CN118064076A - Flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive and preparation method thereof - Google Patents
Flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive and preparation method thereof Download PDFInfo
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- CN118064076A CN118064076A CN202410494333.8A CN202410494333A CN118064076A CN 118064076 A CN118064076 A CN 118064076A CN 202410494333 A CN202410494333 A CN 202410494333A CN 118064076 A CN118064076 A CN 118064076A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 86
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 86
- 238000009966 trimming Methods 0.000 title claims abstract description 74
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000003063 flame retardant Substances 0.000 title claims abstract description 50
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000654 additive Substances 0.000 claims abstract description 69
- 230000000996 additive effect Effects 0.000 claims abstract description 69
- 239000006229 carbon black Substances 0.000 claims abstract description 56
- -1 silane modified white carbon Chemical class 0.000 claims abstract description 52
- 229910000077 silane Inorganic materials 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 75
- 230000001105 regulatory effect Effects 0.000 claims description 51
- 239000002244 precipitate Substances 0.000 claims description 49
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 42
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 34
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 26
- 239000002537 cosmetic Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 9
- 238000009775 high-speed stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229920000578 graft copolymer Polymers 0.000 claims description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000005956 quaternization reaction Methods 0.000 claims description 7
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 2
- 239000003292 glue Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 20
- 230000010355 oscillation Effects 0.000 description 16
- 238000005406 washing Methods 0.000 description 12
- 238000007688 edging Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000004964 aerogel Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000013464 silicone adhesive Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000010622 cold drawing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- 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
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive and a preparation method thereof, belonging to the technical field of beautifying trimming adhesives, wherein the preparation method comprises the following steps: preparing a first additive, preparing a second additive and mixing; the preparation of the first additive consists of the following steps: preparing silane modified white carbon black, grafting a polymer brush and quaternizing; the preparation of the second additive consists of the following steps: preparing silane modified aluminum hydroxide and adding; the preparation method can improve the flame retardant property, the temperature resistance and the antibacterial and mildew-proof properties of the beautifying trimming adhesive, and simultaneously improve the tensile strength, the adhesive force, the weather resistance, the cold and hot impact resistance, the moisture resistance, the extrudability and the toughness of the beautifying trimming adhesive.
Description
Technical Field
The invention relates to the technical field of beautifying trimming glue, in particular to a flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming glue and a preparation method thereof.
Background
The beautifying edge-finishing adhesive is also called as 'beautifying adhesive' and 'edge-sealing adhesive', is a novel household edge-finishing material, and has the following performance characteristics: the sealing performance is good, a good sealing effect can be formed on gaps with different widths, and furniture and decoration main materials are better protected; good waterproof and moistureproof capacity and elasticity, good defending and adapting capacity for damp and hot weather and cold weather, the elasticity can be kept for a long time, and the reduction of the sealing effect caused by cracking due to thermal expansion and cold contraction is avoided; the mildew-proof agent has good mildew-proof function, has certain antibacterial and bacteriostatic capacities on microorganism bacteria attached to colloid, and can not generate mildew or blackening after long-term use; good weather resistance, long service life, and difficult occurrence of color change and aging in use.
The main raw materials of the cosmetic edging glue on the market are silicone glue, which is an ointment-like material that solidifies into a tough rubber-like solid material once the silicone glue is contacted with moisture in the air. The silicone adhesive has strong adhesive force and high tensile strength, has excellent weather resistance and moisture resistance, has excellent cold and hot impact resistance, and can realize the adhesion between most building material products.
Along with the continuous development of the cosmetic edge trimming adhesive industry, the requirements of people on the cosmetic edge trimming adhesive are higher and higher, and besides the advantages brought by the silicone adhesive material, the cosmetic edge trimming adhesive is required to have excellent flame retardant property, temperature resistance and antibacterial and mildew-proof properties. However, because the silicone adhesive has poor flame retardant property, temperature resistance and antibacterial and mildew-proof properties, an additive component is required to be added in the preparation of the beautifying trimming adhesive so as to improve the flame retardant property, the temperature resistance and the antibacterial and mildew-proof properties of the beautifying trimming adhesive.
For improving the flame retardant property, a common method is to add flame retardants such as aluminum phosphate, aluminum hydroxide and the like in the preparation of the cosmetic edge finishing adhesive; aiming at improving the temperature resistance, a common method is to add a high-temperature-resistant filler in the preparation of the beautifying trimming adhesive, wherein the high-temperature-resistant filler comprises calcium carbonate, carbon black and the like; aiming at the antibacterial and mildew-proof performance, the common method is to add an antibacterial and mildew-proof agent in the preparation of the beautifying trimming adhesive, wherein the antibacterial and mildew-proof agent comprises zinc oxide, nano silver and the like.
However, when the flame retardant, the high-temperature-resistant filler and the antibacterial mildew-proof agent are respectively added in the preparation of the beautifying trimming glue according to the method, the flame retardant performance, the temperature resistance and the antibacterial mildew-proof performance of the beautifying trimming glue are improved along with the increase of the addition amount, but the tensile strength of the beautifying trimming glue is influenced due to poor dispersibility of the added components in the beautifying trimming glue and poor interfacial adhesion with other components of the beautifying trimming glue, and meanwhile, the crosslinking density of the cured beautifying trimming glue is influenced due to excessive added components, so that the adhesive force, weather resistance and cold and hot impact resistance are influenced.
In order to improve the flame retardant property, the temperature resistance and the antibacterial and mildew-proof properties of the beautifying trimming adhesive and avoid the influence on other properties of the beautifying trimming adhesive, the addition amount of the additive components is required to be reduced or the surface treatment is required to be carried out on the additive components. The aerogel has excellent flame retardant property and temperature resistance, antibacterial and mildew-proof components are added into the aerogel to prepare composite aerogel, then the composite aerogel is added into the beautifying and edging glue, so that the flame retardant property, the temperature resistance and the antibacterial and mildew-proof properties of the beautifying and edging glue can be simultaneously improved, the addition amount of the added components is reduced, but the surface of the aerogel generally contains a large amount of hydroxyl groups, the hydroxyl groups are hydrophilic groups, so that the water absorbability of the aerogel is strong, the moisture resistance of the beautifying and edging glue is influenced, and in the curing process of the beautifying and edging glue, the pores of the aerogel are filled, and the temperature resistance of the aerogel is reduced; the surface grafting is carried out on the additive component, and the crosslinkable group is introduced, so that the interfacial adhesion between the additive component and other components of the cosmetic edge trimming adhesive and the crosslinking density of the cured cosmetic edge trimming adhesive can be improved, but the interfacial friction resistance between the additive component and the cosmetic edge trimming adhesive is larger than the internal friction of the cosmetic edge trimming adhesive, the extrusion property of the cosmetic edge trimming adhesive is reduced, and in addition, the crosslinkable group is introduced, so that the number of groups required to be crosslinked in the curing process is increased, the crosslinking density is improved, and the toughness of the cured cosmetic edge trimming adhesive is poor.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive and the preparation method thereof, which can improve the flame retardant property, the temperature resistance and the antibacterial mildew-proof property of the beautifying trimming adhesive and simultaneously improve the tensile strength, the cohesive force, the weather resistance, the cold and hot impact resistance, the moisture resistance, the extrusion property and the toughness of the beautifying trimming adhesive.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive comprises the following steps: preparing a first additive, preparing a second additive and mixing;
the preparation of the first additive consists of the following steps: preparing silane modified white carbon black, grafting a polymer brush and quaternizing;
The preparation method of the silane modified white carbon black comprises the steps of mixing gas-phase white carbon black, deionized water and absolute ethyl alcohol, carrying out ultrasonic oscillation at the frequency of 20-30kHz at room temperature, stopping ultrasonic oscillation after 20-30min, transferring into a four-mouth flask, regulating the temperature of the four-mouth flask to 75-85 ℃, regulating the stirring speed to 300-400rpm, regulating the pH value to 4.5-5, dropwise adding vinyl trimethoxy silane solution, stirring for 4-5h after the dropwise adding, centrifuging at the centrifuging speed of 8000-10000rpm for 10-15min, washing the precipitate 3-5 times by using deionized water after centrifuging, washing the precipitate 3-5 times by using absolute ethyl alcohol, and carrying out vacuum drying on the precipitate at the temperature of 70-80 ℃ for 6-8h to obtain the silane modified white carbon black;
in the preparation of the silane modified white carbon black, the mass ratio of the gas phase white carbon black, deionized water, absolute ethyl alcohol and vinyl trimethoxy silane solution is 150-160:100-120:1000-1300:400-450;
The grain diameter of the gas phase white carbon black is 50nm;
The dropping speed of the vinyl trimethoxy silane solution is 8-10g/min;
the preparation method of the vinyl trimethoxy silane solution comprises the steps of adding vinyl trimethoxy silane, deionized water and absolute ethyl alcohol into a four-neck flask, adjusting the pH to 4.5-5, and stirring at room temperature for 20-30min to obtain the vinyl trimethoxy silane solution;
In the preparation of the vinyl trimethoxy silane solution, the mass ratio of the vinyl trimethoxy silane to the deionized water to the absolute ethyl alcohol is 20-23:40-50:400-410;
Adding silane modified white carbon black and deionized water into a four-neck flask, sealing the four-neck flask, using nitrogen to replace air in the four-neck flask, regulating the stirring speed of the four-neck flask to 100-200rpm, stirring for 10-20min, adding dimethylaminoethyl methacrylate, regulating the temperature of the four-neck flask to 70-80 ℃, stirring for 10-20min, adding azo diisobutylamidine hydrochloride, stirring for 5-6h, centrifuging at 8000-10000rpm for 10-15min, cleaning the precipitate 3-5 times by using deionized water after centrifuging, and vacuum drying the precipitate at 70-80 ℃ for 7-9h to obtain grafted white carbon black;
In the grafted polymer brush, the mass ratio of silane modified white carbon black to deionized water to dimethylaminoethyl methacrylate to azodiisobutyl amidine hydrochloride is 100-110:1000-1200:100-130:1.2-1.3;
adding grafted white carbon black and absolute ethyl alcohol into a four-neck flask, regulating the temperature of the four-neck flask to 40-50 ℃, regulating the stirring speed to 100-200rpm, stirring for 10-20min, dropwise adding 1-chlorododecane, stirring for 6-7h after the dropwise adding is finished, centrifuging, wherein the centrifuging speed is 8000-10000rpm, the time is 10-15min, washing the precipitate 3-5 times by using absolute ethyl alcohol after the centrifuging is finished, and vacuum drying the precipitate at 60-70 ℃ for 6-8h to obtain a first additive;
In the quaternization, the mass ratio of the grafted white carbon black to the absolute ethyl alcohol to the 1-chlorododecane is 100-110:700-900:30-35;
The dropping speed of the 1-chlorododecane is 2-3g/min;
The preparation of the second additive consists of the following steps: preparing silane modified aluminum hydroxide and adding;
The preparation method of the silane modified aluminum hydroxide comprises the steps of mixing aluminum hydroxide and toluene, carrying out ultrasonic oscillation at the frequency of 20-30kHz at room temperature, stopping ultrasonic oscillation after 30-40min, transferring into a four-mouth flask with a reflux device, regulating the temperature of the four-mouth flask to 100-110 ℃, regulating the stirring speed to 300-400rpm, adding vinyltrimethoxysilane and octadecyltrimethoxysilane, stirring and refluxing for 7-8h, centrifuging at 9000-10000rpm for 15-20min, cleaning a precipitate by toluene for 4-5 times after centrifuging, and vacuum drying the precipitate at 90-100 ℃ for 8-10h to obtain the silane modified aluminum hydroxide;
In the preparation of the silane modified aluminum hydroxide, the mass ratio of the aluminum hydroxide, toluene, vinyl trimethoxy silane and octadecyl trimethoxy silane is 150-160:600-700:20-25:15-20;
The particle size of the aluminum hydroxide is 50nm;
Adding silane modified aluminum hydroxide, dimethylbenzene and n-butanol into a four-neck flask, sealing the four-neck flask, replacing air in the four-neck flask with nitrogen, regulating the stirring speed of the four-neck flask to 200-400rpm, stirring for 20-30min, adding zinc acrylate, regulating the temperature of the four-neck flask to 80-90 ℃, stirring for 10-20min, dropwise adding an azodiisobutyronitrile solution, stirring for 5-6h after the dropwise adding is finished, centrifuging, wherein the centrifuging speed is 8000-10000rpm, the time is 10-15min, washing a precipitate 3-5 times by using dimethylbenzene after the centrifuging is finished, and vacuum drying the precipitate at 80-90 ℃ for 8-9h to obtain a second additive;
In the addition, the mass ratio of the silane modified aluminum hydroxide, the dimethylbenzene, the n-butyl alcohol, the zinc acrylate and the azodiisobutyronitrile solution is 150-160:900-1000:350-400:20-25:20-25;
The dripping speed of the azodiisobutyronitrile solution is 1-1.5g/min;
The preparation method of the azodiisobutyronitrile solution comprises the steps of adding azodiisobutyronitrile, dimethylbenzene and n-butanol into a four-neck flask, and stirring for 10-15min at room temperature to obtain the azodiisobutyronitrile solution;
In the preparation of the azodiisobutyronitrile solution, the mass ratio of the azodiisobutyronitrile to the dimethylbenzene to the n-butanol is 6.2-6.5:130-150:50-60;
The mixing materials are added into a kneader to mix, the mixing temperature is controlled to be 120-130 ℃ for 70-90min, and then the mixture is cooled to room temperature to obtain a base material; adding the base material, the first additive, the second additive, the methyltriethoxysilane, the methyltrimethoxysilane, the gamma-aminopropyl triethoxysilane and the di-n-butyltin dilaurate into a high-speed stirrer for high-speed stirring, controlling the vacuum degree of the high-speed stirring to be 0.085-0.095MPa, the rotating speed to be 300-400rpm and the time to be 90-110min, and obtaining the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive;
in the mixed material, the mass ratio of alpha, omega-dihydroxypolydimethylsiloxane, methyl silicone oil, vinyl trimethoxysilane, a first additive, a second additive, methyl triethoxysilane, methyl trimethoxysilane, gamma-aminopropyl triethoxysilane and di-n-butyltin dilaurate is 240-260:20-25:3-4:40-45:17-20:3-4:5-6:3-3.5:0.9-1;
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 35000 mPa.s;
the viscosity of the methyl silicone oil at 25 ℃ is 100 mPas.
The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the flame-retardant temperature-resistant antibacterial mildew-proof beautifying edging adhesive, a first additive and a second additive are added in the preparation, when the first additive is prepared, firstly, hydroxyl on the surface of gas-phase white carbon black is utilized to carry out silane modification, carbon-carbon double bonds are introduced on the surface of the gas-phase white carbon black, then, dimethylaminoethyl methacrylate is added in a graft polymer brush, the carbon-carbon double bonds in the dimethylaminoethyl methacrylate and the carbon-carbon double bonds on the surface of the gas-phase white carbon black carry out addition reaction, a layer of tertiary amine groups are grafted on the surface of the gas-phase white carbon black, and finally, in quaternization, 1-chlorododecane and tertiary amine are used to react, and dodecyl is connected on nitrogen atoms, so that a quaternary ammonium group with long-chain alkyl is obtained; when the second additive is prepared, firstly, hydroxyl of aluminum hydroxide is utilized to carry out silane modification, carbon-carbon double bonds and long-chain alkyl are introduced into the surface of the aluminum hydroxide, and when the silane modification is carried out, the silane modification can not be carried out in an acidic environment by utilizing the characteristic that vinyl trimethoxy silane and octadecyl trimethoxy silane are easy to hydrolyze under an acidic condition because of poor acid resistance of the aluminum hydroxide, so toluene is selected as a solvent to carry out high-temperature silane modification, then zinc acrylate is added for addition, and zinc ions are introduced by utilizing the addition reaction of the carbon-carbon double bonds in the zinc acrylate and the carbon-carbon double bonds on the surface of the aluminum hydroxide. The quaternary ammonium group in the first additive and the zinc ion in the second additive are compounded, so that the effect of improving the antibacterial and mildew-proof properties of the beautifying trimming adhesive can be achieved, the gas-phase white carbon black in the first additive can be used for improving the temperature resistance of the beautifying trimming adhesive, and the aluminum hydroxide in the second additive can be used for improving the flame retardance of the beautifying trimming adhesive; in addition, as the surfaces of the first additive and the second additive are provided with long-chain alkyl groups, the long-chain alkyl groups can improve the hydrophobicity of the first additive and the second additive, the compatibility with other components in the beautifying and edging glue and the dispersibility in the beautifying and edging glue, and compared with the unmodified and grafted white carbon black, the first additive with the long-chain alkyl groups on the surface has stronger fluidity in the beautifying and edging glue; after solidification, long-chain alkyl can be bonded into the beautifying trimming adhesive through crosslinking, so that the crosslinking density is improved;
(2) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has good flame retardant property, the fire-resistant integrity is A3 level, and the fire-resistant heat insulation is A3 level;
(3) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has good antibacterial mildew-proof performance, the antibacterial rate on staphylococcus aureus is 97.1-97.8%, the antibacterial rate on escherichia coli is 94.2-95.3%, and the mildew-proof grade is 0 grade;
(4) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has high tensile strength which can reach 4.45-4.58MPa;
(5) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has strong adhesive force, 100% of definite elongation adhesive is nondestructive, and the adhesive is nondestructive after cold drawing and hot pressing +/-50%;
(6) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has good extrudability, and the extrudability can reach 250-280mL/min;
(7) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has good toughness, and the elongation at break can reach 561-578%;
(8) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has good temperature resistance, and has tensile strength of 4.41-4.52MPa after being fully cured and being placed in an environment with the temperature of 180 ℃ for 7 d;
(9) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying edge-finishing adhesive prepared by the invention has good weather resistance, and after being completely cured, the adhesive is treated for 7 days under an ultraviolet lamp with the ultraviolet wavelength of 280nm, and has the tensile strength of 4.05-4.25MPa;
(10) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has strong cold and hot impact resistance, is placed at 120 ℃ for 1d after being completely solidified, is treated at-30 ℃ for 1d, and is used as a cold and hot cycle, and after 5 cold and hot cycles are carried out, the tensile strength is 4.20-4.44MPa;
(11) The flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive prepared by the invention has good moisture resistance, and the water vapor transmittance of the adhesive film after complete curing is 5.4-6.2 g/(m 2.24 h).
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive specifically comprises the following steps:
1. Preparing a first additive:
(1) Preparing silane modified white carbon black: mixing 150g of gas-phase white carbon black, 100g of deionized water and 1000g of absolute ethyl alcohol, carrying out ultrasonic oscillation at a frequency of 20kHz at room temperature for 20min, stopping ultrasonic oscillation, transferring into a four-mouth flask, regulating the temperature of the four-mouth flask to 75 ℃, regulating the stirring speed to 300rpm, regulating the pH to 4.5, dropwise adding 400g of vinyl trimethoxy silane solution, dropwise adding the solution at an acceleration of 8g/min, stirring for 4h after the dropwise adding, centrifuging at a centrifuging speed of 8000rpm for 10min, washing the precipitate 3 times by using deionized water after the centrifuging is finished, washing the precipitate 3 times by using absolute ethyl alcohol, and vacuum drying the precipitate at 70 ℃ for 6h to obtain silane modified white carbon black;
The grain diameter of the gas phase white carbon black is 50nm;
The preparation method of the vinyl trimethoxy silane solution comprises the following steps: adding 20g of vinyltrimethoxysilane, 40g of deionized water and 400g of absolute ethyl alcohol into a four-necked flask, adjusting the pH to 4.5, and stirring at room temperature for 20min to obtain a vinyltrimethoxysilane solution;
(2) Graft polymer brush: adding 100g of silane modified white carbon black and 1000g of deionized water into a four-necked flask, sealing the four-necked flask, using nitrogen to replace air in the four-necked flask, regulating the stirring speed of the four-necked flask to 100rpm, stirring for 10min, adding 100g of dimethylaminoethyl methacrylate, regulating the temperature of the four-necked flask to 70 ℃, stirring for 10min, adding 1.2g of azo-diisobutylamidine hydrochloride, stirring for 5h, centrifuging at 8000rpm for 10min, cleaning the precipitate 3 times by using deionized water after centrifuging, and vacuum drying the precipitate at 70 ℃ for 7h to obtain grafted white carbon black;
(3) Quaternization: adding 100g of grafted white carbon black and 700g of absolute ethyl alcohol into a four-neck flask, regulating the temperature of the four-neck flask to 40 ℃, regulating the stirring speed to 100rpm, stirring for 10min, dripping 30g of 1-chlorododecane, stirring for 2g/min after dripping is finished for 6h, centrifuging, wherein the centrifuging speed is 8000rpm, the time is 10min, washing the precipitate 3 times by using absolute ethyl alcohol after centrifuging is finished, and vacuum drying the precipitate at 60 ℃ for 6h to obtain a first additive;
2. Preparing a second additive:
(1) Preparation of silane modified aluminium hydroxide: mixing 150g of aluminum hydroxide and 600g of toluene, carrying out ultrasonic oscillation at a frequency of 20kHz at room temperature for 30min, stopping ultrasonic oscillation, transferring into a four-neck flask with a reflux device, regulating the temperature of the four-neck flask to 100 ℃, regulating the stirring speed to 300rpm, adding 20g of vinyl trimethoxy silane and 15g of octadecyl trimethoxy silane, stirring and refluxing for 7h, centrifuging, wherein the centrifuging speed is 9000rpm for 15min, cleaning a precipitate by using toluene for 4 times after centrifuging, and vacuum drying the precipitate at 90 ℃ for 8h to obtain silane modified aluminum hydroxide;
The particle size of the aluminum hydroxide is 50nm;
(2) And (3) addition: adding 150g of silane modified aluminum hydroxide, 900g of dimethylbenzene and 350g of n-butanol into a four-necked flask, sealing the four-necked flask, using nitrogen to replace air in the four-necked flask, regulating the stirring speed of the four-necked flask to 200rpm, stirring for 20min, adding 20g of zinc acrylate, regulating the temperature of the four-necked flask to 80 ℃, stirring for 10min, dropwise adding 20g of azobisisobutyronitrile solution, wherein the dropwise adding speed is 1g/min, stirring for 5h after the dropwise adding is finished, centrifuging, the centrifuging speed is 8000rpm, the time is 10min, using dimethylbenzene to clean precipitate for 3 times after the centrifuging is finished, and vacuum drying the precipitate at 80 ℃ for 8h to obtain a second additive;
the preparation method of the azodiisobutyronitrile solution comprises the following steps: adding 6.2g of azobisisobutyronitrile, 130g of dimethylbenzene and 50g of n-butanol into a four-neck flask, and stirring at room temperature for 10min to obtain azobisisobutyronitrile solution;
3. Mixing: adding 240g of alpha, omega-dihydroxypolydimethylsiloxane, 20g of methyl silicone oil and 3g of vinyl trimethoxy silane into a kneader for mixing, controlling the mixing temperature to be 120 ℃ for 70min, and then cooling to room temperature to obtain a base material; adding the base material, 40g of the first additive, 17g of the second additive, 3g of methyltriethoxysilane, 5g of methyltrimethoxysilane, 3g of gamma-aminopropyl triethoxysilane and 0.9g of di-n-butyltin dilaurate into a high-speed stirrer for high-speed stirring, controlling the vacuum degree of the high-speed stirring to be 0.085MPa, the rotating speed to be 300rpm and the time to be 90min, and obtaining the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive;
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 35000 mPa.s;
the viscosity of the methyl silicone oil at 25 ℃ is 100 mPas.
Example 2
A preparation method of flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive specifically comprises the following steps:
1. Preparing a first additive:
(1) Preparing silane modified white carbon black: mixing 155g of gas-phase white carbon black, 110g of deionized water and 1150g of absolute ethyl alcohol, carrying out ultrasonic oscillation at a frequency of 25kHz at room temperature for 25min, stopping ultrasonic oscillation, transferring into a four-mouth flask, regulating the temperature of the four-mouth flask to 80 ℃, regulating the stirring speed to 350rpm, regulating the pH to 4.7, dropwise adding 420g of vinyl trimethoxy silane solution, dropwise adding the solution at a speed of 9g/min, stirring for 4.5h after the dropwise adding is finished, centrifuging at a centrifuging speed of 9000rpm for 12min, washing the precipitate 4 times by using deionized water after the centrifuging is finished, washing the precipitate 4 times by using absolute ethyl alcohol, and carrying out vacuum drying on the precipitate at 75 ℃ for 7h to obtain silane modified white carbon black;
The grain diameter of the gas phase white carbon black is 50nm;
the preparation method of the vinyl trimethoxy silane solution comprises the following steps: 22g of vinyl trimethoxy silane, 45g of deionized water and 405g of absolute ethyl alcohol are added into a four-neck flask, the pH is regulated to 4.7, and the mixture is stirred at room temperature for 25min to obtain a vinyl trimethoxy silane solution;
(2) Graft polymer brush: adding 105g of silane modified white carbon black and 1100g of deionized water into a four-necked flask, sealing the four-necked flask, using nitrogen to replace air in the four-necked flask, regulating the stirring speed of the four-necked flask to 150rpm, stirring for 15min, adding 115g of dimethylaminoethyl methacrylate, regulating the temperature of the four-necked flask to 75 ℃, stirring for 15min, adding 1.2g of azo-diisobutylamidine hydrochloride, stirring for 5.5h, centrifuging at 9000rpm for 12min, cleaning the precipitate with deionized water for 4 times after the centrifuging is finished, and vacuum drying the precipitate at 75 ℃ for 8h to obtain grafted white carbon black;
(3) Quaternization: adding 105g of grafted white carbon black and 800g of absolute ethyl alcohol into a four-neck flask, regulating the temperature of the four-neck flask to 45 ℃, regulating the stirring speed to 150rpm, stirring for 15min, dripping 32g of 1-chlorododecane, stirring for 6.5h after dripping, centrifuging at 9000rpm for 12min, cleaning the precipitate 4 times by using absolute ethyl alcohol after centrifuging, and vacuum drying the precipitate at 65 ℃ for 7h to obtain a first additive;
2. Preparing a second additive:
(1) Preparation of silane modified aluminium hydroxide: mixing 155g of aluminum hydroxide and 650g of toluene, carrying out ultrasonic oscillation at a frequency of 25kHz at room temperature, stopping ultrasonic oscillation after 35min, transferring into a four-neck flask with a reflux device, regulating the temperature of the four-neck flask to 105 ℃, regulating the stirring speed to 350rpm, adding 22g of vinyl trimethoxy silane and 18g of octadecyl trimethoxy silane, stirring and refluxing for 7.5h, centrifuging for 9500rpm for 18min, cleaning the precipitate with toluene for 4 times after the centrifugation is finished, and vacuum drying the precipitate at 95 ℃ for 9h to obtain silane modified aluminum hydroxide;
The particle size of the aluminum hydroxide is 50nm;
(2) And (3) addition: adding 155g of silane modified aluminum hydroxide, 950g of xylene and 370g of n-butanol into a four-necked flask, sealing the four-necked flask, replacing air in the four-necked flask with nitrogen, regulating the stirring speed of the four-necked flask to 300rpm, stirring for 25min, adding 22g of zinc acrylate, regulating the temperature of the four-necked flask to 85 ℃, stirring for 15min, dropwise adding 22g of azobisisobutyronitrile solution, stirring for 5.5h after the dropwise adding, centrifuging, wherein the centrifuging speed is 9000rpm, the time is 12min, cleaning the precipitate 4 times with xylene after the centrifuging, and vacuum drying the precipitate at 85 ℃ for 8.5h to obtain a second additive;
The preparation method of the azodiisobutyronitrile solution comprises the following steps: adding 6.4g of azobisisobutyronitrile, 140g of dimethylbenzene and 55g of n-butanol into a four-neck flask, and stirring at room temperature for 12min to obtain azobisisobutyronitrile solution;
3. mixing: 250g of alpha, omega-dihydroxypolydimethylsiloxane, 22g of methyl silicone oil and 3.5g of vinyl trimethoxy silane are added into a kneader for mixing, the mixing temperature is controlled to be 125 ℃, the time is 80 minutes, and then the mixture is cooled to room temperature to obtain a base material; adding the base material, 42g of the first additive, 18g of the second additive, 3.5g of methyltriethoxysilane, 5.5g of methyltrimethoxysilane, 3.2g of gamma-aminopropyl triethoxysilane and 0.95g of di-n-butyltin dilaurate into a high-speed stirrer for high-speed stirring, controlling the vacuum degree of the high-speed stirring to be 0.09MPa, controlling the rotating speed to be 350rpm and controlling the time to be 100min to obtain the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive;
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 35000 mPa.s;
the viscosity of the methyl silicone oil at 25 ℃ is 100 mPas.
Example 3
A preparation method of flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive specifically comprises the following steps:
1. Preparing a first additive:
(1) Preparing silane modified white carbon black: mixing 160g of gas-phase white carbon black, 120g of deionized water and 1300g of absolute ethyl alcohol, carrying out ultrasonic oscillation at the frequency of 30kHz at room temperature for 30min, stopping ultrasonic oscillation, transferring into a four-mouth flask, regulating the temperature of the four-mouth flask to 85 ℃, regulating the stirring speed to 400rpm, regulating the pH to 5, dropwise adding 450g of vinyl trimethoxy silane solution, dropwise adding the solution at the speed of 10g/min, stirring for 5h after the dropwise adding is finished, centrifuging at the speed of 10000rpm for 15min, washing the precipitate with deionized water for 5 times after the centrifuging is finished, washing the precipitate with absolute ethyl alcohol for 5 times, and carrying out vacuum drying on the precipitate at 80 ℃ for 8h to obtain silane modified white carbon black;
The grain diameter of the gas phase white carbon black is 50nm;
the preparation method of the vinyl trimethoxy silane solution comprises the following steps: 23g of vinyltrimethoxysilane, 50g of deionized water and 410g of absolute ethyl alcohol are added into a four-necked flask, the pH is regulated to 5, and the mixture is stirred for 30min at room temperature to obtain a vinyltrimethoxysilane solution;
(2) Graft polymer brush: adding 110g of silane modified white carbon black and 1200g of deionized water into a four-necked flask, sealing the four-necked flask, using nitrogen to replace air in the four-necked flask, regulating the stirring speed of the four-necked flask to 200rpm, stirring for 20min, adding 130g of dimethylaminoethyl methacrylate, regulating the temperature of the four-necked flask to 80 ℃, stirring for 20min, adding 1.3g of azo-diisobutylamidine hydrochloride, stirring for 6h, centrifuging at 10000rpm for 15min, cleaning the precipitate with deionized water for 5 times after centrifuging, and vacuum drying the precipitate at 80 ℃ for 9h to obtain grafted white carbon black;
(3) Quaternization: adding 110g of grafted white carbon black and 900g of absolute ethyl alcohol into a four-neck flask, regulating the temperature of the four-neck flask to 50 ℃, regulating the stirring speed to 200rpm, stirring for 20min, dropwise adding 35g of 1-chlorododecane, stirring for 3g/min after the dropwise adding is finished, stirring for 7h, centrifuging, wherein the centrifuging speed is 10000rpm, the time is 15min, washing a precipitate 3-5 times by using absolute ethyl alcohol after the centrifuging is finished, and vacuum drying the precipitate at 70 ℃ for 8h to obtain a first additive;
2. Preparing a second additive:
(1) Preparation of silane modified aluminium hydroxide: mixing 160g of aluminum hydroxide and 700g of toluene, carrying out ultrasonic oscillation at a frequency of 30kHz at room temperature, stopping ultrasonic oscillation after 40min, transferring into a four-neck flask with a reflux device, regulating the temperature of the four-neck flask to 110 ℃, regulating the stirring speed to 400rpm, adding 25g of vinyl trimethoxy silane and 20g of octadecyl trimethoxy silane, stirring and refluxing for 8h, centrifuging, wherein the centrifuging speed is 10000rpm, the time is 20min, cleaning a precipitate by toluene after centrifuging is finished, and vacuum drying the precipitate for 10h at 100 ℃ to obtain silane modified aluminum hydroxide;
The particle size of the aluminum hydroxide is 50nm;
(2) And (3) addition: adding 160g of silane modified aluminum hydroxide, 1000g of dimethylbenzene and 400g of n-butanol into a four-necked flask, sealing the four-necked flask, replacing air in the four-necked flask with nitrogen, regulating the stirring speed of the four-necked flask to 400rpm, stirring for 30min, adding 25g of zinc acrylate, regulating the temperature of the four-necked flask to 90 ℃, stirring for 20min, dropwise adding 25g of azobisisobutyronitrile solution, stirring for 6h after the dropwise adding, centrifuging, wherein the centrifuging speed is 10000rpm, the time is 15min, cleaning the precipitate with dimethylbenzene for 5 times after the centrifuging is finished, and vacuum drying the precipitate at 90 ℃ for 9h to obtain a second additive;
The preparation method of the azodiisobutyronitrile solution comprises the following steps: adding 6.5g of azobisisobutyronitrile, 150g of dimethylbenzene and 60g of n-butanol into a four-neck flask, and stirring at room temperature for 15min to obtain azobisisobutyronitrile solution;
3. Mixing: adding 260g of alpha, omega-dihydroxypolydimethylsiloxane, 25g of methyl silicone oil and 4g of vinyl trimethoxy silane into a kneader for mixing, controlling the mixing temperature to be 130 ℃ for 90min, and then cooling to room temperature to obtain a base material; adding base material, 45g of first additive, 20g of second additive, 4g of methyltriethoxysilane, 6g of methyltrimethoxysilane, 3.5g of gamma-aminopropyl triethoxysilane and 1g of di-n-butyltin dilaurate into a high-speed stirrer, and stirring at high speed, wherein the vacuum degree of the high-speed stirring is controlled to be 0.095MPa, the rotating speed is 400rpm, and the time is 110min, so as to obtain the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive;
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 35000 mPa.s;
the viscosity of the methyl silicone oil at 25 ℃ is 100 mPas.
Comparative example 1
The purpose of this comparative example was to verify the effect of the first additive, the technical solution being modified on the basis of example 2, with the following specific modifications: the step 1 of preparing the first additive is omitted, and in the step 3 of mixing, the addition of the first additive is omitted, and 40g of fumed silica with the particle size of 50nm and 2g of dodecyl trimethyl ammonium chloride are additionally added.
Comparative example 2
The purpose of this comparative example was to verify the effect of the second additive, the technical solution was modified on the basis of example 2, with the following specific modifications: the step of preparing the second additive in step 2 was omitted, and in the step 3 blend, the addition of the second additive was omitted, and 17g of aluminum hydroxide having a particle size of 50nm and 1g of zinc acrylate were additionally added.
Test example 1
The cosmetic edging adhesives prepared in examples 1-3 and comparative examples 1-2 were tested for fire resistance integrity, fire resistance and heat insulation, bacteriostasis to staphylococcus aureus, bacteriostasis to escherichia coli, mildew resistance rating, tensile strength, 100% stretching adhesion, cold-drawn hot-press ± 50% adhesion, extrudability, elongation at break, and the test results were as follows:
When testing the antibacterial rate of staphylococcus aureus and the antibacterial rate of escherichia coli, the edge-trimming adhesive is completely cured at the temperature of 25 ℃ and the humidity of 50% to obtain an adhesive film, and then the adhesive film is tested according to the GB/T20944-2007 test standard.
Test example 2
The cosmetic edge-finishing adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 were completely cured at 25℃and 50% humidity to prepare test specimens, and the test specimens were treated at 180℃for 7d and then naturally cooled to room temperature, and then tested for tensile strength, with the following test results:
Test example 3
The cosmetic edge-finishing adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 were completely cured at 25℃and 50% humidity to prepare test specimens, and after the test specimens were subjected to a treatment for 7d under an ultraviolet lamp having an ultraviolet wavelength of 280nm, the tensile strength of the test specimens was measured as follows:
Test example 4
The cosmetic edging adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 were completely cured at 25℃and 50% humidity to prepare test specimens, the test specimens were treated at 120℃for 1d and at-30℃for 1d, and then the above treatments were used as one heat and cold cycle, and after 5 heat and cold cycles, the tensile strength of the test specimens was measured as follows:
Test example 5
The edge-finishing adhesives prepared in examples 1-3 and comparative examples 1-2 were tested for water vapor transmission rate and the test results were as follows:
When the water vapor transmittance of the edge finishing adhesive is tested, the edge finishing adhesive is completely solidified into an adhesive film with the thickness of 1mm under the environment of the temperature of 25 ℃ and the humidity of 50%, and then the adhesive film is tested according to the GB/T26153-2010 test standard.
As can be seen from the results of test examples 1 to 5, although the first additive is replaced by the fumed silica and the dodecyl trimethyl ammonium chloride, and the second additive is replaced by the aluminum hydroxide and the zinc acrylate, the respective performances of the fumed silica, the dodecyl trimethyl ammonium chloride, the aluminum hydroxide and the zinc acrylate are utilized to respectively play roles, namely the temperature resistance of the beautifying trimming adhesive can be improved through the fumed silica, the flame retardant property of the beautifying trimming adhesive can be improved through the aluminum hydroxide, the antibacterial and mildew-proof properties of the beautifying trimming adhesive can be improved through the dodecyl trimethyl ammonium chloride and the zinc acrylate, and thus the fireproof integrity, the fireproof heat insulation, the antibacterial rate to staphylococcus aureus, the antibacterial rate to escherichia coli and the mildew-proof grade of the beautifying trimming adhesive are improved; however, because of poor compatibility among the gas-phase white carbon black, aluminum hydroxide, zinc acrylate and other components of the cosmetic edge finishing adhesive, the dispersibility in the cosmetic edge finishing adhesive is poor, and the cured crosslinking density is influenced, the tensile strength, 100% stretching cohesiveness, cold-drawing hot-pressing +/-50% cohesiveness, elongation at break, high temperature resistance, weather resistance and cold-hot impact resistance of the cosmetic edge finishing adhesive are influenced; because the aluminum hydroxide and the zinc acrylate have poor fluidity in the beautifying trimming adhesive, the extrudability of the beautifying trimming adhesive is also influenced; because the gas-phase white carbon black and the aluminum hydroxide have hydrophilicity, the dodecyl trimethyl ammonium chloride is easy to dissolve in water, and the hydrophobicity of the cosmetic edge trimming glue can be reduced after the gas-phase white carbon black, the dodecyl trimethyl ammonium chloride and the aluminum hydroxide are directly added into the cosmetic edge trimming glue, so that the moisture resistance of the cosmetic edge trimming glue is reduced, and the water vapor transmittance is further influenced.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive is characterized by comprising the following steps of: preparing a first additive, preparing a second additive and mixing;
the preparation of the first additive consists of the following steps: preparing silane modified white carbon black, grafting a polymer brush and quaternizing;
the preparation of the second additive consists of the following steps: and (3) preparing silane modified aluminum hydroxide and adding.
2. The method for preparing the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 1, which is characterized in that the preparation of the silane modified white carbon black is carried out by mixing gas-phase white carbon black, deionized water and absolute ethyl alcohol, dispersing uniformly, transferring into a reactor, regulating the temperature of the reactor to 75-85 ℃, starting stirring, regulating the pH to 4.5-5, dripping vinyl trimethoxy silane solution, stirring after dripping, centrifuging, cleaning and drying precipitate to obtain the silane modified white carbon black;
in the preparation of the silane modified white carbon black, the mass ratio of the gas phase white carbon black, deionized water, absolute ethyl alcohol and vinyl trimethoxy silane solution is 150-160:100-120:1000-1300:400-450;
The grain diameter of the gas phase white carbon black is 50nm;
The dripping speed of the vinyl trimethoxy silane solution is 8-10g/min.
3. The method for preparing the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 2, which is characterized in that the preparation method of the vinyl trimethoxy silane solution is that vinyl trimethoxy silane, deionized water and absolute ethyl alcohol are added into a reactor, the pH is regulated to 4.5-5, and the mixture is stirred uniformly at room temperature to obtain the vinyl trimethoxy silane solution;
in the preparation of the vinyl trimethoxy silane solution, the mass ratio of the vinyl trimethoxy silane to the deionized water to the absolute ethyl alcohol is 20-23:40-50:400-410.
4. The method for preparing the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 1, wherein the grafted polymer brush is characterized in that silane modified white carbon black and deionized water are added into a reactor, the reactor is closed, air in the reactor is replaced by nitrogen, the reactor is stirred, dimethylaminoethyl methacrylate is added, the temperature of the reactor is regulated to 70-80 ℃, the reactor is stirred, azo diisobutylamidine hydrochloride is added, the mixture is stirred, centrifuged, and the precipitate is washed and dried to obtain grafted white carbon black;
in the grafted polymer brush, the mass ratio of the silane modified white carbon black to the deionized water to the dimethylaminoethyl methacrylate to the azodiisobutyl amidine hydrochloride is 100-110:1000-1200:100-130:1.2-1.3.
5. The method for preparing the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 1, wherein the quaternization is carried out, grafted white carbon black and absolute ethyl alcohol are added into a reactor, the temperature of the reactor is regulated to 40-50 ℃, the reactor is stirred, 1-chlorododecane is dropwise added, the stirring is carried out after the dropwise addition is finished, and the precipitate is centrifugally washed and dried to obtain a first additive;
In the quaternization, the mass ratio of the grafted white carbon black to the absolute ethyl alcohol to the 1-chlorododecane is 100-110:700-900:30-35;
the dropping speed of the 1-chlorododecane is 2-3g/min.
6. The method for preparing the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 1, which is characterized in that the preparation of silane modified aluminum hydroxide is carried out by mixing aluminum hydroxide and toluene, dispersing uniformly, transferring into a reactor equipped with a reflux device, adjusting the temperature of the reactor to 100-110 ℃, starting stirring, adding vinyl trimethoxysilane and octadecyl trimethoxysilane, stirring, refluxing, centrifuging, cleaning, and drying precipitate to obtain silane modified aluminum hydroxide;
In the preparation of the silane modified aluminum hydroxide, the mass ratio of the aluminum hydroxide, toluene, vinyl trimethoxy silane and octadecyl trimethoxy silane is 150-160:600-700:20-25:15-20;
The particle size of the aluminum hydroxide is 50nm.
7. The method for preparing the flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 1, wherein the addition is characterized in that silane modified aluminum hydroxide, dimethylbenzene and n-butyl alcohol are added into a reactor, the reactor is closed, nitrogen is used for replacing air of the reactor, zinc acrylate is stirred, the temperature of the reactor is adjusted to 80-90 ℃, an azodiisobutyronitrile solution is dropwise added, stirring is carried out after the dropwise addition is finished, and the precipitate is centrifugally cleaned and dried to obtain a second additive;
In the addition, the mass ratio of the silane modified aluminum hydroxide, the dimethylbenzene, the n-butyl alcohol, the zinc acrylate and the azodiisobutyronitrile solution is 150-160:900-1000:350-400:20-25:20-25;
The dripping speed of the azodiisobutyronitrile solution is 1-1.5g/min;
The preparation method of the azodiisobutyronitrile solution comprises the steps of adding azodiisobutyronitrile, dimethylbenzene and n-butanol into a reactor, and uniformly stirring at room temperature to obtain the azodiisobutyronitrile solution;
in the preparation of the azodiisobutyronitrile solution, the mass ratio of the azodiisobutyronitrile to the dimethylbenzene to the n-butanol is 6.2-6.5:130-150:50-60.
8. The method for preparing the flame-retardant and temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 1, wherein the mixing is carried out by adding alpha, omega-dihydroxy polydimethylsiloxane, methyl silicone oil and vinyl trimethoxy silane into a kneader for mixing, and then cooling to room temperature to obtain a base material; adding the base material, the first additive, the second additive, the methyltriethoxysilane, the methyltrimethoxysilane, the gamma-aminopropyl triethoxysilane and the di-n-butyltin dilaurate into a high-speed stirrer for high-speed stirring to obtain the flame-retardant temperature-resistant antibacterial mildew-proof beautifying edge-trimming adhesive.
9. The method for preparing the flame-retardant and temperature-resistant antibacterial mildew-proof beautifying trimming adhesive according to claim 8, wherein in the mixture, the mass ratio of alpha, omega-dihydroxypolydimethylsiloxane, methyl silicone oil, vinyl trimethoxysilane, first additive, second additive, methyltriethoxysilane, methyltrimethoxysilane, gamma-aminopropyl triethoxysilane and di-n-butyltin dilaurate is 240-260:20-25:3-4:40-45:17-20:3-4:5-6:3-3.5:0.9-1;
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 35000 mPa.s;
the viscosity of the methyl silicone oil at 25 ℃ is 100 mPas;
The temperature of the mixing is 120-130 ℃ and the time is 70-90min;
The vacuum degree of the high-speed stirring is 0.085-0.095MPa, the rotating speed is 300-400rpm, and the time is 90-110min.
10. A flame retardant, temperature resistant, antibacterial, mildew resistant, cosmetic edge finishing adhesive prepared according to the method of any one of claims 1-9.
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