubber blank sheets with the mould shape requirement, adding a trivet guanidine organic antibacterial agent XT-11 and an anti-aging agent BHT, and heating and pressing for 3-5 min in a four-column oil press with the temperature of 150-166 ℃ and the pressure of 20-25 MPa to obtain the antibacterial sealing rubber.
3. The process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 2, wherein the preparation method of the modified nitrile rubber in the step S1 is as follows: under the protection of nitrogen, taking nitrile rubber, dissolving the nitrile rubber in acetone, adding a Pd/resin catalyst, carrying out three-time replacement by hydrogen, reacting for 6-8 hours at the temperature of 50-55 ℃ and the pressure of 5-7 MPa, carrying out suction filtration to recover the Pd/resin catalyst, carrying out vacuum drying for 6-8 hours at the temperature of 55-60 ℃ to obtain hydrogenated nitrile rubber, heating and melting the hydrogenated nitrile rubber and ethylene propylene diene monomer, adding a hydrogenated styrene-butadiene block copolymer, stirring, naturally cooling to 25-35 ℃, tabletting and granulating.
4. The production process of the antibacterial sealing rubber for the water delivery pipeline of the dish washer, according to claim 3, is characterized in that the modified nitrile rubber is prepared from 8-10 mass percent of hydrogenated nitrile rubber, ethylene propylene diene monomer rubber and hydrogenated styrene-butadiene block copolymer: 2-3: 1, and mixing.
5. The process for producing an antibacterial sealing rubber for a water delivery pipeline of a dish washer according to claim 3, wherein the Pd/resin catalyst is a heterogeneous catalyst with palladium supported on a resin, and the resin is a chelate resin.
6. The process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 2, wherein the preparation method of the modification accelerator M in the step S1 is as follows: dissolving the accelerator M and potassium hydroxide with ethanol, adding 1-ethyl-3-methylimidazole chloride, stirring for 40-60 min at room temperature by an electric stirrer, filtering inorganic solids, evaporating ethanol, extracting with anhydrous acetone, filtering potassium chloride, evaporating acetone, and drying in a vacuum drying oven at 85-95 ℃ for 9-10 h to obtain the modified accelerator M.
7. The process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 6, wherein the mass ratio of the accelerator M to the potassium hydroxide to the 1-ethyl-3-methylimidazole chloride is 3:1: 2-3.
8. The process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 2, wherein the preparation method of the modified white carbon black in the step S1 specifically comprises the following steps:
s101: weighing white carbon black and a silane coupling agent KH450, preparing a white carbon black/polyvinyl alcohol suspension by taking polyvinyl alcohol as a dispersing agent, and then mixing the white carbon black and the polyvinyl alcohol suspension according to a volume ratio of 3:6:50 preparing a mixed solution of a silane coupling agent KH450, water and absolute ethyl alcohol, mixing the two components, reacting for 4-5 hours at 85-90 ℃, centrifugally separating solids, washing the solids with absolute ethyl alcohol for multiple times, and drying the solids at 95-105 ℃ for 2-3 hours to obtain a component A;
s102: cleaning and drying a flask, wherein the mass ratio of the flask to the flask is 1:2:5, sequentially adding loose polyisoprene rubber particles, sodium bicarbonate and ethyl acetate into distilled water, magnetically stirring for 2-3 hours at a water bath temperature of 35-45 ℃, then cooling to 8-12 ℃, adding acetone, slowly dropwise adding ammonium persulfate solution into a flask by using a constant pressure dropping funnel, reacting for 6-8 hours, and then carrying out suction filtration, washing for three times and drying to obtain epoxidized polyisoprene;
s103: and adding the epoxidized polyisoprene and the component A into a pulverizer, stirring for 3-5 minutes, fully and uniformly mixing the epoxidized polyisoprene and the component A, and placing the mixture into a baking oven at 140-160 ℃ for heat treatment for 20-30 minutes to obtain the modified white carbon black.
9. The process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 8, wherein the mass ratio of the white carbon black to the silane coupling agent KH450 in the step S101 is 5:1.
10. the process for producing the antibacterial sealing rubber for the water delivery pipeline of the dish washer according to claim 8, wherein the mass ratio of the epoxidized polyisoprene to the component A in the step S103 is 1:10.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015154492A1 (en) * | 2014-04-10 | 2015-10-15 | 戴李宗 | Organic-inorganic composite vulcanized nitrile rubber for sealing element and preparation method therefor |
| CN105131377A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | Aging-resistant cable |
| CN105924690A (en) * | 2016-05-13 | 2016-09-07 | 吉林师范大学 | Anti-aging modified natural rubber composite material |
| CN109096560A (en) * | 2018-08-07 | 2018-12-28 | 浙江久运汽车零部件有限公司 | A kind of high-low temperature resistant oiliness nitrile rubber pipe and preparation method thereof |
| CN112980064A (en) * | 2021-02-25 | 2021-06-18 | 浙江双箭橡胶股份有限公司 | Nano inorganic modified rubber composite material and preparation method thereof |
| WO2022041930A1 (en) * | 2020-08-27 | 2022-03-03 | 茂泰(福建)鞋材有限公司 | Leather scrap-modified rubber outsole and preparation method therefor |
| CN114716742A (en) * | 2022-04-02 | 2022-07-08 | 众邦电缆集团有限公司 | Rubber outer sheath of cable and preparation method thereof |
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015154492A1 (en) * | 2014-04-10 | 2015-10-15 | 戴李宗 | Organic-inorganic composite vulcanized nitrile rubber for sealing element and preparation method therefor |
| CN105131377A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | Aging-resistant cable |
| CN105924690A (en) * | 2016-05-13 | 2016-09-07 | 吉林师范大学 | Anti-aging modified natural rubber composite material |
| CN109096560A (en) * | 2018-08-07 | 2018-12-28 | 浙江久运汽车零部件有限公司 | A kind of high-low temperature resistant oiliness nitrile rubber pipe and preparation method thereof |
| WO2022041930A1 (en) * | 2020-08-27 | 2022-03-03 | 茂泰(福建)鞋材有限公司 | Leather scrap-modified rubber outsole and preparation method therefor |
| CN112980064A (en) * | 2021-02-25 | 2021-06-18 | 浙江双箭橡胶股份有限公司 | Nano inorganic modified rubber composite material and preparation method thereof |
| CN114716742A (en) * | 2022-04-02 | 2022-07-08 | 众邦电缆集团有限公司 | Rubber outer sheath of cable and preparation method thereof |
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