CN117661365A - Environment-friendly nanometer negative ion decorative paper and preparation method thereof - Google Patents
Environment-friendly nanometer negative ion decorative paper and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 quaternary ammonium salt modified acrylic ester Chemical class 0.000 claims abstract description 143
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 239000003063 flame retardant Substances 0.000 claims abstract description 43
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 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 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 22
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 abstract description 17
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims abstract description 11
- 229940119177 germanium dioxide Drugs 0.000 claims abstract description 11
- 229940119545 isobornyl methacrylate Drugs 0.000 claims abstract description 11
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 150000002500 ions Chemical class 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 10
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 claims description 9
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 8
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 7
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 102100027116 Low-density lipoprotein receptor-related protein 10 Human genes 0.000 claims description 7
- 101710136829 Low-density lipoprotein receptor-related protein 10 Proteins 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- MSAQXBWFCRKTLJ-UHFFFAOYSA-M CO.[OH-].C(C)[N+](CC)(CC)CC Chemical compound CO.[OH-].C(C)[N+](CC)(CC)CC MSAQXBWFCRKTLJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical group [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Abstract
The invention relates to the technical field of anion decorative paper, and discloses environment-friendly nanometer anion decorative paper and a preparation method thereof; the method comprises the following steps: uniformly stirring ethyl acrylate, methyl methacrylate, styrene, hydroxyethyl acrylate, isobornyl methacrylate, quaternary ammonium salt modified acrylic ester, flame-retardant modified POSS grafted vinyl siloxane and a reactive emulsifier, adding propylene glycol methyl ether acetate and AIBN, heating to 100-105 ℃ for reacting for 1.5-2 hours to obtain composite acrylic ester; adding germanium dioxide into the composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
Description
Technical Field
The invention relates to the technical field of negative ion decorative paper, in particular to environment-friendly nanometer negative ion decorative paper and a preparation method thereof.
Background
Negative ions have great benefits for the environment and for the health of the human body, especially in the case of increasingly severe pollution nowadays. The demand of people for negative ions is also increasing, and when people select materials in the decoration process, furniture products capable of releasing negative ions are often selected; the negative ion decorative paper is widely applied to occasions such as furniture manufacture, interior decoration and the like because of the characteristics of various colors, rich patterns, high quality, low price, convenience, rapidness and the like, and the negative ion release performance of the negative ion decorative paper is paid attention to the freshness of the hydrophobic, antibacterial and flame retardant performance of the decorative paper.
Therefore, the invention discloses the environment-friendly nanometer negative ion decorative paper and the preparation method thereof.
Disclosure of Invention
The invention aims to provide an environment-friendly nanometer negative ion decorative paper and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps:
s1: adding 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol and 1-bromohexadecane into acetonitrile, stirring uniformly, heating to 80-85 ℃ for reaction for 96-108h, vacuum distillation, and washing to obtain an intermediate; adding an intermediate, isocyanoethyl methacrylate, dibutyl tin dilauryl silicate and hydroquinone into tetrahydrofuran, stirring uniformly, heating to 45-50 ℃ for reaction, vacuum distilling, washing, centrifuging, and drying at 40-45 ℃ to obtain quaternary ammonium salt modified acrylic ester when the content of isocyanate groups is 0;
s2: uniformly stirring ethyl acrylate, methyl methacrylate, styrene, hydroxyethyl acrylate, isobornyl methacrylate, quaternary ammonium salt modified acrylic ester, flame-retardant modified POSS grafted vinyl siloxane and a reactive emulsifier, adding propylene glycol methyl ether acetate and AIBN, heating to 100-105 ℃ for reacting for 1.5-2 hours to obtain composite acrylic ester; adding germanium dioxide into the composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
Further, the preparation method of the flame-retardant modified POSS grafted vinyl siloxane comprises the following steps: uniformly stirring octamethyl cyclotetrasiloxane, hexamethyl and silane and KH563, adding a catalyst C, heating to 100-105 ℃ for reaction for 2-3h, adding tetramethyl tetravinyl cyclotetrasiloxane, continuously preserving heat for reaction for 2-3h, and performing rotary evaporation to obtain epoxy vinyl siloxane; adding the aminopropyl flame-retardant modified POSS into tetrahydrofuran, uniformly stirring, adding epoxy vinyl siloxane, adjusting the pH to 9-10, heating to 50-55 ℃ for reacting for 5-6h, filtering, steaming, washing and drying to obtain the flame-retardant modified POSS grafted vinyl siloxane.
Further, the octamethyl cyclotetrasiloxane: hexamethyl and silane: KH563: the mass ratio of the tetramethyl tetravinyl cyclotetrasiloxane is 1 (0.3-0.5): 1 (0.2-0.25); the aminopropyl flame retardant modified POSS: the molar ratio of the epoxy vinyl siloxane is (1.2-1.5): 1-1.25; the catalyst C is concentrated hydrochloric acid with the concentration of 12-14 mol/L.
Further, the preparation method of the aminopropyl flame retardant modified POSS comprises the following steps: adding the catalyst A into acetone and methanol, uniformly stirring, heating to a reflux state, adding allyl trimethoxy silane to perform heat preservation reaction for 20-24 hours in the reflux state, neutralizing, filtering, washing and drying to obtain silanol polyallyl POSS; adding silanol polyallylate POSS into tetrahydrofuran, adding a silane coupling agent KH540 and a catalyst B, stirring at room temperature for reaction for 24 hours, steaming, washing and filtering to obtain aminopropyl polyallylate POSS; under the nitrogen atmosphere, adding the aminopropyl polyallyl POSS, DOPO, AIBN into toluene, stirring uniformly, heating to 80-85 ℃ for reaction for 10-12h, adding the lower reactant into dichloromethane, adding ethyl acetate for precipitation, filtering, and drying to obtain the aminopropyl flame-retardant modified POSS.
Further, the allyltrimethoxysilane: the mass ratio of the catalyst A is (4.32-4.56): 1; the silanol polyallylboss: the mass ratio of the silane coupling agent KH540 is 1 (1.2-1.5); the aminopropyl polyallylses: the mass ratio of DOPO is 1:3, a step of; the catalyst A is a lithium aluminum hydride monohydrate and a secondary distilled water mixture with the mass ratio of 1:1; the catalyst B is 28-30wt% of tetraethylammonium hydroxide methanol solution;
further, the preparation method of the reactive emulsifier comprises the following steps: adding a phosphate emulsifier into sodium methoxide, adding allyl glycidyl ether, hypophosphorous acid and triphenyl phosphite under the nitrogen atmosphere, and heating to 90-110 ℃ for reaction for 3.5-4h to obtain an emulsifier A; adding the emulsifier A into potassium hydroxide, heating to 120-140 ℃ under the condition of 0.1-0.2MPa, introducing ethylene oxide, and reacting for 3-4h under the condition of heat preservation to obtain an emulsifier B; adding urea into the emulsifier B, heating to 90-110 ℃ under the nitrogen atmosphere, adding sulfamic acid, and reacting for 3-5h to obtain the reactive emulsifier.
Further, the phosphate ester emulsifier: the mol ratio of the allyl glycidyl ether is 1 (2.1-2.3); the emulsifier A: the molar ratio of the ethylene oxide is 1 (2-2.1); the emulsifier B: the mole ratio of sulfamic acid is 1 (2.02-2.22); the phosphate ester emulsifier is LRP-10.
Further, the 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol: 1-bromohexadecane: the mass ratio of the isocyanoethyl methacrylate is 1 (4-5) to 1-1.2.
Further, the composite acrylic ester comprises, by mass, 5-10 parts of ethyl acrylate, 5-10 parts of methyl methacrylate, 5-10 parts of styrene, 5-10 parts of hydroxyethyl acrylate, 10-20 parts of isobornyl methacrylate, 8-16 parts of quaternary ammonium salt modified acrylic ester, 10-15 parts of flame-retardant modified POSS grafted vinyl siloxane, 3-5 parts of reactive emulsifier, 30-50 parts of propylene glycol methyl ether acetate and 0.1-0.2 part of AIBN; the addition of germanium dioxide is 2-3wt% of the mass of the composite acrylic ester; the solid content of the acrylic ester emulsion is 55-60%.
Compared with the prior art, the invention has the following beneficial effects:
the application uses a phosphate emulsifier LRP-10 as a matrix emulsifier, and obtains a reactive emulsifier through reaction with sulfamic acid and uric acid; the acrylic ester is added into an acrylic ester monomer to be copolymerized and grafted into an acrylic ester chain segment, and is permanently bonded into a polymer chain segment, so that the problem that a traditional emulsifier remains in a polymer is avoided, and the adhesive property of an acrylic ester emulsion is greatly improved; the self-polymerization phenomenon of the emulsifier in the acrylic ester emulsion can be avoided, and the stability of the emulsion is improved; the large-volume flexible side group of the self structure can play a role in steric hindrance and shielding, so that the decomposition reaction of substances is delayed, and the thermal stability of the decorative paper is greatly improved; the hydrophilic groups in the emulsifier, namely the phosphate and sulfamic acid, can enhance the hydrophilicity of the acrylic ester to enhance the emulsifying performance of the acrylic ester, but more hydrophilic groups also have influence on the water resistance of the decorative paper, so that the water resistance of the decorative paper is reduced.
The silanol polyallylate POSS is prepared by taking allyl trimethoxysilane as a monomer; adding KH540 to react with three alcohol hydroxyl groups on silanol polyallylate POSS, successfully connecting amino groups into a POSS structure, and finally reacting with DOPO to prepare aminopropyl flame-retardant modified POSS; then reacts with epoxy groups on self-made epoxy vinyl siloxane, and is successfully grafted on the side chain of the epoxy vinyl siloxane, and the vinyl on the epoxy vinyl siloxane participates in polymerization of acrylic acid monomers and is successfully grafted into an acrylic ester chain segment, on one hand, the introduction of long-chain siloxane utilizes the characteristics of a soft hydrophobic chain segment and low surface energy of the long-chain siloxane, and the long-chain siloxane tends to move to the surface of a polymer in the process of forming a coating on the surface of decorative paper, so that the entry of water molecules is prevented, and the hydrophobic property of the decorative paper is improved; on the other hand, the POSS structure of the side chain of the siloxane chain segment can move towards the surface of the polymer along with the siloxane, and uniformly distributed granular bulges are formed on the surface of the polymer, so that the roughness of the surface of the decorative paper is greatly enhanced, and the uniformly distributed POSS forms a lotus leaf-like microstructure on the surface, so that the hydrophobic property of the decorative paper is further enhanced; solves the problem of hydrophobicity reduction caused by more hydrophilic groups in the emulsifier.
Different from the traditional DOPO modified octavinyl polysilsesquioxane, the DOPO flame retardant is directly introduced into an acrylic ester chain segment through the reaction of amino grafted on POSS and epoxy groups on epoxy vinyl siloxane while the DOPO groups on the periphery of the POSS structure are reserved, so that the problem that the traditional flame retardant is poor in dispersibility and needs to be additionally added with a dispersing agent is solved; meanwhile, the polymer is grafted on the siloxane chain segment, and the siloxane chain segment moves to the surface of the polymer due to the characteristics of the hydrophobic property and the low surface energy of the siloxane chain segment, so that DOPO groups can be uniformly dispersed in the polymer, and on the other hand, when the DOPO groups are decomposed or burnt by heating, the DOPO groups can be formed into carbon by solid phase at the first time due to the distribution of the DOPO groups on the surface of the polymer, and the flame retardant effect is achieved by cooperation with the silicon-phosphorus structure of the DOPO groups, so that the flame retardant property of the decorative paper is greatly improved. The DOPO modified POSS chain segment not only endows the decorative paper with excellent hydrophobic and flame retardant properties, but also greatly improves the heat resistance and mechanical properties of the decorative paper due to the highly symmetrical structure.
According to the preparation method, 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol is used as a matrix to prepare quaternary ammonium salt modified acrylic ester, and the quaternary ammonium salt modified acrylic ester is introduced into an acrylic ester resin molecular chain segment through polymerization, on one hand, bacteria are killed through electrostatic interaction between N+ ions and negative charges on the surface of bacteria and hydrophobic interaction between N-alkyl chains and a bacterial film, so that the antibacterial performance of the decorative paper is greatly improved, and the application range of the decorative paper is enlarged; on the other hand, the hexadecyl long chain segment can cooperate with the emulsifier to form micelle, so that the stability of emulsion can be enhanced, meanwhile, ionic bonds are provided for the polymer, the acting force of the polymer on the surface is enhanced, and the adhesive force of the acrylic ester emulsion in the dipping process of the decorative base paper is further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the phosphate ester emulsifier LRP-10 was purchased from nanjing chess, a new materials limited; 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol was purchased from sigma aldrich (Shanghai) trade limited; the rest raw materials are all sold in the market.
Example 1: the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps: s1: adding 0.5g of lithium aluminum hydride monohydrate and 0.5g of secondary distilled water into 110mL of acetone and 20mL of methanol, uniformly stirring, heating to a reflux state, adding 4.32g of allyl trimethoxysilane to perform heat preservation reaction for 20 hours in the reflux state, neutralizing, filtering, washing and drying to obtain silanol polyallyl POSS; adding 10g of silanol polyallylate POSS into 100mL of tetrahydrofuran, adding 12g of silane coupling agent KH540 and 30wt% of methanol solution of tetraethylammonium hydroxide, stirring at room temperature for reaction for 24 hours, performing rotary evaporation, washing and filtering to obtain aminopropyl polyallylate POSS; adding 10g of aminopropyl polyallylate POSS, 30g of DOPO and 0.5g of AIBN into 200mL of toluene under the nitrogen atmosphere, uniformly stirring, heating to 80 ℃ for reaction for 10 hours, adding the lower reactant into dichloromethane, adding ethyl acetate for precipitation, filtering, and drying to obtain aminopropyl flame-retardant modified POSS;
s2: uniformly stirring 10g of octamethyl cyclotetrasiloxane, 3g of hexamethyl silane and 10gKH563, adding 12mol/L of concentrated hydrochloric acid, heating to 100 ℃ for reaction for 2 hours, adding 2g of tetramethyl tetravinyl cyclotetrasiloxane, continuously preserving heat for reaction for 2 hours, and performing rotary evaporation to obtain epoxy vinyl siloxane; adding 12g of aminopropyl flame-retardant modified POSS into 100mL of tetrahydrofuran, uniformly stirring, adding 10g of epoxy vinyl siloxane, adjusting the pH to 9, heating to 50 ℃ for reaction for 5h,
filtering, rotary steaming, washing and drying to obtain flame-retardant modified POSS grafted vinyl siloxane;
s3: 10g of phosphate emulsifier LRP-10 is added into 50mL of sodium methoxide, 21g of allyl glycidyl ether, 0.3g of hypophosphorous acid and 0.5g of triphenyl phosphite are added under the nitrogen atmosphere, and the mixture is heated to 90 ℃ to react for 3.5 hours to obtain an emulsifier A; adding 10g of an emulsifier A into 0.5g of potassium hydroxide, heating to 120 ℃ under the condition of 0.1MPa, introducing 20g of ethylene oxide, and reacting for 3 hours under the condition of heat preservation to obtain an emulsifier B; adding 0.5g of urea into 10g of emulsifier B, heating to 90 ℃ under nitrogen atmosphere, adding 20.2g of sulfamic acid, and reacting for 3 hours to obtain a reactive emulsifier;
s4: adding 1g of 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol and 4g of 1-bromohexadecane into 50mL of acetonitrile, uniformly stirring, heating to 80 ℃ for reaction for 96 hours, vacuum distilling, and washing to obtain an intermediate; adding the intermediate, 1g of isocyanoethyl methacrylate, 0.2g of dibutyl tin dilauryl silicate and 0.1g of hydroquinone into 100mL of tetrahydrofuran, stirring uniformly, heating to 45 ℃ for reaction, vacuum distilling, washing, centrifuging and drying at 40 ℃ to obtain quaternary ammonium salt modified acrylic ester when the content of isocyanate groups is 0;
s5: uniformly stirring 5g of ethyl acrylate, 5g of methyl methacrylate, 5g of styrene, 5g of hydroxyethyl acrylate, 10g of isobornyl methacrylate, 8g of quaternary ammonium salt modified acrylate, 10g of flame-retardant modified POSS grafted vinyl siloxane and 3g of reactive emulsifier, adding 30g of propylene glycol methyl ether acetate and 0.1g of AIBN, and heating to 100 ℃ for reaction for 1.5 hours to obtain composite acrylic ester; adding 2g of germanium dioxide into 100g of composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion with the solid content of 55%; dipping the decorative base paper in acrylic ester emulsion for 1-2min,
taking out and drying to obtain the environment-friendly nanometer negative ion decorative paper.
Example 2: the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps: s5: uniformly stirring 8g of ethyl acrylate, 8g of methyl methacrylate, 8g of styrene, 8g of hydroxyethyl acrylate, 15g of isobornyl methacrylate, 12g of quaternary ammonium salt modified acrylate, 13g of flame-retardant modified POSS grafted vinyl siloxane and 4g of reactive emulsifier, adding 40g of propylene glycol methyl ether acetate and 0.1g of AIBN, and heating to 100 ℃ for reaction for 1.5 hours to obtain composite acrylic ester; adding 2.5g of germanium dioxide into 100g of composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion with the solid content of 55%; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
The remaining steps were the same as in example 1.
Example 3: the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps: s5: uniformly stirring 8g of ethyl acrylate, 8g of methyl methacrylate, 8g of styrene, 8g of hydroxyethyl acrylate, 15g of isobornyl methacrylate, 16g of quaternary ammonium salt modified acrylate, 15g of flame-retardant modified POSS grafted vinyl siloxane and 5g of reactive emulsifier, adding 40g of propylene glycol methyl ether acetate and 0.1g of AIBN, and heating to 100 ℃ for reaction for 1.5 hours to obtain composite acrylic ester; adding 3g of germanium dioxide into 100g of composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion with the solid content of 55%; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
The remaining steps were the same as in example 1.
Comparative example 1: the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps: s1: under the nitrogen atmosphere, adding 10g of octavinyl polysilsesquioxane, 30g of DOPO and 0.5g of AIBN into 200mL of toluene, uniformly stirring, heating to 80 ℃ for reaction for 10 hours, adding a lower reactant into dichloromethane, adding ethyl acetate for precipitation, filtering, and drying to obtain flame-retardant modified POSS;
s2: uniformly stirring 10g of octamethyl cyclotetrasiloxane, 3g of hexamethyl silane and 10gKH563, adding 12mol/L of concentrated hydrochloric acid, heating to 100 ℃ for reaction for 2 hours, adding 2g of tetramethyl tetravinyl cyclotetrasiloxane, continuously preserving heat for reaction for 2 hours, and performing rotary evaporation to obtain epoxy vinyl siloxane;
s3: 10g of phosphate emulsifier LRP-10 is added into 50mL of sodium methoxide, 21g of allyl glycidyl ether, 0.3g of hypophosphorous acid and 0.5g of triphenyl phosphite are added under the nitrogen atmosphere, and the mixture is heated to 90 ℃ to react for 3.5 hours to obtain an emulsifier A; adding 10g of an emulsifier A into 0.5g of potassium hydroxide, heating to 120 ℃ under the condition of 0.1MPa, introducing 20g of ethylene oxide, and reacting for 3 hours under the condition of heat preservation to obtain an emulsifier B; adding 0.5g of urea into 10g of emulsifier B, heating to 90 ℃ under nitrogen atmosphere, adding 20.2g of sulfamic acid, and reacting for 3 hours to obtain a reactive emulsifier;
s4: adding 1g of 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol and 4g of 1-bromohexadecane into 50mL of acetonitrile, uniformly stirring, heating to 80 ℃ for reaction for 96 hours, vacuum distilling, and washing to obtain an intermediate; adding the intermediate, 1g of isocyanoethyl methacrylate, 0.2g of dibutyl tin dilauryl silicate and 0.1g of hydroquinone into 100mL of tetrahydrofuran, stirring uniformly, heating to 45 ℃ for reaction, vacuum distilling, washing, centrifuging and drying at 40 ℃ to obtain quaternary ammonium salt modified acrylic ester when the content of isocyanate groups is 0;
s5: uniformly stirring 5g of ethyl acrylate, 5g of methyl methacrylate, 5g of styrene, 5g of hydroxyethyl acrylate, 10g of isobornyl methacrylate, 8g of quaternary ammonium salt modified acrylate, 5g of epoxy vinyl siloxane, 5g of flame-retardant modified POSS and 3g of reactive emulsifier, adding 30g of propylene glycol methyl ether acetate and 0.1g of AIBN, and heating to 100 ℃ to react for 1.5 hours to obtain composite acrylic ester; adding 2g of germanium dioxide into 100g of composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion with the solid content of 55%; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
Comparative example 2: the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps: s1: adding 0.5g of lithium aluminum hydride monohydrate and 0.5g of secondary distilled water into 110mL of acetone and 20mL of methanol, uniformly stirring, heating to a reflux state, adding 4.32g of allyl trimethoxysilane to perform heat preservation reaction for 20 hours in the reflux state, neutralizing, filtering, washing and drying to obtain silanol polyallyl POSS; adding 10g of silanol polyallylate POSS into 100mL of tetrahydrofuran, adding 12g of silane coupling agent KH540 and 30wt% of methanol solution of tetraethylammonium hydroxide, stirring at room temperature for reaction for 24 hours, performing rotary evaporation, washing and filtering to obtain aminopropyl polyallylate POSS; adding 10g of aminopropyl polyallylate POSS, 30g of DOPO and 0.5g of AIBN into 200mL of toluene under the nitrogen atmosphere, uniformly stirring, heating to 80 ℃ for reaction for 10 hours, adding the lower reactant into dichloromethane, adding ethyl acetate for precipitation, filtering, and drying to obtain aminopropyl flame-retardant modified POSS;
s2: uniformly stirring 10g of octamethyl cyclotetrasiloxane, 3g of hexamethyl silane and 10gKH563, adding 12mol/L of concentrated hydrochloric acid, heating to 100 ℃ for reaction for 2 hours, adding 2g of tetramethyl tetravinyl cyclotetrasiloxane, continuously preserving heat for reaction for 2 hours, and performing rotary evaporation to obtain epoxy vinyl siloxane; adding 12g of aminopropyl flame-retardant modified POSS into 100mL of tetrahydrofuran, uniformly stirring, adding 10g of epoxy vinyl siloxane, adjusting the pH to 9, heating to 50 ℃ for reaction for 5h,
filtering, rotary steaming, washing and drying to obtain flame-retardant modified POSS grafted vinyl siloxane;
s3: 10g of phosphate emulsifier LRP-10 is added into 50mL of sodium methoxide, 21g of allyl glycidyl ether, 0.3g of hypophosphorous acid and 0.5g of triphenyl phosphite are added under the nitrogen atmosphere, and the mixture is heated to 90 ℃ to react for 3.5 hours to obtain an emulsifier A; adding 10g of an emulsifier A into 0.5g of potassium hydroxide, heating to 120 ℃ under the condition of 0.1MPa, introducing 20g of ethylene oxide, and reacting for 3 hours under the condition of heat preservation to obtain an emulsifier B; adding 0.5g of urea into 10g of emulsifier B, heating to 90 ℃ under nitrogen atmosphere, adding 20.2g of sulfamic acid, and reacting for 3 hours to obtain a reactive emulsifier;
s5: uniformly stirring 5g of ethyl acrylate, 5g of methyl methacrylate, 5g of styrene, 5g of hydroxyethyl acrylate, 10g of isobornyl methacrylate, 10g of flame-retardant modified POSS grafted vinyl siloxane and 3g of reactive emulsifier, adding 30g of propylene glycol methyl ether acetate and 0.1g of AIBN, and heating to 100 ℃ to react for 1.5 hours to obtain composite acrylic ester; adding 2g of germanium dioxide into 100g of composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion with the solid content of 55%; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
Comparative example 3: the preparation method of the environment-friendly nanometer negative ion decorative paper comprises the following steps: s1: adding 0.5g of lithium aluminum hydride monohydrate and 0.5g of secondary distilled water into 110mL of acetone and 20mL of methanol, uniformly stirring, heating to a reflux state, adding 4.32g of allyl trimethoxysilane to perform heat preservation reaction for 20 hours in the reflux state, neutralizing, filtering, washing and drying to obtain silanol polyallyl POSS; adding 10g of silanol polyallylate POSS into 100mL of tetrahydrofuran, adding 12g of silane coupling agent KH540 and 30wt% of methanol solution of tetraethylammonium hydroxide, stirring at room temperature for reaction for 24 hours, performing rotary evaporation, washing and filtering to obtain aminopropyl polyallylate POSS; adding 10g of aminopropyl polyallylate POSS, 30g of DOPO and 0.5g of AIBN into 200mL of toluene under the nitrogen atmosphere, uniformly stirring, heating to 80 ℃ for reaction for 10 hours, adding the lower reactant into dichloromethane, adding ethyl acetate for precipitation, filtering, and drying to obtain aminopropyl flame-retardant modified POSS;
s2: uniformly stirring 10g of octamethyl cyclotetrasiloxane, 3g of hexamethyl silane and 10gKH563, adding 12mol/L of concentrated hydrochloric acid, heating to 100 ℃ for reaction for 2 hours, adding 2g of tetramethyl tetravinyl cyclotetrasiloxane, continuously preserving heat for reaction for 2 hours, and performing rotary evaporation to obtain epoxy vinyl siloxane; adding 12g of aminopropyl flame-retardant modified POSS into 100mL of tetrahydrofuran, uniformly stirring, adding 10g of epoxy vinyl siloxane, adjusting the pH to 9, heating to 50 ℃ for reaction for 5h,
filtering, rotary steaming, washing and drying to obtain flame-retardant modified POSS grafted vinyl siloxane;
s3: adding 1g of 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol and 4g of 1-bromohexadecane into 50mL of acetonitrile, uniformly stirring, heating to 80 ℃ for reaction for 96 hours, vacuum distilling, and washing to obtain an intermediate; adding the intermediate, 1g of isocyanoethyl methacrylate, 0.2g of dibutyl tin dilauryl silicate and 0.1g of hydroquinone into 100mL of tetrahydrofuran, stirring uniformly, heating to 45 ℃ for reaction, vacuum distilling, washing, centrifuging and drying at 40 ℃ to obtain quaternary ammonium salt modified acrylic ester when the content of isocyanate groups is 0;
s4: uniformly stirring 5g of ethyl acrylate, 5g of methyl methacrylate, 5g of styrene, 5g of hydroxyethyl acrylate, 10g of isobornyl methacrylate, 8g of quaternary ammonium salt modified acrylate, 10g of flame-retardant modified POSS grafted vinyl siloxane and 3g of fatty alcohol polyoxyethylene ether, adding 30g of propylene glycol methyl ether acetate and 0.1g of AIBN, and heating to 100 ℃ for reaction for 1.5 hours to obtain composite acrylate; adding 2g of germanium dioxide into 100g of composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion with the solid content of 55%; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
And (3) testing: negative ion performance test: the environment-friendly nanometer negative ion decorative paper prepared in the embodiment 1-3 is tested by adopting a DLY-4G-232 negative ion measuring instrument.
Contact angle test: the environment-friendly nano negative ion decorative papers prepared in examples 1 to 3 and comparative example 1 were tested using a contact angle tester.
Flame retardant performance test: the environmental protection type nano negative ion decorative papers prepared in examples 1 to 3 and comparative example 1 were subjected to a limiting oxygen index test and a vertical burning grade test according to astm d 2863-2008 and astm d 3801.
Adhesion test: hundred lattices are marked on the surfaces of the environment-friendly nanometer negative ion decorative papers prepared in the examples 1-3 and the comparative example 2 by using a hundred grits, and the coating is observed to fall off by using a 600-1PK test packaging adhesive tape for testing.
Emulsion stability test: the acrylate emulsions prepared in examples 1-3 and comparative example 3 were tested for mechanical stability of the latex using a centrifuge with a rotational speed of 4000rpm for 30 min. Stability is considered poor if flocculation, sedimentation and delamination occur.
Table one decorative paper test data
Conclusion: the decorative papers prepared in examples 1-3 have excellent flame retardant properties, hydrophobic properties and adhesion.
The addition of the ordinary DOPO modified vinyl POSS in comparative example 1 does not introduce the DOPO-POSS structure into the acrylate structure, resulting in reduced flame retardant and hydrophobic properties;
the quaternary ammonium salt acrylic ester structure is not introduced in the comparative example 2, so that the adhesive force of the acrylic ester emulsion is reduced, and the antibacterial performance is not realized;
the addition of the conventional emulsifier in comparative example 3 did not introduce the emulsifier into the acrylate structure, resulting in a decrease in emulsion stability.
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 environment-friendly nanometer negative ion decorative paper is characterized by comprising the following steps of: comprises the following steps:
s1: adding 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol and 1-bromohexadecane into acetonitrile, stirring uniformly, heating to 80-85 ℃ for reaction for 96-108h, vacuum distillation, and washing to obtain an intermediate; adding an intermediate, isocyanoethyl methacrylate, dibutyl tin dilauryl silicate and hydroquinone into tetrahydrofuran, stirring uniformly, heating to 45-50 ℃ for reaction, vacuum distilling, washing, centrifuging, and drying at 40-45 ℃ to obtain quaternary ammonium salt modified acrylic ester when the content of isocyanate groups is 0;
s2: uniformly stirring ethyl acrylate, methyl methacrylate, styrene, hydroxyethyl acrylate, isobornyl methacrylate, quaternary ammonium salt modified acrylic ester, flame-retardant modified POSS grafted vinyl siloxane and a reactive emulsifier, adding propylene glycol methyl ether acetate and AIBN, heating to 100-105 ℃ for reacting for 1.5-2 hours to obtain composite acrylic ester; adding germanium dioxide into the composite acrylic ester, uniformly stirring, and adding deionized water to obtain acrylic ester emulsion; immersing the decorative base paper in the acrylic ester emulsion for 1-2min, taking out and drying to obtain the environment-friendly nanometer anion decorative paper.
2. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 1, which is characterized in that: the preparation method of the flame-retardant modified POSS grafted vinyl siloxane comprises the following steps: uniformly stirring octamethyl cyclotetrasiloxane, hexamethyl and silane and KH563, adding a catalyst C, heating to 100-105 ℃ for reaction for 2-3h, adding tetramethyl tetravinyl cyclotetrasiloxane, continuously preserving heat for reaction for 2-3h, and performing rotary evaporation to obtain epoxy vinyl siloxane; adding the aminopropyl flame-retardant modified POSS into tetrahydrofuran, uniformly stirring, adding epoxy vinyl siloxane, adjusting the pH to 9-10, heating to 50-55 ℃ for reacting for 5-6h, filtering, steaming, washing and drying to obtain the flame-retardant modified POSS grafted vinyl siloxane.
3. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 2, which is characterized in that: the octamethyl cyclotetrasiloxane: hexamethyl and silane: KH563: the mass ratio of the tetramethyl tetravinyl cyclotetrasiloxane is 1 (0.3-0.5): 1 (0.2-0.25); the aminopropyl flame retardant modified POSS: the molar ratio of the epoxy vinyl siloxane is (1.2-1.5): 1-1.25; the catalyst C is concentrated hydrochloric acid with the concentration of 12-14 mol/L.
4. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 2, which is characterized in that: the preparation method of the aminopropyl flame retardant modified POSS comprises the following steps: adding the catalyst A into acetone and methanol, uniformly stirring, heating to a reflux state, adding allyl trimethoxy silane to perform heat preservation reaction for 20-24 hours in the reflux state, neutralizing, filtering, washing and drying to obtain silanol polyallyl POSS; adding silanol polyallylate POSS into tetrahydrofuran, adding a silane coupling agent KH540 and a catalyst B, stirring at room temperature for reaction for 24 hours, steaming, washing and filtering to obtain aminopropyl polyallylate POSS; under the nitrogen atmosphere, adding the aminopropyl polyallyl POSS, DOPO, AIBN into toluene, stirring uniformly, heating to 80-85 ℃ for reaction for 10-12h, adding the lower reactant into dichloromethane, adding ethyl acetate for precipitation, filtering, and drying to obtain the aminopropyl flame-retardant modified POSS.
5. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 4, which is characterized in that: the allyltrimethoxysilane: the mass ratio of the catalyst A is (4.32-4.56): 1; the silanol polyallylboss: the mass ratio of the silane coupling agent KH540 is 1 (1.2-1.5); the aminopropyl polyallylses: the mass ratio of DOPO is 1:3, a step of; the catalyst A is a lithium aluminum hydride monohydrate and a secondary distilled water mixture with the mass ratio of 1:1; the catalyst B is 28-30wt% of tetraethylammonium hydroxide methanol solution.
6. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 1, which is characterized in that: the preparation method of the reactive emulsifier comprises the following steps: adding a phosphate emulsifier into sodium methoxide, adding allyl glycidyl ether, hypophosphorous acid and triphenyl phosphite under the nitrogen atmosphere, and heating to 90-110 ℃ for reaction for 3.5-4h to obtain an emulsifier A; adding the emulsifier A into potassium hydroxide, heating to 120-140 ℃ under the condition of 0.1-0.2MPa, introducing ethylene oxide, and reacting for 3-4h under the condition of heat preservation to obtain an emulsifier B; adding urea into the emulsifier B, heating to 90-110 ℃ under the nitrogen atmosphere, adding sulfamic acid, and reacting for 3-5h to obtain the reactive emulsifier.
7. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 6, which is characterized in that: the phosphate ester emulsifier: the mol ratio of the allyl glycidyl ether is 1 (2.1-2.3); the emulsifier A: the molar ratio of the ethylene oxide is 1 (2-2.1); the emulsifier B: the mole ratio of sulfamic acid is 1 (2.02-2.22); the phosphate ester emulsifier is LRP-10.
8. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 1, which is characterized in that: the 2- [ [2- (dimethylamino) ethyl ] methylamino ] ethanol: 1-bromohexadecane: the mass ratio of the isocyanoethyl methacrylate is 1 (4-5) to 1-1.2.
9. The method for preparing the environment-friendly nanometer negative ion decorative paper according to claim 1, which is characterized in that: the composite acrylic ester comprises, by mass, 5-10 parts of ethyl acrylate, 5-10 parts of methyl methacrylate, 5-10 parts of styrene, 5-10 parts of hydroxyethyl acrylate, 10-20 parts of isobornyl methacrylate, 8-16 parts of quaternary ammonium salt modified acrylic ester, 10-15 parts of flame-retardant modified POSS grafted vinyl siloxane, 3-5 parts of reactive emulsifier, 30-50 parts of propylene glycol methyl ether acetate and 0.1-0.2 part of AIBN; the addition of germanium dioxide is 2-3wt% of the mass of the composite acrylic ester; the solid content of the acrylic ester emulsion is 55-60%.
10. An environment-friendly nanometer negative ion decorative paper according to any one of claims 1-9 and a preparation method thereof.
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