CN117304866B - Indoor anti-pollution decorative adhesive for wallhanging stone - Google Patents
Indoor anti-pollution decorative adhesive for wallhanging stone Download PDFInfo
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- CN117304866B CN117304866B CN202311583108.3A CN202311583108A CN117304866B CN 117304866 B CN117304866 B CN 117304866B CN 202311583108 A CN202311583108 A CN 202311583108A CN 117304866 B CN117304866 B CN 117304866B
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- 239000004575 stone Substances 0.000 title claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 title claims description 16
- 239000000853 adhesive Substances 0.000 title claims description 15
- 239000002071 nanotube Substances 0.000 claims abstract description 63
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 47
- 239000011737 fluorine Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003292 glue Substances 0.000 claims abstract description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 230000003796 beauty Effects 0.000 claims abstract description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 35
- 229910052621 halloysite Inorganic materials 0.000 claims description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002537 cosmetic Substances 0.000 claims description 27
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000003449 preventive effect Effects 0.000 claims description 22
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 claims description 11
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 11
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- NCCHARWOCKOHIH-UHFFFAOYSA-N n-methylbenzamide Chemical compound CNC(=O)C1=CC=CC=C1 NCCHARWOCKOHIH-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005034 decoration Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JEVCLNJEBFWVPD-UHFFFAOYSA-N n-methyl-2-[[2-(methylcarbamoyl)phenyl]disulfanyl]benzamide Chemical compound CNC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(=O)NC JEVCLNJEBFWVPD-UHFFFAOYSA-N 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002972 grafting catalyst Substances 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The indoor anti-pollution wall cloth stone beautifying glue consists of alpha, omega-dihydroxy polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotube, organosilicon modified fumed silica, catalyst, cross-linking agent and mildew inhibitor; the obtained beauty glue has the tensile bonding strength of 3.86-4.14 MPa at 23 ℃, the bonding breaking area of 0%, the surface drying time of 13-18 min, the curing speed of 7.51-7.82 mm/24h, the tensile strength of 3.39-3.64 MPa at 23 ℃, the tensile strength of 2.57-2.71 MPa at-40 ℃, the Shore hardness of 48-53 at 23 ℃, the extrusion performance of 56-60 at-40 ℃, and the anti-fouling performance of 2.0-2.6: the pollution width and the pollution depth are 0mm, and the pollution is used for the surfaces of stones and aluminum plates, and the pollution is free in 1 month, 3 months and 6 months.
Description
Technical Field
The invention relates to indoor anti-pollution beautifying glue for wallcovering stone, and belongs to the technical field of high polymer materials.
Background
Along with the rapid development of economy, people have higher and higher aesthetic requirements on home decoration, such as living rooms usually design background decoration, and materials such as wallpaper, wallcoverings and natural stone veneers are selected to add colors and enrich the texture of living environments. However, the materials are different in construction process and materials, so that gaps are inevitably generated, and the cosmetic glue is needed for sealing edges and joints, so that not only can the gaps which are rough to cover be covered, but also the wall cloth of the wallpaper can be effectively prevented from tilting and falling off stone, and the cosmetic glue is rich in color and can meet the requirements of different decoration styles and application scenes.
The beautifying glue for indoor wall cloth stone material caulking has the advantages of environmental protection, no toxicity, no smell, good adhesive force and good flexibility, and has pollution resistance, and is convenient to clean daily and clean. A great deal of research work is done in the sealant industry to obtain a cosmetic gel with high anti-pollution performance. For example, chinese patent CN108148541A discloses a method for producing a special silicone weather-resistant sealant for anti-pollution stone, which is prepared by mixing room temperature vulcanized methyl silicone rubber, nano calcium carbonate, heavy calcium carbonate, methyl tributyl ketoxime silane, vinyl tributyl ketoxime silane, methyl mixed ketoxime cross-linking agent, N- (B-aminoethyl) -Y-aminopropyl trimethyl (ethyleneoxy) silane, gamma-glycidol ether oxypropyl trimethoxy silane and dibutyl tin dilaurate according to weight proportion. The silicone weather-resistant sealant prepared by the patent adopts ketoxime substances as the cross-linking agent, has high toxicity, is not suitable for indoor decoration, has pollution resistance, is not easy to pollute stone, has poor pollution resistance, is easy to be stained with dust and has high cleaning difficulty when being used for indoor decoration.
Chinese patent CN115322738A discloses an anti-pollution silicone structural sealant and a preparation method thereof, comprising the following materials: imidazoline-based polydimethylsiloxane, siloxane-thinning agent, carbon black, methyl silicone oil, coupling agent, cross-linking agent, polymethyl trioxyethyl silane, catalyst, alpha, omega-dihydroxy polydimethylsiloxane, nano calcium carbonate, methyl tributyl ketoximyl silane and grafting catalyst; the plasticizer for adsorbing small molecules in the colloid is added into the carbon black, so that the pollution to the bonding surface caused by the migration of the plasticizer is avoided, but the color masking force of the carbon black is too strong, and other colors cannot be endowed to the colloid, so that the carbon black is not suitable for the beautifying glue for indoor decoration.
The above can show that the current sealant is difficult to be used as the beautifying glue for interior decoration, so that the development of the wallcovering stone anti-pollution beautifying glue has very important practical significance for improving the grade of the sealant in the whole home decoration industry.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides indoor anti-pollution decorative adhesive for wallcovering stone, which realizes the following aims: the prepared beautifying glue for interior decoration has the advantages of environmental protection, no toxicity or smell, strong adhesive force, good flexibility and excellent pollution resistance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the indoor anti-pollution type wall cloth stone beautifying glue comprises the following specific formula in parts by weight:
80-120 parts of alpha, omega-dihydroxy polydimethylsiloxane,
10-20 parts of hydroxyl-containing fluorosilicone resin,
5-15 parts of fluorine modified halloysite nanotube,
3-8 parts of organosilicon modified fumed silica,
1-2 parts of catalyst,
2-7 parts of cross-linking agent,
0.2-0.6 parts of mildew inhibitor;
the hydroxyl value of the hydroxyl-containing fluorosilicone resin is 40-65 mgKOH/g, the acid value is 1-4 mgKOH/g, and the fluorine content is 25-40 wt%;
the catalyst is one of isopropyl titanate and tert-butyl titanate;
the cross-linking agent is one of methyltrimethoxysilane and methyltriethoxysilane;
the mildew preventive is one of N, N-dimethyl-N '-phenyl (fluorodichloro methyl thio) sulfonamide and 2,2' -dithiobis (N-methylbenzamide);
the following is a further improvement of the above technical scheme:
step 1, preparation of fluorine modified halloysite nanotubes
Drying halloysite nanotubes at 100-130 ℃ for 2-5 hours, adding the halloysite nanotubes into a reaction kettle, adding dimethylbenzene into the reaction kettle, then dispersing at high speed for 2-4 hours at a dispersion rate of 10000-20000 rpm, stopping high-speed dispersion, starting stirring, controlling the stirring rate to be 800-1300 rpm, adding triethylamine and fluorocarbon resin into the reaction kettle, adding 3-isocyanatopropyl triethoxysilane after the fluorocarbon resin is completely dissolved, heating to 140-170 ℃, stirring for reacting for 7-11 hours under a condensing reflux, cooling to room temperature, filtering, washing the obtained solid with absolute ethyl alcohol for 2-4 times, and vacuum drying at 75-90 ℃ for 3-6 hours to obtain fluorine modified halloysite nanotubes;
the halloysite nanotubes have the length of 500-1000 nm and the diameter of 30-100 nm;
the number average molecular weight of the fluorocarbon resin is 20000-35000 g/mol, the fluorine content is 22-35 wt%, the hydroxyl value is 20-45 mgKOH/g, and the acid value is 2-5 mgKOH/g;
the mass ratio of the halloysite nanotube to the dimethylbenzene to the triethylamine to the fluorocarbon resin to the 3-isocyanatopropyl triethoxysilane is 25-45:150-200:0.4-1:5-12:2-5.
Step 2, preparation of organosilicon modified fumed silica
Adding hydrophilic fumed silica and absolute ethyl alcohol into a reaction kettle, dispersing at a high speed for 4-8 hours at a speed of 25000-40000 r/min, stopping dispersing, starting stirring, controlling the stirring speed to be 1000-2000 r/min, adding octadecylphosphonic acid, n-hexadecyl triethoxysilane and tetraethoxysilane, heating to 60-90 ℃, stirring for reacting for 9-14 hours in a condensing reflux state, cooling to room temperature, filtering, washing the filtered solid with absolute ethyl alcohol for 3-5 times, putting into a baking oven, and drying at 70-95 ℃ for 2-5 hours to obtain the organosilicon modified fumed silica;
the particle size of the hydrophilic fumed silica is 10-100 nm;
the mass ratio of the hydrophilic fumed silica to the absolute ethyl alcohol to the octadecylphosphonic acid to the n-hexadecyl triethoxysilane to the tetraethoxysilane is 15-35:150-190:2-7:1-4:1-6.
Step 3, preparation of the beauty glue
According to the specific formula in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotubes and organosilicon modified fumed silica into a dispersion kettle, dispersing at a high speed of 25000-40000 rpm for 4-8 hours, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 2-4 hours, discharging, filling, and sealing by nitrogen to obtain the wallhanging stone anti-pollution indoor cosmetic glue.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, fluorocarbon resin and 3-isocyanatopropyl triethoxysilane are used for carrying out surface modification on the halloysite nanotube, and fluorine is chemically bonded on the surface of the halloysite nanotube with large specific surface area, so that the halloysite nanotube has strong hydrophobicity, the compatibility of the halloysite nanotube and the organic silicon matrix of the beauty gel is improved by the modification, the halloysite nanotube is easier to uniformly disperse in the organic silicon matrix of the beauty gel, and meanwhile, the overall hydrophobicity of the beauty gel is improved, so that the beauty gel has very good anti-pollution capability and self-cleaning capability;
2. the invention uses three substances of octadecylphosphonic acid, n-hexadecyl triethoxysilane and tetraethoxysilane to carry out surface modification on the hydrophilic fumed silica, reduces the surface energy of the hydrophilic fumed silica, ensures that the hydrophilic fumed silica is easier to uniformly disperse in an organosilicon matrix of the beauty gel, and endows the overall beauty gel with more excellent hydrophobic anti-pollution performance;
3. the hydroxyl-containing fluorosilicone resin with smaller viscosity and fluorine element is added into the formula of the beauty glue, and the addition of the resin can firstly improve the fluidity of the beauty glue, so that the beauty glue is easier to extrude and construct; hydroxyl in the second hydroxyl-containing fluorosilicone resin can improve the adhesive property of the beauty glue; the introduction of the third fluorine element can further provide a more hydrophobic surface, so that the improvement of the anti-pollution performance is promoted;
4. the anti-pollution indoor cosmetic glue for wallcovering stone, which is disclosed by the invention, has the advantages that the tensile bonding strength at 23 ℃ is 3.86-4.14 MPa, the bonding damage area is 0%, the surface drying time is 13-18 min, the curing speed is 7.51-7.82 mm/24h, the tensile strength at 23 ℃ is 3.39-3.64 MPa, the tensile strength at-40 ℃ is 2.57-2.71 MPa, the Shore hardness at 23 ℃ is 48-53, the extrusion performance at-40 ℃ is 56-60, the anti-pollution performance is 2.0-2.6: the pollution width and the pollution depth are 0mm, and the pollution is used for the surfaces of stones and aluminum plates, and the pollution is free in 1 month, 3 months and 6 months.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1: indoor anti-pollution decorative adhesive for wallhanging stone
Step 1, preparation of fluorine modified halloysite nanotubes
Drying halloysite nanotubes at 120 ℃ for 4 hours, adding the halloysite nanotubes into a reaction kettle, adding dimethylbenzene into the reaction kettle, then dispersing at a high speed for 3 hours at a dispersing rate of 18000 rpm, stopping high-speed dispersion, starting stirring, controlling stirring rate to 1100 rpm, adding triethylamine and fluorocarbon resin into the reaction kettle, after the fluorocarbon resin is completely dissolved, adding 3-isocyanatopropyl triethoxysilane, heating to 160 ℃, stirring for reaction for 10 hours under a condensing reflux, cooling to room temperature, filtering, washing the obtained solid with absolute ethyl alcohol for 3 times, and vacuum drying at 80 ℃ for 5 hours to obtain fluorine modified halloysite nanotubes;
the length of the halloysite nanotube is 900nm, and the diameter of the halloysite nanotube is 80nm;
the number average molecular weight of the fluorocarbon resin is 29000g/mol, the fluorine content is 30wt%, the hydroxyl value is 36mgKOH/g, and the acid value is 3 mgKOH/g;
the mass ratio of the halloysite nanotubes to the xylene to the triethylamine to the fluorocarbon resin to the 3-isocyanatopropyl triethoxysilane is 34:180:0.8:10:4.
Step 2, preparation of organosilicon modified fumed silica
Adding hydrophilic fumed silica and absolute ethyl alcohol into a reaction kettle, dispersing at a high speed for 7 hours at 36000 r/min, stopping dispersing, starting stirring, controlling the stirring speed to 1600 r/min, adding octadecylphosphonic acid, n-hexadecyl triethoxysilane and tetraethoxysilane, heating to 75 ℃, stirring for reacting for 12 hours in a condensing reflux state, cooling to room temperature, filtering, washing the filtered solid with absolute ethyl alcohol for 4 times, and drying at 85 ℃ for 4 hours to obtain organosilicon modified fumed silica;
the particle size of the hydrophilic fumed silica is 70nm;
the mass ratio of the hydrophilic fumed silica to the absolute ethyl alcohol to the octadecylphosphonic acid to the n-hexadecyltriethoxysilane to the tetraethoxysilane is 25:175:6:2:3.
Step 3, preparation of the beauty glue
The indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
110 parts of alpha, omega-dihydroxy polydimethylsiloxane,
16 parts of hydroxyl-containing fluorosilicone resin,
13 parts of fluorine modified halloysite nanotube,
5 parts of organosilicon modified fumed silica,
1.5 parts of catalyst,
4 parts of cross-linking agent,
0.5 parts of mildew preventive;
the hydroxyl value of the hydroxyl-containing fluorine-containing silicone resin is 50mgKOH/g, the acid value is 2mgKOH/g, and the fluorine content is 35wt%;
the catalyst is isopropyl titanate;
the cross-linking agent is methyltrimethoxysilane;
the mildew preventive is N, N-dimethyl-N' -phenyl (fluorodichloro methyl thio) sulfonamide;
according to the specific formula of the wall cloth stone anti-pollution type indoor cosmetic glue in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotubes and organosilicon modified fumed silica into a dispersing kettle, dispersing at a dispersing rate of 30000 revolutions per minute for 7 hours at a high speed, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 3 hours, discharging and filling, and filling nitrogen and sealing to obtain the wall cloth stone anti-pollution type indoor cosmetic glue.
Example 2: indoor anti-pollution decorative adhesive for wallhanging stone
Step 1, preparation of fluorine modified halloysite nanotubes
Drying halloysite nanotubes at 100 ℃ for 2 hours, adding the halloysite nanotubes into a reaction kettle, adding dimethylbenzene into the reaction kettle, then dispersing at a high speed for 2 hours at a dispersion rate of 10000 revolutions per minute, stopping high-speed dispersion, starting stirring, controlling the stirring rate to be 800 revolutions per minute, adding triethylamine and fluorocarbon resin into the reaction kettle, adding 3-isocyanatopropyl triethoxysilane after the fluorocarbon resin is completely dissolved, heating to 140 ℃, stirring for reaction for 7 hours under a condensing reflux, cooling to room temperature, filtering, washing the obtained solid with absolute ethyl alcohol for 2 times, and vacuum drying at 75 ℃ for 3 hours to obtain fluorine modified halloysite nanotubes;
the halloysite nanotube has a length of 500nm and a diameter of 30nm;
the number average molecular weight of the fluorocarbon resin is 20000g/mol, the fluorine content is 22wt%, the hydroxyl value is 20mgKOH/g, and the acid value is 2mgKOH/g;
the mass ratio of the halloysite nanotube to the xylene to the triethylamine to the fluorocarbon resin to the 3-isocyanatopropyl triethoxysilane is 25:150:0.4:5:2.
Step 2, preparation of organosilicon modified fumed silica
Adding hydrophilic fumed silica and absolute ethyl alcohol into a reaction kettle, dispersing at a high speed for 4 hours at 25000 r/min, stopping dispersing, starting stirring, controlling the stirring speed to be 1000 r/min, adding octadecylphosphonic acid, n-hexadecyl triethoxysilane and tetraethoxysilane, heating to 60 ℃, stirring for reacting for 9 hours in a condensing reflux state, cooling to room temperature, filtering, washing the filtered solid with absolute ethyl alcohol for 3 times, putting into a baking oven, and drying at 70 ℃ for 2 hours to obtain the organosilicon modified fumed silica;
the particle size of the hydrophilic fumed silica is 10nm;
the mass ratio of the hydrophilic fumed silica to the absolute ethyl alcohol to the octadecylphosphonic acid to the n-hexadecyltriethoxysilane to the tetraethoxysilane is 15:150:2:1:1.
Step 3, preparation of the beauty glue
The indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
80 parts of alpha, omega-dihydroxy polydimethylsiloxane,
10 parts of hydroxyl-containing fluorosilicone resin,
5 parts of fluorine modified halloysite nanotube,
3 parts of organosilicon modified fumed silica,
1 part of catalyst,
2 parts of cross-linking agent,
0.2 parts of mildew preventive;
the hydroxyl value of the hydroxyl-containing fluorosilicone resin is 40mgKOH/g, the acid value is 1mgKOH/g, and the fluorine content is 25wt%;
the catalyst is tert-butyl titanate;
the cross-linking agent is methyltriethoxysilane;
the mildew preventive is 2,2' -dithiobis (N-methylbenzamide);
according to the specific formula of the wallhanging stone anti-pollution type indoor cosmetic glue in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotubes and organosilicon modified fumed silica into a dispersing kettle, dispersing at a high speed of 25000 revolutions per minute for 4 hours, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 2 hours, discharging and filling, and filling nitrogen and sealing to obtain the wallhanging stone anti-pollution type indoor cosmetic glue.
Example 3: indoor anti-pollution decorative adhesive for wallhanging stone
Step 1, preparation of fluorine modified halloysite nanotubes
Drying halloysite nanotubes at 130 ℃ for 5 hours, adding the halloysite nanotubes into a reaction kettle, adding dimethylbenzene into the reaction kettle, then dispersing at a high speed for 4 hours at a dispersion rate of 20000 revolutions per minute, stopping high-speed dispersion, starting stirring, controlling a stirring rate of 1300 revolutions per minute, adding triethylamine and fluorocarbon resin into the reaction kettle, after the fluorocarbon resin is completely dissolved, adding 3-isocyanatopropyl triethoxysilane, heating to 170 ℃, stirring for reacting for 11 hours under a condensing reflux, cooling to room temperature, filtering, washing the obtained solid with absolute ethyl alcohol for 4 times, and vacuum drying at 90 ℃ for 6 hours to obtain fluorine modified halloysite nanotubes;
the length of the halloysite nanotube is 1000nm, and the diameter of the halloysite nanotube is 100nm;
the number average molecular weight of the fluorocarbon resin is 35000g/mol, the fluorine content is 35wt%, the hydroxyl value is 45mgKOH/g, and the acid value is 5 mgKOH/g;
the mass ratio of the halloysite nanotube to the xylene to the triethylamine to the fluorocarbon resin to the 3-isocyanatopropyl triethoxysilane is 45:200:1:12:5.
Step 2, preparation of organosilicon modified fumed silica
Adding hydrophilic fumed silica and absolute ethyl alcohol into a reaction kettle, dispersing at a high speed of 40000 r/min for 8 hours, stopping dispersing, starting stirring, controlling the stirring speed to be 2000 r/min, adding octadecylphosphonic acid, n-hexadecyl triethoxysilane and tetraethoxysilane, heating to 90 ℃, stirring for reaction for 14 hours in a condensing reflux state, cooling to room temperature, filtering, washing the filtered solid with absolute ethyl alcohol for 5 times, and drying at 95 ℃ for 5 hours to obtain organosilicon modified fumed silica;
the particle size of the hydrophilic fumed silica is 100nm;
the mass ratio of the hydrophilic fumed silica to the absolute ethyl alcohol to the octadecylphosphonic acid to the n-hexadecyltriethoxysilane to the tetraethoxysilane is 35:190:7:4:6.
Step 3, preparation of the beauty glue
The indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
120 parts of alpha, omega-dihydroxy polydimethylsiloxane,
20 parts of hydroxyl-containing fluorosilicone resin,
15 parts of fluorine modified halloysite nanotube,
8 parts of organosilicon modified fumed silica,
2 parts of catalyst,
7 parts of cross-linking agent,
0.6 parts of mildew preventive;
the hydroxyl value of the hydroxyl-containing fluorine-containing silicone resin is 65mgKOH/g, the acid value is 4 mgKOH/g, and the fluorine content is 40wt%;
the catalyst is isopropyl titanate;
the cross-linking agent is methyltrimethoxysilane;
the mildew preventive is N, N-dimethyl-N' -phenyl (fluorodichloro methyl thio) sulfonamide;
according to the specific formula of the wallhanging stone anti-pollution type indoor cosmetic glue in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotubes and organosilicon modified fumed silica into a dispersing kettle, dispersing at a dispersing rate of 40000 revolutions per minute for 8 hours at a high speed, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 4 hours, discharging and filling, and filling nitrogen and sealing to obtain the wallhanging stone anti-pollution type indoor cosmetic glue.
Comparative example 1: based on the example 1, the preparation of the fluorine modified halloysite nanotubes in the step 1 is not performed, and in the preparation of the beauty gel in the step 3, 13 parts of fluorine modified halloysite nanotubes are replaced by 13 parts of halloysite nanotubes in equal quantity, and the specific operation is as follows:
step 1, preparing fluorine modified halloysite nanotubes;
step 2, the operation is the same as in example 1;
step 3, preparation of the beauty glue
The indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
110 parts of alpha, omega-dihydroxy polydimethylsiloxane,
16 parts of hydroxyl-containing fluorosilicone resin,
13 parts of halloysite nanotube,
5 parts of organosilicon modified fumed silica,
1.5 parts of catalyst,
4 parts of cross-linking agent,
0.5 parts of mildew preventive;
the hydroxyl value of the hydroxyl-containing fluorine-containing silicone resin is 50mgKOH/g, the acid value is 2mgKOH/g, and the fluorine content is 35wt%;
the length of the halloysite nanotube is 900nm, and the diameter of the halloysite nanotube is 80nm;
the catalyst is isopropyl titanate;
the cross-linking agent is methyltrimethoxysilane;
the mildew preventive is N, N-dimethyl-N' -phenyl (fluorodichloro methyl thio) sulfonamide;
according to the specific formula of the wall cloth stone anti-pollution type indoor cosmetic glue in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, halloysite nanotubes and organosilicon modified fumed silica into a dispersing kettle, dispersing at a dispersing rate of 30000 revolutions per minute for 7 hours at a high speed, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 3 hours, discharging and filling, and sealing by nitrogen filling to obtain the wall cloth stone anti-pollution type indoor cosmetic glue.
Comparative example 2: based on the example 1, the preparation of the organosilicon modified fumed silica in the step 2 is not carried out, and in the preparation of the organosilicon modified fumed silica in the step 3 and the cosmetic glue, 5 parts of organosilicon modified fumed silica is replaced by 5 parts of hydrophilic fumed silica in equal quantity, and the specific operation is as follows:
step 1, the operation is the same as in example 1;
step 2, preparation of organosilicon modified fumed silica is not carried out;
step 3, preparation of the beauty glue
The indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
110 parts of alpha, omega-dihydroxy polydimethylsiloxane,
16 parts of hydroxyl-containing fluorosilicone resin,
13 parts of fluorine modified halloysite nanotube,
5 parts of hydrophilic fumed silica,
1.5 parts of catalyst,
4 parts of cross-linking agent,
0.5 parts of mildew preventive;
the hydroxyl value of the hydroxyl-containing fluorine-containing silicone resin is 50mgKOH/g, the acid value is 2mgKOH/g, and the fluorine content is 35wt%;
the particle size of the hydrophilic fumed silica is 70nm;
the catalyst is isopropyl titanate;
the cross-linking agent is methyltrimethoxysilane;
the mildew preventive is N, N-dimethyl-N' -phenyl (fluorodichloro methyl thio) sulfonamide;
according to the specific formula of the wallhanging stone anti-pollution type indoor cosmetic glue in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotubes and hydrophilic fumed silica into a dispersing kettle, dispersing at a dispersing rate of 30000 revolutions per minute for 7 hours at a high speed, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 3 hours, discharging, filling, and sealing by nitrogen to obtain the wallhanging stone anti-pollution type indoor cosmetic glue.
Comparative example 3: based on example 1, in step 3, the preparation of the beauty gel, the hydroxyl-containing fluorosilicone resin is not added, and 16 parts of the hydroxyl-containing fluorosilicone resin is replaced by 16 parts of alpha, omega-dihydroxy polydimethylsiloxane in equal quantity, and the specific operation is as follows:
steps 1 and 2 are the same as in example 1;
step 3, preparation of the beauty glue
The indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
126 parts of alpha, omega-dihydroxy polydimethylsiloxane,
13 parts of fluorine modified halloysite nanotube,
5 parts of organosilicon modified fumed silica,
1.5 parts of catalyst,
4 parts of cross-linking agent,
0.5 parts of mildew preventive;
the catalyst is isopropyl titanate;
the cross-linking agent is methyltrimethoxysilane;
the mildew preventive is N, N-dimethyl-N' -phenyl (fluorodichloro methyl thio) sulfonamide;
according to the specific formula of the wallhanging stone anti-pollution type indoor cosmetic glue in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, fluorine modified halloysite nanotubes and organosilicon modified fumed silica into a dispersing kettle, dispersing at a dispersing rate of 30000 revolutions per minute for 7 hours at a high speed, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 3 hours, discharging, filling, and sealing by nitrogen to obtain the wallhanging stone anti-pollution type indoor cosmetic glue.
Performance test:
the wallcovering stone anti-pollution type indoor cosmetic glue obtained in examples 1, 2 and 3 and comparative examples 1, 2 and 3 was subjected to the following performance tests:
1. stretch-bonding: tensile bond strength and bond failure area at 23 ℃ were tested with reference to GB/T16776-2005;
2. surface drying time: reference GB/T13477.3-2017 test;
3. curing speed: reference GB/T13477.3-2017 test;
4. tensile strength: tensile strength at 23 ℃ and-40 ℃ was tested with reference to GB/T528-2009;
5. shore hardness: shore hardness at 23 ℃ and-40 ℃ is tested by referring to GB/T531.1-2008;
6. extrusion properties: the extrudability was tested with reference to GB16776-2005, whereby the workability of the cosmetic gel was evaluated;
7. anti-pollution performance: infiltration contamination tests on porous substrates were performed with reference to GB/T23261-2009; the self-cleaning capability of the beauty glue is represented by a vertical flow pollution test, the surfaces of stones and aluminum plates are selected as the test base materials, and the pollution level is classified from light to heavy into pollution-free, basically pollution-free, pollution-free and obvious pollution;
the specific test results are shown in Table 1:
TABLE 1
As can be seen from the data in table 1, the halloysite nanotubes in comparative example 1 were not fluorine-modified, had poor tensile adhesion, had long tack-free time, significantly slowed cure speed, and had lower tensile strength than the three examples, had greater shore hardness and poor toughness and extrudability, probably because the halloysite nanotubes were not fluorine-modified, resulting in poor dispersibility in the silicone matrix of the cosmetic gel, were difficult to uniformly disperse and thus severely affected the above properties, and had poor anti-contamination properties due to non-uniform dispersion; comparative example 2 is similar to comparative example 1 in that the hydrophilic fumed silica is not subjected to silicone modification, the dispersion uniformity is difficult to ensure, and from the test data, the properties of comparative example 2 are significantly inferior to those of comparative example 1, which means that the hydrophilic fumed silica is more difficult to disperse than halloysite nanotubes, and uneven dispersion of the hydrophilic fumed silica is more likely to cause deterioration of the anti-pollution capability of the cosmetic gel; the comparative example 3 was free of the addition of the hydroxyl-containing fluorosilicone resin, and the properties listed in the table were slightly better than those of comparative examples 1 and 2, but were still significantly reduced compared to the three examples, and the extrudability was the worst in all examples and comparative examples, because the hydroxyl-containing fluorosilicone resin was low in viscosity, the workability of the cosmetic gel could be greatly improved, and in addition, the anti-contamination property of comparative example 3 was also significantly deteriorated, and it was seen that the hydroxyl-containing fluorosilicone resin had a very critical effect on the anti-contamination property of the cosmetic gel itself.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (2)
1. The utility model provides a wall cloth stone material antipollution formula is cosmetic glue for indoor which characterized in that:
the indoor anti-pollution decorative adhesive for wallcovering stone comprises the following specific formula in parts by weight:
80-120 parts of alpha, omega-dihydroxy polydimethylsiloxane,
10-20 parts of hydroxyl-containing fluorosilicone resin,
5-15 parts of fluorine modified halloysite nanotube,
3-8 parts of organosilicon modified fumed silica,
1-2 parts of catalyst,
2-7 parts of cross-linking agent,
0.2-0.6 parts of mildew inhibitor;
the preparation method of the fluorine modified halloysite nanotube comprises the following steps: drying halloysite nanotubes at 100-130 ℃ for 2-5 hours, adding the halloysite nanotubes into a reaction kettle, adding dimethylbenzene into the reaction kettle, then dispersing at high speed for 2-4 hours at a dispersion rate of 10000-20000 rpm, stopping high-speed dispersion, starting stirring, controlling the stirring rate to be 800-1300 rpm, adding triethylamine and fluorocarbon resin into the reaction kettle, adding 3-isocyanatopropyl triethoxysilane after the fluorocarbon resin is completely dissolved, heating to 140-170 ℃, stirring for reacting for 7-11 hours under a condensing reflux, cooling to room temperature, filtering, washing the obtained solid with absolute ethyl alcohol for 2-4 times, and vacuum drying at 75-90 ℃ for 3-6 hours to obtain fluorine modified halloysite nanotubes;
the halloysite nanotubes have the length of 500-1000 nm and the diameter of 30-100 nm;
the number average molecular weight of the fluorocarbon resin is 20000-35000 g/mol, the fluorine content is 22-35 wt%, the hydroxyl value is 20-45 mgKOH/g, and the acid value is 2-5 mgKOH/g;
the mass ratio of the halloysite nanotube to the dimethylbenzene to the triethylamine to the fluorocarbon resin to the 3-isocyanatopropyl triethoxysilane is 25-45:150-200:0.4-1:5-12:2-5;
the preparation method of the organosilicon modified fumed silica comprises the following steps: adding hydrophilic fumed silica and absolute ethyl alcohol into a reaction kettle, dispersing at a high speed for 4-8 hours at a speed of 25000-40000 r/min, stopping dispersing, starting stirring, controlling the stirring speed to be 1000-2000 r/min, adding octadecylphosphonic acid, n-hexadecyl triethoxysilane and tetraethoxysilane, heating to 60-90 ℃, stirring for reacting for 9-14 hours in a condensing reflux state, cooling to room temperature, filtering, washing the filtered solid with absolute ethyl alcohol for 3-5 times, putting into a baking oven, and drying at 70-95 ℃ for 2-5 hours to obtain the organosilicon modified fumed silica;
the particle size of the hydrophilic fumed silica is 10-100 nm;
the mass ratio of the hydrophilic fumed silica to the absolute ethyl alcohol to the octadecylphosphonic acid to the n-hexadecyl triethoxysilane to the tetraethoxysilane is 15-35:150-190:2-7:1-4:1-6;
the hydroxyl value of the hydroxyl-containing fluorosilicone resin is 40-65 mgKOH/g, the acid value is 1-4 mgKOH/g, and the fluorine content is 25-40 wt%;
the catalyst is one of isopropyl titanate and tert-butyl titanate;
the cross-linking agent is one of methyltrimethoxysilane and methyltriethoxysilane;
the mildew preventive is one of N, N-dimethyl-N '-phenyl (fluorodichloro methyl thio) sulfonamide and 2,2' -dithiobis (N-methylbenzamide).
2. The wallhanging stone anti-pollution type indoor cosmetic glue according to claim 1, wherein:
the preparation method of the beauty glue comprises the following steps: according to the specific formula in parts by weight, adding alpha, omega-dihydroxyl polydimethylsiloxane, hydroxyl-containing fluorosilicone resin, fluorine modified halloysite nanotubes and organosilicon modified fumed silica into a dispersion kettle, dispersing at a high speed of 25000-40000 rpm for 4-8 hours, adding a catalyst, a cross-linking agent and a mildew preventive, continuing dispersing for 2-4 hours, discharging, filling, and sealing by nitrogen to obtain the wallhanging stone anti-pollution indoor cosmetic glue.
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