CN114752320A - Humidity-induced butyl rubber sealant with high cohesiveness and good antibacterial performance, preparation method and application - Google Patents
Humidity-induced butyl rubber sealant with high cohesiveness and good antibacterial performance, preparation method and application Download PDFInfo
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- CN114752320A CN114752320A CN202210426562.7A CN202210426562A CN114752320A CN 114752320 A CN114752320 A CN 114752320A CN 202210426562 A CN202210426562 A CN 202210426562A CN 114752320 A CN114752320 A CN 114752320A
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- Prior art keywords
- butyl rubber
- modified inorganic
- rubber sealant
- cohesiveness
- inorganic nanoparticles
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Links
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 149
- 239000004589 rubber sealant Substances 0.000 title claims abstract description 110
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 162
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000292 calcium oxide Substances 0.000 claims abstract description 40
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000006698 induction Effects 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 6
- 229920000098 polyolefin Polymers 0.000 claims abstract description 6
- 239000012945 sealing adhesive Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- 239000000463 material Substances 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- 239000007864 aqueous solution Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 40
- 229920002367 Polyisobutene Polymers 0.000 claims description 38
- 229920001661 Chitosan Polymers 0.000 claims description 35
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 30
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000004014 plasticizer Substances 0.000 claims description 18
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 17
- 229940047670 sodium acrylate Drugs 0.000 claims description 17
- 230000003712 anti-aging effect Effects 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 5
- 239000011087 paperboard Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 229920006267 polyester film Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004200 microcrystalline wax Substances 0.000 claims description 3
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- 229940099259 vaseline Drugs 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 7
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- 239000004698 Polyethylene Substances 0.000 description 17
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- 230000000052 comparative effect Effects 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 13
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- 238000011282 treatment Methods 0.000 description 9
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- 125000003277 amino group Chemical group 0.000 description 6
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- 239000003999 initiator Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 6
- 229920001690 polydopamine Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
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- 241000588724 Escherichia coli Species 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical group 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
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- 238000002411 thermogravimetry Methods 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance, a preparation method and application thereof, the butyl rubber sealant has performance indexes reaching and exceeding the performance indexes of the existing similar products, has high cohesiveness and antibacterial performance triggered by specific humidity, slows down the viscosity failure and the microbial degradation process of the butyl rubber sealant, and prolongs the service life; the functions of the functionalized crosslinked network modified inorganic nanoparticles and the calcium oxide particles under the action of water molecules (humidity) can be effectively regulated, the two particles are not used independently, and have a certain synergistic effect when acting with the water molecules, so that the effect of retarding the bonding property failure of the butyl rubber sealant by humidity induction is facilitated, and meanwhile, the antibacterial performance is improved; the adhesive can be used as a sealing adhesive for substrates such as glass, polyolefin films and the like, and has wide universality and strong practicability. The preparation method disclosed by the invention is simple in operation steps and high in preparation implementation feasibility.
Description
Technical Field
The invention relates to the technical field of automotive sealants, in particular to a butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance, and a preparation method and application thereof.
Background
Butyl rubber is an elastic polymer formed by copolymerizing isobutene and a small amount of isoprene, has the characteristics of low air permeability, good air tightness, high adhesive force, low temperature resistance and aging resistance, is widely used in bonding and sealing materials for the automobile field and the building industry, and can be used as a main bonding agent, a tackifier and a modifier. These bonding and sealing materials containing butyl rubber are relatively weak and are susceptible to creep under load, for example, reinforcing agents or fillers (e.g., kaolin) are often added to further improve the mechanical and physical properties. When used as a rubber adhesive sealing material for vehicles, butyl rubber is required to be mixed with various component materials (such as reinforcing agents, coloring agents, tackifying resins, plasticizers and the like) for processing and molding, so as to prepare rubber products such as rubber compounds, adhesive tapes, rubber hoses, adhesives and waterproof coils, which have high adhesion, good sealing performance and excellent aging resistance.
Butyl rubber sealants for vehicles include both non-vulcanized and vulcanized types. Compared with a vulcanized and crosslinked sealing material, the non-vulcanized butyl rubber sealing and protecting material is a non-permanent crosslinked curing material, has the characteristics of no solvent, good flexibility and strong plasticity and adaptability, does not generate stress concentration, and is better suitable for the surfaces of various materials. In recent years, non-vulcanized butyl rubber sealing and protecting materials have been gradually applied to the fields of rail transit, automobiles and aviation. However, the butyl rubber sealant used in the field of automobiles generally has the problems of poor air tightness, low temperature resistance, easy falling and the like. Scholars at home and abroad mainly study the influence of the selection of components such as matrix rubber, matrix resin, tackifying resin, filler, plasticizer and the like and different formula designs on the adhesive strength and the peel strength of the sealant. When the butyl rubber sealant for the vehicle is aged and damaged under the action of external ultraviolet rays, oxygen, ozone and microorganisms for a long time, a protection mechanism cannot be generated spontaneously to slow down the bonding property failure process of butyl rubber and various base layer interfaces, the further corrosion action of the microorganisms is difficult to prevent, and the service life is greatly influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance, a preparation method and application thereof, the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance has performance indexes reaching and exceeding those of the existing similar products, has high cohesiveness and antibacterial performance triggered by specific humidity, slows down the viscosity failure and microbial degradation process of the butyl rubber sealant and prolongs the service life; the designed and prepared functionalized crosslinked network modified inorganic nanoparticles are used for replacing inorganic reinforcing agent components in the existing butyl rubber sealant, and the components and the formula of the rubber do not need to be changed to a great extent; the functional crosslinking network modified inorganic nano particles and the calcium oxide particles can be effectively regulated and controlled under the action of water molecules (humidity), the two particles are not used independently, and have a certain synergistic effect when acting with the water molecules, so that the effect of slowing down the bonding property failure of the butyl rubber sealant through humidity induction is facilitated, and meanwhile, the antibacterial performance is improved. The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance can be used as a sealing adhesive for glass, polyolefin films, polyester films, polyvinyl chloride films, stainless steel, paperboards and sheepskin, and has wide universality and strong practicability. The preparation method of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance, disclosed by the invention, has the advantages of simple operation steps and high feasibility of preparation and implementation, and lays a foundation for smooth large-scale application of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance.
In order to achieve the purpose, the technical scheme of the invention is to design a butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance, which comprises the following components in parts by weight: 100 parts of butyl rubber, 250 parts of polyisobutylene 150, 150 parts of functionalized crosslinked network modified inorganic nanoparticles, 15-30 parts of calcium oxide, 60-80 parts of tackifying resin, 10-15 parts of carbon black, 10-15 parts of anti-aging agent and 20-30 parts of plasticizer.
The preferable technical scheme is that the polyisobutylene comprises 40% mass fraction of low molecular weight polyisobutylene, 20% mass fraction of medium molecular weight polyisobutylene and 40% mass fraction of high molecular weight polyisobutylene, wherein the number average molecular weight of the low molecular weight polyisobutylene is 200-.
Further preferably, the particle size range of the calcium oxide is 100-160 nm; the tackifying resin is one of C5 petroleum resin, rosin resin and terpene resin; the specific surface area of the carbon black is 400-1000m2(iv) g; the anti-aging agent is antioxidant 1010 or antioxidant 168; the plasticizer is one of paraffin oil, naphthenic oil, dioctyl phthalate, vaseline and microcrystalline wax.
A preparation method of a butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance comprises the following steps:
h1: according to the weight component formula of the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance, the functionalized crosslinked network modified inorganic nano-particles, the calcium oxide and part of the tackifying resin are placed in a mixer, and are uniformly mixed at the temperature of 120 ℃, and a premixed material A is obtained after cooling, wherein the mass feed ratio of the functionalized crosslinked network modified inorganic nano-particles, the calcium oxide and the tackifying resin is 150: 15-30: 30-40;
h2: according to the weight component formula of the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance, placing butyl rubber and polyisobutylene in a plasticator, plasticating and mixing uniformly at the temperature of 110 ℃ to obtain a premixed material B;
h3: according to the weight component formula of the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance, the rest of tackifying resin, carbon black, anti-aging agent and plasticizer are sequentially added into an internal mixer, and are mixed for 15min at the temperature of 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 10-15 min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial property.
In the preferred technical solution, in the step H1, the method for preparing the functionalized crosslinked network modified inorganic nanoparticles includes the following steps:
s1: preparing modified inorganic nano particles, dispersing the inorganic nano particles in absolute ethyl alcohol, performing ultrasonic dispersion for more than 30min, and mechanically stirring uniformly to obtain an ethanol dispersion liquid of the inorganic nano particles, wherein the mass concentration of the inorganic nano particles is 16.7-20 mg/mL; dissolving gamma-methacryloxypropyl trimethoxy silane in absolute ethyl alcohol, adding a proper amount of deionized water, and adjusting the pH to 4 with inorganic acid to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxy silane, wherein the mass feed ratio of the gamma-methacryloxypropyl trimethoxy silane to the absolute ethyl alcohol to the deionized water is 3-5: 16: 2; placing the ethanol dispersion liquid of the inorganic nano-particles into a reaction bottle, slowly adding the prehydrolysis solution of the gamma-methacryloxypropyltrimethoxysilane into the reaction bottle, heating to 80 ℃, stirring, refluxing and reacting for 6 hours, and sequentially centrifuging, washing, drying and grinding the reaction product mixed liquid to obtain modified inorganic nano-particles;
s2: preparing dispersion liquid of modified inorganic nano particles, and dissolving chitosan in acetic acid aqueous solution to obtain acetic acid aqueous solution of chitosan, wherein the volume fraction of acetic acid in the acetic acid aqueous solution is 5%, and the mass concentration of chitosan is 20-25 mg/mL; dispersing the modified inorganic nano-particles prepared in the step S1 in the acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain a dispersion liquid of the modified inorganic nano-particles, wherein the mass concentration of the modified inorganic nano-particles is 15-20 mg/mL;
S3: adding acrylic acid into a sodium hydroxide aqueous solution, and reacting for 5-10 h at normal temperature to obtain an aqueous solution of acrylic acid and sodium acrylate, wherein the molar feed ratio of the acrylic acid to a sodium hydroxide solute is 2.2-3: 1; and (2) sequentially adding the dispersion of the modified inorganic nanoparticles prepared in the step (S2), dopamine hydrochloride and ammonium persulfate into an aqueous solution of acrylic acid and sodium acrylate, introducing nitrogen to remove oxygen, heating to 80 ℃, reacting for 12 hours, removing unreacted monomers and small molecules by a dialysis method after the reaction is finished, and freeze-drying to obtain the functionalized crosslinked network modified inorganic nanoparticles coated with a macromolecular crosslinked shell layer on the surface, wherein the mass feed ratio of the acrylic acid, the sodium acrylate, the modified inorganic nanoparticles, the dopamine hydrochloride and the ammonium persulfate is 1: 0.015: 0.2-0.25: 0.05.
In a further preferred technical solution, in the step S1, the inorganic nanoparticles are one of calcium carbonate, talc, ferroferric oxide, silica, and titanium dioxide.
Further preferably, in the step S3, the particle size of the functionalized crosslinked network modified inorganic nanoparticles is 20-100nm, and the mass percentage of the polymer crosslinked shell layer in the functionalized crosslinked network modified inorganic nanoparticles is 15-30%.
The butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance is applied as a sealing adhesive for glass, polyolefin films, polyester films, polyvinyl chloride films, stainless steel, paperboards and sheepskins.
The preparation principle of the functionalized crosslinked network modified inorganic nanoparticles (see the attached figure 1): through hydrolysis and condensation of silicon-oxygen methyl in gamma-methacryloxypropyl trimethoxy silane, a siloxane monomer containing double bonds is grafted to the surface of inorganic nano particles, and the surface of the inorganic nano particles has negative charges as a whole due to the existence of hydroxyl and silanol groups; through electrostatic interaction, positively charged chitosan (the surface of which is rich in amino) is adsorbed to the surface of the gamma-methacryloxypropyltrimethoxysilane modified inorganic nanoparticles, and meanwhile, the surface of the inorganic nanoparticles is rich in double-bond groups, so that the gamma-methacryloxypropyltrimethoxysilane modified inorganic nanoparticles are promoted to become a cross-linking agent (called a double-bond-containing modified particle cross-linking agent); in an aqueous phase system, taking double-bond-containing gamma-methacryloxypropyltrimethoxysilane modified inorganic nanoparticles as a cross-linking agent, taking acrylic acid, sodium acrylate and dopamine hydrochloride as monomers, taking ammonium persulfate as an initiator, heating to promote polymerization and cross-linking reaction to occur, forming a semi-interpenetrating high-molecular cross-linked network shell layer (swelling-state functionalized cross-linked network modified inorganic nanoparticles) on the surface of the inorganic nanoparticles, wherein the shell layer is in a hydrophilic swelling state and has carboxylic acid groups, carboxylate groups, catechol functions and amino groups; after dialysis and freeze drying, the original swollen cross-linked network shrinks and collapses due to dehydration and is tightly attached to the surface of the inorganic nano-particles to form the functionalized cross-linked network modified inorganic nano-particles with a dry core-shell structure. The mass fraction of the functionalized crosslinked network shell layer finally formed on the surface of the functionalized crosslinked network modified inorganic nano-particle can be effectively regulated and controlled by regulating and controlling the using amount of the double-bond-containing gamma-methacryloxypropyltrimethoxysilane monomer.
In step H1, the blending principle of the functionalized crosslinked network modified inorganic nanoparticles, calcium oxide and partial tackifying resin is as follows: adding the dried functionalized crosslinked network modified inorganic nanoparticles, calcium oxide and part of tackifying resin into a mixer, uniformly mixing, setting the hot mixing temperature to be 120 ℃, uniformly dispersing the functionalized crosslinked network modified inorganic nanoparticles and the calcium oxide, coating the functionalized crosslinked network modified inorganic nanoparticles and the calcium oxide with the tackifying resin, and cooling after mixing to obtain a premixed material A; the mixing of the functional cross-linked network modified inorganic nanoparticles in a dry state and calcium oxide is beneficial to the mutual contact of the two particles and the performance of the adhesion and antibacterial functions under the induction of humidity during subsequent use; when the hot mixing temperature is higher than 100 ℃, the moisture adsorption of the dry functionalized crosslinked network modified inorganic nanoparticles can be effectively avoided, the resin can be coated with the two inorganic nanoparticles above the softening temperature of the tackifying resin, and the premixed material A obtained by cooling can well isolate the permeation of water vapor, so that the premixed material A can be dispersed in the butyl rubber matrix without affecting the performance of the butyl rubber matrix.
The principle that the humidity triggers the butyl rubber sealant to generate high cohesiveness and excellent antibacterial performance (see the attached figure 2): when the butyl rubber sealant is normally used and is aged and damaged under the action of external ultraviolet rays, oxygen, ozone and microorganisms { see (a) in the attached figure 2 }, under the condition of relative humidity of 20-60%, water molecules permeate into the butyl rubber, and contact and interact with the functionalized crosslinked network modified inorganic nanoparticles and calcium oxide { see (b) in the attached figure 2 }. Firstly, calcium hydroxide is generated by the reaction of calcium oxide and water, and certain heat is generated, so that the butyl rubber has certain corrosivity and is beneficial to improving the antimicrobial and antibacterial properties of the butyl rubber; the functional crosslinking network of the inorganic nanoparticle shell layer contains rich functional groups, such as carboxylic acid groups, carboxylate groups, catechol functional groups and amino groups, under the action of water, the crosslinking network on the surface of the inorganic nanoparticles swells, and due to the existence of the functional groups, the butyl rubber sealant has active groups, can be well combined with the surfaces of various substrates, and has high bonding performance; due to the existence of acrylic acid, calcium hydroxide can further release calcium ions under an acidic condition, and the calcium ions can diffuse into a cross-linked network structure of an adjacent inorganic nanoparticle shell layer, for example, chitosan is rich in amino groups and can be chelated and coordinated with the calcium ions to further swell the network structure of the shell layer, thereby being beneficial to the exertion of the adhesive property of the butyl rubber sealant; chitosan itself has bacteriostatic effect, in which the positive charge carried by the amino group of chitosan combines with the negative charge of the bacterial cell wall, thereby inhibiting bacterial growth. Therefore, under the condition of relative humidity of 20-60%, water molecules permeate into the butyl rubber, contact and interact with the functionalized crosslinked network modified inorganic nanoparticles and calcium oxide, the high viscosity and antibacterial performance of the functionalized crosslinked network modified inorganic nanoparticles are induced, the bonding performance failure process of butyl rubber and a steel plate (taking the steel plate as an example) and a sealing and protecting film is slowed, and the service life is prolonged.
The invention has the advantages and beneficial effects that:
1. when the traditional butyl rubber sealant for vehicles is aged and damaged due to the action of external ultraviolet rays, oxygen, ozone, water and microorganisms for a long time, a protection mechanism cannot be spontaneously generated to slow down the bonding performance failure process of butyl rubber and various base layer interfaces, the further corrosion action of microorganisms is difficult to prevent, and the service life is greatly influenced. Aiming at the problem, the invention provides a butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance, the performance index of the butyl rubber sealant reaches or exceeds that of the existing similar products, the butyl rubber sealant has the special humidity-triggered high cohesiveness and antibacterial performance, the viscosity failure and the microbial degradation process of the butyl rubber sealant are slowed down, and the service life is prolonged.
2. The invention discloses a butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance, which is characterized in that designed and prepared functionalized crosslinked network modified inorganic nanoparticles are used for replacing inorganic reinforcing agent components in the existing butyl rubber sealant, and the components and the formula of rubber do not need to be changed to a great extent.
3. The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance disclosed by the invention can effectively regulate and control the functions of the functionalized crosslinked network modified inorganic nanoparticles and the calcium oxide particles under the action of water molecules (humidity), and the two particles are not used independently, and have a certain synergistic effect when acting with the water molecules, so that the effect of slowing down the cohesive performance failure of the butyl rubber sealant by humidity induction is facilitated, and meanwhile, the antibacterial performance is improved.
4. The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance can be used as a sealing adhesive for glass, polyolefin films, polyester films, polyvinyl chloride films, stainless steel, paperboards and sheepskin, and has wide universality and strong practicability.
5. The preparation method of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance, disclosed by the invention, has the advantages of simple operation steps and high feasibility of preparation and implementation, and lays a foundation for smooth large-scale application of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance.
Drawings
FIG. 1 is a flow chart of the preparation principle of the functionalized crosslinked network modified inorganic nanoparticles;
fig. 2 is a principle that humidity triggers the butyl rubber sealant to generate high cohesiveness and excellent antibacterial performance, fig. 2 (a) is a schematic structural diagram of the butyl rubber sealant which is aged and damaged by external ultraviolet rays, oxygen, ozone and microorganisms in normal use, and fig. 2 (b) is a schematic structural diagram of the butyl rubber sealant after humidity induction;
FIG. 3 is a TEM image of the functionalized crosslinked network-modified inorganic nanoparticles prepared in example 1;
FIG. 4 is a diagram showing an initial state in which a humidity-induced high-adhesiveness and antibacterial butyl rubber sealant prepared in example 1 is adhered to a polyethylene film;
FIG. 5 (a) is an electron microscope scan of the initial state of the butyl rubber sealant with humidity-induced high adhesiveness and good antibacterial property prepared in example 1 adhered to a polyethylene film;
FIG. 5 is an electron microscope scanning image of the butyl rubber sealant prepared in example 1 and having high adhesion and good antibacterial property induced by humidity, adhered to a polyethylene film, after being induced by humidity of 50% for 10 h.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance comprises the following components in parts by weight:
100 parts of butyl rubber;
the polyisobutylene comprises 150 parts of low molecular weight polyisobutylene (the number average molecular weight is 200-;
The inorganic nanoparticles are calcium carbonate, and the particle size of the functionalized crosslinked network modified inorganic nanoparticles is 20nm and is 100 parts;
15 parts of calcium oxide which is nano-scale particles with the particle size range of 100 nm;
60 parts of tackifying resin C5 petroleum resin;
the specific surface area of the carbon black is 1000m 210 parts of per gram;
the anti-aging agent is 1010 parts of antioxidant, 10 parts;
the plasticizer is paraffin oil, and 20 parts.
(II) preparing the functionalized crosslinked network modified inorganic nano-particles, which comprises the following steps:
s1: dispersing 2g of inorganic nanoparticles in 120mL of ethanol, ultrasonically dispersing the mixture for 30min, and mechanically stirring at room temperature at 500rpm to obtain an ethanol dispersion of the inorganic nanoparticles; dissolving 3mL of gamma-methacryloxypropyl trimethoxysilane in 20mL of absolute ethanol, adding 2mL of deionized water, adjusting the pH value to 4 by using dilute HCl, and carrying out prehydrolysis to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxysilane; slowly dropping a prehydrolysis solution of gamma-methacryloxypropyltrimethoxysilane into an ethanol dispersion solution of the inorganic nanoparticles, refluxing for 6 hours at 80 ℃, repeatedly washing a reaction product for 3 times by using high-speed centrifugation (6000rpm and 5min), performing vacuum drying for 24 hours at 60 ℃, and performing grinding treatment to obtain modified inorganic nanoparticles;
S2: dissolving 2g of chitosan in 100mL of acetic acid aqueous solution (acetic acid volume fraction is 5%) to obtain a transparent and uniform acetic acid aqueous solution of chitosan; dispersing 1.5g of the modified inorganic nanoparticles prepared in the step S1 in 100mL of acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain a dispersion liquid of the modified inorganic nanoparticles;
s3: dissolving 1.8g of acrylic acid in 10mL of sodium hydroxide aqueous solution (the mass of the sodium hydroxide is 0.45g), and reacting for 5-10h to obtain an aqueous solution of acrylic acid and sodium acrylate; adding 10mL of the dispersion liquid of the modified inorganic nanoparticles prepared in the step S2, 0.2g of dopamine hydrochloride and 50mg of initiator ammonium persulfate into the aqueous solution of acrylic acid and sodium acrylate in sequence, introducing nitrogen to remove oxygen, and magnetically stirring for 2min to obtain uniform mixed dispersion liquid; raising the temperature of the mixed dispersion liquid to 80 ℃ for reaction for 12h, and forming a (polyacrylic acid-co-sodium polyacrylate)/polydopamine/chitosan/poly gamma-methacryloxypropyltrimethoxysilane modified functional cross-linked network shell structure on the surface of the inorganic nano particles after the reaction is finished; putting the obtained reaction product into a dialysis bag, dialyzing in deionized water, removing unreacted monomers and other small molecular impurities, and freeze-drying to obtain the functionalized crosslinked network modified inorganic nanoparticles; through thermal weight loss analysis, the mass percentage of the macromolecular crosslinked shell layer in the whole functionalized crosslinked network modified inorganic nano-particles is 15%. Fig. 3 is a transmission electron micrograph of the functionalized crosslinked network modified inorganic nanoparticle prepared in example 1, and it can be seen from fig. 3 that the particle size of the whole particle is about 20nm, the edge of the surface of the whole particle is irregular, the light-colored part on the outer side is a shell layer, and the solid black part on the inner side is a core, which is a typical functionalized crosslinked network modified inorganic nanoparticle with a core-shell structure.
(III) the preparation of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance comprises the following steps:
h1: adding the functionalized crosslinked network modified inorganic nano particles, calcium oxide and part of tackifying resin (30 parts) into a high-speed mixer according to the weight component formula, uniformly mixing, setting the hot mixing temperature to be 120 ℃, uniformly dispersing the inorganic nano particles and the calcium oxide, coating the inorganic nano particles and the calcium oxide by the tackifying resin, and cooling after mixing to obtain a premixed material A;
h2: according to the weight component formula, respectively cutting the butyl rubber and the polyisobutylene into small blocks, then putting the small blocks into a plasticator, and plasticating at the temperature of 110 ℃ until the butyl rubber and the polyisobutylene are uniformly mixed to obtain a premixed material B;
h3: according to the weight component formula, the rest of tackifying resin, carbon black, anti-aging agent and plasticizer are sequentially added into an internal mixer, and are mixed for 15min at 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 10min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial property.
Example 2
The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance comprises the following components in parts by weight:
100 parts of butyl rubber;
the polyisobutylene comprises 175 parts of low-molecular-weight polyisobutylene with the mass fraction of 40% (the number-average molecular weight is 200-10000), medium-molecular-weight polyisobutylene with the mass fraction of 20% (the number-average molecular weight is 20000-45000) and high-molecular-weight polyisobutylene with the mass fraction of 40% (the number-average molecular weight is 75000-600000);
the inorganic nano-particles are talcum powder, and the particle size of the functional cross-linked network modified inorganic nano-particles is 40nm and is 115 parts;
the calcium oxide is nano-scale particles, the particle size range is 120nm, and 18 parts of calcium oxide are used;
65 parts of rosin resin serving as tackifying resin;
the specific surface area of the carbon black is 900m212 parts of per gram;
the anti-aging agent is antioxidant 168, 11 shares;
the plasticizer is naphthenic oil, 23 parts.
(II) preparing the functionalized crosslinked network modified inorganic nano-particles, which comprises the following steps:
s1: dispersing 2g of inorganic nanoparticles in 120mL of ethanol, ultrasonically dispersing the mixture for 30min, and mechanically stirring at room temperature at 500rpm to obtain an ethanol dispersion of the inorganic nanoparticles; dissolving 3.5mL of gamma-methacryloxypropyl trimethoxysilane in 20mL of absolute ethanol, adding 2mL of deionized water, adjusting the pH value to 4 by using dilute HCl, and carrying out prehydrolysis to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxysilane; slowly dropping a prehydrolysis solution of gamma-methacryloxypropyltrimethoxysilane into an ethanol dispersion solution of the inorganic nanoparticles, refluxing for 6 hours at 80 ℃, repeatedly washing a reaction product for 3 times by using high-speed centrifugation (6000rpm and 5min), performing vacuum drying for 24 hours at 60 ℃, and performing grinding treatment to obtain modified inorganic nanoparticles;
S2: dissolving 2g of chitosan in 100mL of acetic acid aqueous solution (the volume fraction of acetic acid is 5 percent) to obtain transparent and uniform acetic acid aqueous solution of chitosan; dispersing 1.5g of the modified inorganic nanoparticles prepared in the step S1 in 100mL of acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain dispersion liquid of the modified inorganic nanoparticles;
s3: dissolving 1.8g of acrylic acid in 10mL of sodium hydroxide aqueous solution (the mass of the sodium hydroxide is 0.45g), and reacting for 5-10h to obtain an aqueous solution of acrylic acid and sodium acrylate; sequentially adding 10mL of the dispersion liquid of the modified inorganic nanoparticles prepared in the step S2, 0.2g of dopamine hydrochloride and 50mg of initiator ammonium persulfate into the aqueous solution of acrylic acid and sodium acrylate, then introducing nitrogen to remove oxygen, and magnetically stirring for 2min to obtain a uniform mixed dispersion liquid; heating the temperature of the mixed dispersion liquid to 80 ℃ for reaction for 12 hours, and forming a (polyacrylic acid-co-sodium polyacrylate)/polydopamine/chitosan/poly gamma-methacryloxypropyltrimethoxysilane modified functional cross-linked network shell structure on the surface of the inorganic nanoparticles after the reaction is finished; putting the obtained reaction product into a dialysis bag, dialyzing the product in deionized water to remove unreacted monomers and other small molecular impurities, and freeze-drying the product to obtain the inorganic nanoparticles modified by the functional cross-linked network; through thermogravimetric analysis, the mass percentage of the macromolecular cross-linked shell layer in the whole functionalized cross-linked network modified inorganic nano-particle is 17%.
(III) the preparation of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance comprises the following steps:
h1: according to the weight component formula, adding the functional cross-linked network modified inorganic nano particles, calcium oxide and part of tackifying resin (32 parts) into a high-speed mixer, uniformly mixing, setting the hot mixing temperature to be 120 ℃, uniformly dispersing the inorganic nano particles and the calcium oxide, coating the inorganic nano particles and the calcium oxide by the tackifying resin, and cooling after mixing to obtain a premixed material A;
h2: according to the weight component formula, respectively cutting the butyl rubber and the polyisobutylene into small blocks, then putting the small blocks into a plasticator, and plasticating at the temperature of 110 ℃ until the butyl rubber and the polyisobutylene are uniformly mixed to obtain a premixed material B;
h3: according to the weight component formula, sequentially adding the balance of tackifying resin, carbon black, anti-aging agent and plasticizer into an internal mixer, and mixing for 15min at 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 12min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial property.
Example 3
The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance comprises the following components in parts by weight:
100 parts of butyl rubber;
the polyisobutylene comprises 200 parts of low-molecular-weight polyisobutylene with the mass fraction of 40% (the number-average molecular weight is 200-;
the inorganic nano particles are ferroferric oxide, and the particle size of the functional cross-linked network modified inorganic nano particles is 60nm and 130 parts;
20 parts of calcium oxide which is nano-scale particles with the particle size range of 130 nm;
the tackifying resin is terpene resin, 70 parts;
the specific surface area of the carbon black is 800m213 parts of per gram;
the anti-aging agent is 1010 parts of antioxidant and 13 parts of antioxidant;
25 parts of dioctyl phthalate serving as a plasticizer.
(II) preparing the functionalized crosslinked network modified inorganic nano-particles, which comprises the following steps:
s1: dispersing 2g of inorganic nanoparticles in 120mL of ethanol, ultrasonically dispersing the mixture for 30min, and mechanically stirring at room temperature at 500rpm to obtain an ethanol dispersion of the inorganic nanoparticles; dissolving 4mL of gamma-methacryloxypropyl trimethoxysilane in 20mL of absolute ethyl alcohol, adding 2mL of deionized water, adjusting the pH value to 4 by using dilute HCl, and carrying out prehydrolysis to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxysilane; slowly dropping a prehydrolysis solution of gamma-methacryloxypropyltrimethoxysilane into an ethanol dispersion solution of the inorganic nanoparticles, refluxing for 6 hours at 80 ℃, repeatedly washing a reaction product for 3 times by using high-speed centrifugation (6000rpm and 5min), performing vacuum drying for 24 hours at 60 ℃, and performing grinding treatment to obtain modified inorganic nanoparticles;
S2: dissolving 2g of chitosan in 100mL of acetic acid aqueous solution (the volume fraction of acetic acid is 5 percent) to obtain transparent and uniform acetic acid aqueous solution of chitosan; dispersing 1.5g of the modified inorganic nanoparticles prepared in the step S1 in 100mL of acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain dispersion liquid of the modified inorganic nanoparticles;
s3: dissolving 1.8g of acrylic acid in 10mL of sodium hydroxide aqueous solution (the mass of the sodium hydroxide is 0.45g), and reacting for 5-10h to obtain an aqueous solution of acrylic acid and sodium acrylate; sequentially adding 10mL of the dispersion liquid of the modified inorganic nanoparticles prepared in the step S2, 0.2g of dopamine hydrochloride and 50mg of initiator ammonium persulfate into the aqueous solution of acrylic acid and sodium acrylate, then introducing nitrogen to remove oxygen, and magnetically stirring for 2min to obtain a uniform mixed dispersion liquid; heating the temperature of the mixed dispersion liquid to 80 ℃ for reaction for 12 hours, and forming a (polyacrylic acid-co-sodium polyacrylate)/polydopamine/chitosan/poly gamma-methacryloxypropyltrimethoxysilane modified functional cross-linked network shell structure on the surface of the inorganic nanoparticles after the reaction is finished; putting the obtained reaction product into a dialysis bag, dialyzing in deionized water, removing unreacted monomers and other small molecular impurities, and freeze-drying to obtain the functionalized crosslinked network modified inorganic nanoparticles; through thermogravimetric analysis, the mass percentage of the macromolecular cross-linked shell layer in the whole functionalized cross-linked network modified inorganic nano-particle is 20%.
(III) the preparation of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance comprises the following steps:
h1: according to the weight component formula, adding the functional cross-linked network modified inorganic nano particles, calcium oxide and part of tackifying resin (35 parts) into a high-speed mixer, uniformly mixing, setting the hot mixing temperature to be 120 ℃, uniformly dispersing the inorganic nano particles and the calcium oxide, coating the inorganic nano particles and the calcium oxide by the tackifying resin, and cooling after mixing to obtain a premixed material A;
h2: according to the weight component formula, respectively cutting the butyl rubber and the polyisobutylene into small blocks, then putting the small blocks into a plasticator, and plasticating at the temperature of 110 ℃ until the butyl rubber and the polyisobutylene are uniformly mixed to obtain a premixed material B;
h3: according to the weight component formula, sequentially adding the balance of tackifying resin, carbon black, anti-aging agent and plasticizer into an internal mixer, and mixing for 15min at 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 15min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance.
Example 4
The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance comprises the following components in parts by weight:
100 parts of butyl rubber;
the polyisobutylene comprises 225 parts of low-molecular-weight polyisobutylene with the mass fraction of 40% (the number-average molecular weight is 200-10000), medium-molecular-weight polyisobutylene with the mass fraction of 20% (the number-average molecular weight is 20000-45000) and high-molecular-weight polyisobutylene with the mass fraction of 40% (the number-average molecular weight is 75000-600000);
the inorganic nano particles are ferroferric oxide, and the particle size of the functional cross-linked network modified inorganic nano particles is 80nm and 140 parts;
the calcium oxide is nano-scale particles with the particle size range of 150nm, and 25 parts;
75 parts of tackifying resin C5 petroleum resin;
the specific surface area of the carbon black is 600m214 parts of/g;
the anti-aging agent is antioxidant 168, 14 parts;
27 parts of plasticizer is vaseline.
(II) preparing the functionalized crosslinked network modified inorganic nano-particles, which comprises the following steps:
s1: dispersing 2g of inorganic nanoparticles in 120mL of ethanol, ultrasonically dispersing the mixture for 30min, and mechanically stirring at room temperature at 500rpm to obtain an ethanol dispersion of the inorganic nanoparticles; dissolving 4mL of gamma-methacryloxypropyl trimethoxysilane in 20mL of absolute ethyl alcohol, adding 2mL of deionized water, adjusting the pH value to 4 by using dilute HCl, and carrying out prehydrolysis to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxysilane; slowly dropping a prehydrolysis solution of gamma-methacryloxypropyltrimethoxysilane into an ethanol dispersion solution of the inorganic nanoparticles, refluxing for 6 hours at 80 ℃, repeatedly washing a reaction product for 3 times by using high-speed centrifugation (6000rpm and 5min), performing vacuum drying for 24 hours at 60 ℃, and performing grinding treatment to obtain modified inorganic nanoparticles;
S2: dissolving 2g of chitosan in 100mL of acetic acid aqueous solution (the volume fraction of acetic acid is 5 percent) to obtain transparent and uniform acetic acid aqueous solution of chitosan; dispersing 1.5g of the modified inorganic nanoparticles prepared in the step S1 in 100mL of acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain dispersion liquid of the modified inorganic nanoparticles;
s3: dissolving 1.8g of acrylic acid in 10mL of sodium hydroxide aqueous solution (the mass of the sodium hydroxide is 0.45g), and reacting for 5-10h to obtain an aqueous solution of acrylic acid and sodium acrylate; sequentially adding 10mL of the dispersion liquid of the modified inorganic nanoparticles prepared in the step S2, 0.2g of dopamine hydrochloride and 50mg of initiator ammonium persulfate into the aqueous solution of acrylic acid and sodium acrylate, then introducing nitrogen to remove oxygen, and magnetically stirring for 2min to obtain a uniform mixed dispersion liquid; heating the temperature of the mixed dispersion liquid to 80 ℃ for reaction for 12 hours, and forming a (polyacrylic acid-co-sodium polyacrylate)/polydopamine/chitosan/poly gamma-methacryloxypropyltrimethoxysilane modified functional cross-linked network shell structure on the surface of the inorganic nanoparticles after the reaction is finished; putting the obtained reaction product into a dialysis bag, dialyzing the product in deionized water to remove unreacted monomers and other small molecular impurities, and freeze-drying the product to obtain the inorganic nanoparticles modified by the functional cross-linked network; through thermogravimetric analysis, the mass percentage of the macromolecular cross-linked shell layer in the whole functionalized cross-linked network modified inorganic nano-particle is 25%.
(III) the preparation of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance comprises the following steps:
h1: adding the functionalized crosslinked network modified inorganic nano particles, calcium oxide and part of tackifying resin (38 parts) into a high-speed mixer according to the weight component formula, uniformly mixing, setting the hot mixing temperature to be 120 ℃, uniformly dispersing the inorganic nano particles and the calcium oxide, coating the inorganic nano particles and the calcium oxide by the tackifying resin, and cooling after mixing to obtain a premixed material A;
h2: according to the weight component formula, respectively cutting the butyl rubber and the polyisobutylene into small blocks, then putting the small blocks into a plasticator, and plasticating at the temperature of 110 ℃ until the butyl rubber and the polyisobutylene are uniformly mixed to obtain a premixed material B;
h3: according to the weight component formula, sequentially adding the balance of tackifying resin, carbon black, anti-aging agent and plasticizer into an internal mixer, and mixing for 15min at 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 14min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance.
Example 5
The butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance comprises the following components in parts by weight:
100 parts of butyl rubber;
the polyisobutylene comprises 250 parts of low molecular weight polyisobutylene (the number average molecular weight is 200-;
the inorganic nanoparticles are titanium dioxide, and the particle size of the functionalized crosslinked network modified inorganic nanoparticles is 100nm and 150 parts;
30 parts of calcium oxide which is nano-scale particles with the particle size range of 160 nm;
80 parts of tackifying resin C5 petroleum resin;
the specific surface area of the carbon black is 400m215 parts of per gram;
the anti-aging agent is 1010 parts of antioxidant and 15 parts of antioxidant;
the plasticizer is microcrystalline wax, and 30 parts.
(II) preparing the functionalized crosslinked network modified inorganic nano-particles, which comprises the following steps:
s1: dispersing 2g of inorganic nanoparticles in 120mL of ethanol, ultrasonically dispersing the mixture for 30min, and mechanically stirring at room temperature at 500rpm to obtain an ethanol dispersion of the inorganic nanoparticles; dissolving 4mL of gamma-methacryloxypropyl trimethoxysilane in 20mL of absolute ethyl alcohol, adding 2mL of deionized water, adjusting the pH value to 4 by using dilute HCl, and carrying out prehydrolysis to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxysilane; slowly dropping a prehydrolysis solution of gamma-methacryloxypropyltrimethoxysilane into an ethanol dispersion solution of the inorganic nanoparticles, refluxing for 6 hours at 80 ℃, repeatedly washing a reaction product for 3 times by using high-speed centrifugation (6000rpm and 5min), performing vacuum drying for 24 hours at 60 ℃, and performing grinding treatment to obtain modified inorganic nanoparticles;
S2: dissolving 2g of chitosan in 100mL of acetic acid aqueous solution (the volume fraction of acetic acid is 5 percent) to obtain transparent and uniform acetic acid aqueous solution of chitosan; dispersing 1.5g of the modified inorganic nanoparticles prepared in the step S1 in 100mL of acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain a dispersion liquid of the modified inorganic nanoparticles;
s3: dissolving 1.8g of acrylic acid in 10mL of sodium hydroxide aqueous solution (the mass of the sodium hydroxide is 0.45g), and reacting for 5-10h to obtain an aqueous solution of acrylic acid and sodium acrylate; adding 10mL of the dispersion liquid of the modified inorganic nanoparticles prepared in the step S2, 0.2g of dopamine hydrochloride and 50mg of initiator ammonium persulfate into the aqueous solution of acrylic acid and sodium acrylate in sequence, introducing nitrogen to remove oxygen, and magnetically stirring for 2min to obtain uniform mixed dispersion liquid; raising the temperature of the mixed dispersion liquid to 80 ℃ for reaction for 12h, and forming a (polyacrylic acid-co-sodium polyacrylate)/polydopamine/chitosan/poly gamma-methacryloxypropyltrimethoxysilane modified functional cross-linked network shell structure on the surface of the inorganic nano particles after the reaction is finished; putting the obtained reaction product into a dialysis bag, dialyzing in deionized water, removing unreacted monomers and other small molecular impurities, and freeze-drying to obtain the functionalized crosslinked network modified inorganic nanoparticles; through thermal weight loss analysis, the mass percentage of the macromolecular crosslinked shell layer in the whole functionalized crosslinked network modified inorganic nano-particles is 30%.
(III) the preparation of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance comprises the following steps:
h1: according to the weight component formula, adding the functional cross-linked network modified inorganic nano particles, calcium oxide and part of tackifying resin (40 parts) into a high-speed mixer, uniformly mixing, setting the hot mixing temperature to be 120 ℃, uniformly dispersing the inorganic nano particles and the calcium oxide, coating the inorganic nano particles and the calcium oxide by the tackifying resin, and cooling after mixing to obtain a premixed material A;
h2: according to the weight component formula, respectively cutting the butyl rubber and the polyisobutylene into small blocks, then putting the small blocks into a plasticator, and plasticating at the temperature of 110 ℃ until the butyl rubber and the polyisobutylene are uniformly mixed to obtain a premixed material B;
h3: according to the weight component formula, the rest of tackifying resin, carbon black, anti-aging agent and plasticizer are sequentially added into an internal mixer, and are mixed for 15min at 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 10min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial property.
Comparative example 1
The butyl rubber sealant is characterized in that 100 parts of calcium carbonate powder particles with the particle size of 20nm are replaced by the functionalized crosslinked network modified inorganic nanoparticles.
And (II) the preparation method of the butyl rubber sealant is the same as the preparation method of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance in the step (III) in the embodiment 1.
The butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance prepared in examples 1-5 and the butyl rubber sealant prepared in comparative example 1 were subjected to the following performance test experiments, respectively.
a. The butyl rubber sealant prepared in example 1 and having high humidity-induced adhesion and good antibacterial property was respectively adhered to different substrates, and the results showed that the butyl rubber sealant had good adhesion properties on polyolefin films, glass, polyester films, polyvinyl chloride films, stainless steel, paper boards, and sheepskins.
b. The butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance prepared in example 1 is used as an automobile sealant to bond an automobile steel plate and a polyethylene film, as shown in fig. 4, the butyl rubber sealant has strong adhesion on the surface of the polyethylene film, good firmness and no obvious peeling phenomenon.
c. The butyl rubber sealant prepared in the embodiments 1 to 5 and having high humidity-induced cohesiveness and good antibacterial property and the butyl rubber sealant prepared in the comparative example 1 are respectively used as automotive sealants to bond automotive steel plates and polyethylene films, and the right-angle peel strength between the butyl rubber sealant and the polyethylene films is tested, and the test results are shown in table 1:
Table 1 results of right angle peel strength test between the butyl rubber sealants prepared in examples 1 to 5 and the butyl rubber sealants prepared in comparative example 1 and the polyethylene film
The data in table 1 shows: the right-angle peel strength of the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance prepared in the examples 1-5, which is used as an automobile sealant for bonding an automobile steel plate and a polyethylene film, is about 20% higher than that of the butyl rubber sealant prepared in the comparative example 1.
d. The humidity-induced high adhesion prepared in examples 1 to 5The adhesive is respectively used as an automobile sealant to bond an automobile steel plate and a polyethylene film with the butyl rubber sealant with good antibacterial performance and the butyl rubber sealant prepared in the comparative example 1, the polyethylene film (with the size of 150 x 70mm) adhered with the sealant is placed in an ultraviolet aging test box, a fluorescent ultraviolet lamp (with the wavelength of 340nm) is used as a light source, the temperature is controlled to be 50 ℃, and the irradiance is 1.0W/m2And testing the right-angle peel strength between the butyl rubber sealant and the polyethylene film after 7 days and testing the right-angle peel strength after induction treatment for 10 hours under different humidities (20%, 30%, 40%, 50%, 60%), wherein the test results are shown in table 2:
table 2 results of right-angle peel strength tests after aging tests and humidity induction treatments of the butyl rubber sealants prepared in examples 1 to 5 and the butyl rubber sealants prepared in comparative example 1 and polyethylene films
The experimental data in table 2 show that the butyl rubber seals with high humidity-induced cohesiveness and good antibacterial property prepared in examples 1-5 and the butyl rubber sealants prepared in comparative example 1 both decrease in the right-angle peel strength after aging experiments in an ultraviolet aging box, but the butyl rubber sealants with high humidity-induced cohesiveness and good antibacterial property prepared in examples 1-5 show an upward trend in the right-angle peel strength (i.e., the cohesiveness increases) after induction treatment along with the increase of the humidity index, while the butyl rubber sealants in comparative example 1 show a downward trend in the right-angle peel strength (i.e., the cohesiveness decreases) along with the increase of the humidity index, which indicates that the butyl rubber sealants with high humidity-induced cohesiveness and good antibacterial property prepared by the method swell the macromolecule crosslinking shell layer on the surface of the functionalized crosslinked network modified inorganic nanoparticle after humidity induction treatment, the surface of the butyl rubber sealant has active groups (carboxylic acid groups, carboxylate groups, catechol functions and amino groups), and can be well combined with the surfaces of various substrates to generate high bonding performance; the butyl rubber seal of comparative example 1, however, showed an aging and deterioration effect of humidity on the butyl rubber sealant without the introduction of functionalized crosslinked network particles, and therefore the right angle peel strength was continuously decreased.
Wherein, fig. 5 (a) is an electron microscope scanning image of the initial state that the butyl rubber sealant with high humidity-induced adhesion and good antibacterial property prepared in example 1 is adhered on the polyethylene film, fig. 5 (b) is an electron microscope scanning image of the initial state that the butyl rubber sealant with high humidity-induced adhesion and good antibacterial property prepared in example 1 is adhered on the polyethylene film, and after being induced by humidity 50% for 10h, the butyl rubber sealant with high humidity-induced adhesion and good antibacterial property has a smooth surface in the initial state from fig. 5 (a), and the butyl rubber sealant with high humidity-induced adhesion and good antibacterial property has a rough surface after humidity-induced treatment from fig. 5 (b), and the principle that the adhesion property is improved after humidity-induced is consistent.
e. The butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance prepared in the embodiments 1-5 and the butyl rubber sealant prepared in the comparative example 1 are respectively used as automotive sealants to bond an automotive steel plate and a polyethylene film, the polyethylene film (with the size of 150 x 70mm) adhered with the sealants is placed in an ultraviolet aging test box, a fluorescent ultraviolet lamp (with the wavelength of 340nm) is used as a light source, the temperature is controlled to be 50 ℃, and the irradiance is 1.0W/m2And testing the bacteriostasis rate of the butyl rubber sealant on escherichia coli after 7 days and the bacteriostasis rate of the butyl rubber sealant on the escherichia coli after induced treatment for 10 hours by different humidities (20%, 30%, 40%, 50%, 60%), wherein the test results are shown in a table 3:
Table 3 test results of inhibition rates of the butyl rubber sealants prepared in examples 1 to 5 and the butyl rubber sealants prepared in comparative example 1 on Escherichia coli after aging tests and humidity treatments
The experimental data in table 3 show that, for the inhibition effect of escherichia coli, the inhibition rates of the butyl rubber seals with high humidity-induced cohesiveness and good antibacterial performance prepared in examples 1-5 before the experiment of the ultraviolet aging box all show high inhibition rates of 99%, while comparative example 1 only shows low inhibition rates of 90%; after the ultraviolet ageing oven is used for carrying out the ageing test, the bacteriostatic rate of all the examples and the comparative examples is reduced. Compared with the low antibacterial performance of the ultraviolet aging box just after the aging test, the butyl rubber seal prepared in the embodiment 1-5 and having high humidity induction cohesiveness and good antibacterial performance has an antibacterial rate of 99% after being subjected to different humidity induction treatment for 10 hours; the butyl rubber prepared in the comparative example 1 has performance degradation after induced treatment for 10 hours at different humidity, and the bacteriostasis rate is gradually reduced. The butyl rubber seal with high humidity induction cohesiveness and good antibacterial performance prepared by the method is proved to contain (polyacrylic acid-co-sodium polyacrylate)/polydopamine/chitosan/poly gamma-methacryloxypropyltrimethoxysilane (macromolecular cross-linked shell) modified functional cross-linked network modified inorganic nanoparticles, the shell structure has a good swelling effect, the chitosan has an antibacterial effect, and positive charges carried by amino groups of the chitosan are combined with negative charges of bacterial cell walls, so that bacterial growth is inhibited.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Claims (8)
1. A butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance is characterized by comprising the following components in parts by weight: 100 parts of butyl rubber, 150 parts of polyisobutylene, 150 parts of functionalized cross-linked network modified inorganic nanoparticles, 15-30 parts of calcium oxide, 60-80 parts of tackifying resin, 10-15 parts of carbon black, 10-15 parts of anti-aging agent and 20-30 parts of plasticizer.
2. The butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance as claimed in claim 1, wherein the polyisobutylene comprises 40% by mass of low molecular weight polyisobutylene, 20% by mass of medium molecular weight polyisobutylene and 40% by mass of high molecular weight polyisobutylene, the number average molecular weight of the low molecular weight polyisobutylene is 200-.
3. The humidity-induced butyl rubber sealant with high cohesiveness and good antibacterial performance as claimed in claim 1, wherein the particle size range of the calcium oxide is 100-160 nm; the tackifying resin is one of C5 petroleum resin, rosin resin and terpene resin; the specific surface area of the carbon black is 400-1000m2(iv) g; the anti-aging agent is antioxidant 1010 or antioxidant 168; the plasticizer is one of paraffin oil, naphthenic oil, dioctyl phthalate, vaseline and microcrystalline wax.
4. A preparation method of a butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance is characterized in that the preparation method of the butyl rubber sealant as claimed in any one of claims 1-3 comprises the following steps:
h1: the method comprises the following steps of putting the functionalized crosslinked network modified inorganic nanoparticles, calcium oxide and part of tackifying resin into a mixer according to the weight component formula in claim 1, uniformly mixing at 120 ℃, and cooling to obtain a premixed material A, wherein the mass feed ratio of the functionalized crosslinked network modified inorganic nanoparticles, the calcium oxide and the tackifying resin is 100-150: 15-30: 30-40;
h2: according to the weight component formula in claim 1, placing butyl rubber and polyisobutylene in a plasticator, plasticating and mixing uniformly at 110 ℃ to obtain a premixed material B;
H3: according to the weight component formula in claim 1, the rest of tackifying resin, carbon black, anti-aging agent and plasticizer are sequentially added into an internal mixer, and are mixed for 15min at the temperature of 120 ℃ to obtain a premixed material C;
h4: and (3) placing the premixed material A, the premixed material B and the premixed material C in an internal mixer, mixing for 10-15 min at the temperature of 110 ℃, and then extruding and molding at the temperature of 40 ℃ to obtain the butyl rubber sealant with high humidity induction cohesiveness and good antibacterial performance.
5. The method for preparing butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance as claimed in claim 4, wherein in step H1, the method for preparing the functionalized crosslinked network modified inorganic nanoparticles comprises the following steps:
s1: preparing modified inorganic nano particles, dispersing the inorganic nano particles in absolute ethyl alcohol, performing ultrasonic dispersion for more than 30min, and mechanically stirring uniformly to obtain an ethanol dispersion liquid of the inorganic nano particles, wherein the mass concentration of the inorganic nano particles is 16.7-20 mg/mL; dissolving gamma-methacryloxypropyl trimethoxy silane in absolute ethyl alcohol, adding a proper amount of deionized water, and adjusting the pH to 4 with inorganic acid to obtain a prehydrolysis solution of the gamma-methacryloxypropyl trimethoxy silane, wherein the mass feed ratio of the gamma-methacryloxypropyl trimethoxy silane to the absolute ethyl alcohol to the deionized water is 3-5: 16: 2; placing the ethanol dispersion liquid of the inorganic nano-particles into a reaction bottle, slowly adding the prehydrolysis solution of the gamma-methacryloxypropyltrimethoxysilane into the reaction bottle, heating to 80 ℃, stirring, refluxing and reacting for 6 hours, and sequentially centrifuging, washing, drying and grinding the reaction product mixed liquid to obtain modified inorganic nano-particles;
S2: preparing dispersion liquid of modified inorganic nano particles, and dissolving chitosan in acetic acid aqueous solution to obtain acetic acid aqueous solution of chitosan, wherein the volume fraction of acetic acid in the acetic acid aqueous solution is 5%, and the mass concentration of chitosan is 20-25 mg/mL; dispersing the modified inorganic nano-particles prepared in the step S1 in the acetic acid aqueous solution of chitosan, and performing ultrasonic dispersion for 60-90min to obtain a dispersion liquid of the modified inorganic nano-particles, wherein the mass concentration of the modified inorganic nano-particles is 15-20 mg/mL;
s3: adding acrylic acid into a sodium hydroxide aqueous solution, and reacting for 5-10 h at normal temperature to obtain an aqueous solution of acrylic acid and sodium acrylate, wherein the molar feed ratio of the acrylic acid to a sodium hydroxide solute is 2.2-3: 1; and (2) sequentially adding the dispersion of the modified inorganic nanoparticles prepared in the step (S2), dopamine hydrochloride and ammonium persulfate into an aqueous solution of acrylic acid and sodium acrylate, introducing nitrogen to remove oxygen, heating to 80 ℃, reacting for 12 hours, removing unreacted monomers and small molecules by a dialysis method after the reaction is finished, and freeze-drying to obtain the functionalized crosslinked network modified inorganic nanoparticles coated with a macromolecular crosslinked shell layer on the surface, wherein the mass feed ratio of the acrylic acid, the sodium acrylate, the modified inorganic nanoparticles, the dopamine hydrochloride and the ammonium persulfate is 1: 0.015: 0.2-0.25: 0.05.
6. The method for preparing a butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance as claimed in claim 5, wherein in step S1, the inorganic nanoparticles are one of calcium carbonate, talc, ferroferric oxide, silica and titanium dioxide.
7. The method for preparing the butyl rubber sealant with high humidity-induced cohesiveness and good antibacterial performance as claimed in claim 5, wherein in step S3, the particle size range of the functionalized crosslinked network modified inorganic nanoparticles is 20-100nm, and the mass percentage of the polymer crosslinked shell layer in the functionalized crosslinked network modified inorganic nanoparticles is 15-30%.
8. The use of the humidity-induced butyl rubber sealant with high adhesion and good antibacterial property as claimed in any one of claims 1 to 3, wherein the butyl rubber sealant is used as a sealing adhesive for glass, polyolefin films, polyester films, polyvinyl chloride films, stainless steel, paperboards and sheepskin.
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| CN105505240A (en) * | 2015-12-21 | 2016-04-20 | 保定市金月美工贸有限公司 | Butyl rubber sealing tape used for automobile and preparing method thereof |
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| CN110872477A (en) * | 2018-09-03 | 2020-03-10 | 中国石油天然气集团有限公司 | Butyl pressure-sensitive adhesive and preparation method and application thereof |
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| CN105505240A (en) * | 2015-12-21 | 2016-04-20 | 保定市金月美工贸有限公司 | Butyl rubber sealing tape used for automobile and preparing method thereof |
| CN107134590A (en) * | 2017-05-09 | 2017-09-05 | 哈尔滨工业大学 | Inorganic nano-particle that a kind of surface is modified and preparation method and application |
| CN107141951A (en) * | 2017-06-29 | 2017-09-08 | 苏州安特实业有限公司 | A kind of preparation method of the styrene-acrylic emulsion aqueous rust-proof coatings composite modified based on poly-dopamine/nano-titanium oxide |
| CN110872477A (en) * | 2018-09-03 | 2020-03-10 | 中国石油天然气集团有限公司 | Butyl pressure-sensitive adhesive and preparation method and application thereof |
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