CN112708320B - Anti-aging nano TiO2Modified acrylic resin composite material and preparation method thereof - Google Patents
Anti-aging nano TiO2Modified acrylic resin composite material and preparation method thereof Download PDFInfo
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 88
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 88
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002057 nanoflower Substances 0.000 claims abstract description 46
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 44
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012989 trithiocarbonate Substances 0.000 claims abstract description 13
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000005406 washing Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 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 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- KUGVQHLGVGPAIZ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KUGVQHLGVGPAIZ-UHFFFAOYSA-N 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 9
- 239000012024 dehydrating agents Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000007112 amidation reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of acrylic resin and discloses an anti-aging nano TiO2Modified acrylic resin composite, TiO2The unique nanoflower structure of the nanoflower has higher specific surface area, and is more beneficial to TiO2Absorbing ultraviolet light, reflecting and scattering ultraviolet light, taking S, S ' -di (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate with two carboxyl groups at two ends as RAFT chain transfer agent, obtaining carboxyl-terminated acrylic resin through reversible addition-fragmentation chain transfer polymerization, and further under the catalytic action of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, enabling the carboxyl group at the chain end and TiO to be in contact with the carboxyl group at the chain end2Carrying out amidation reaction on amino on the surface of the nanoflower to obtain nano TiO2Modified acrylic resin, linking TiO by chemical covalent bond2The nanoflower is organically combined with the acrylic resin chain end, so that TiO is avoided2The agglomeration phenomenon of the nanoflower endows the acrylic resin with the advantages of excellent ultraviolet shielding, ultraviolet aging resistance and the like.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to an anti-aging nano TiO2A modified acrylic resin composite material and a preparation method thereof.
Background
The acrylic resin is a high molecular material obtained by free radical polymerization by using acrylic monomers, has good film forming property, color and gloss retention, simple polymerization method and low cost, can use water as a dispersion medium, has little pollution to the environment, is widely used for coating, adhesives and the like, and has important application in the fields of mechanical manufacture, electronic appliances, medical equipment and the like
In order to further improve the comprehensive properties of the acrylic resin such as water resistance, ultraviolet aging resistance and the like, the acrylic resin needs to be modified by introducing functional monomers, organic silicon, organic fluorine, epoxy resin, nano materials and the like, and nano TiO2Is a non-toxic and pollution-free nano semiconductor material, has excellent photochemical activity, and has ultraviolet shielding, photocatalytic degradation, antibacterial effectHas wide application, so that the nano TiO can be used2The nano TiO modified acrylic resin is combined with acrylic resin to endow the acrylic resin with unique ultraviolet aging resistance, and the mechanical strength reduction of the material caused by aging is avoided, but the nano TiO is2The interface bonding force with acrylic resin is weak, the compatibility is poor, and nano TiO is caused2Easy to agglomerate, and reduces the nano TiO2The photochemical activity can affect the mechanical property and the service performance of the acrylic resin.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides anti-aging nano TiO2The modified acrylic resin composite material and the preparation method solve the problem that the acrylic resin has poor ultraviolet aging resistance, so that the mechanical properties such as tensile strength and the like are reduced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: anti-aging nano TiO2Modified acrylic resin composite material and anti-aging nano TiO2The preparation method of the modified acrylic resin composite material is as follows:
(1) adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:2-4 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 10-20min, pouring the solution into a high-pressure reaction kettle, heating to 20-30h, cooling to room temperature, centrifugally separating to remove the solvent, washing the precipitate product with distilled water and ethanol, placing the product into a muffle furnace, and calcining at 380-420 ℃ for 2-4h to obtain TiO2And (4) nano flowers.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanoflower, adding aminosilane coupling agent, placing in water bath, heating to 50-80 deg.C, reacting for 6-12h, cooling to room temperature, filtering to remove solvent, washing solid product with distilled water and ethanol to obtain aminated TiO2And (4) nano flowers.
(3) Adding a 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctyl ethyl methacrylate, RAFT chain transfer agent S, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and an initiator azobisisobutyronitrile into a sealed reaction bottle, introducing nitrogen to remove oxygen, carrying out RAFT polymerization in a nitrogen atmosphere, cooling in an ice water bath, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO into a flask2Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylamino pyridine, reacting for 18-36h at 20-40 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO2Modified acrylic resin, organic silicon defoamer and acrylate flatting agent, emulsifying at high speed, pouring the solution into a mould, curing and forming a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Preferably, the aminosilane coupling agent in step (2) is any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-aminopropylmethyldiethoxysilane, and the aminosilane coupling agent is mixed with TiO2The mass ratio of the nanoflower is 5-15: 100.
Preferably, the mass ratio of methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctylethyl methacrylate, S '-bis (α, α' -methyl- α "-acetic acid) trithiocarbonate and azobisisobutyronitrile in the step (3) is 20-28:40-60:100:30-40:5-6: 0.35-0.45.
Preferably, the temperature of RART polymerization in the step (3) is 60-80 ℃, and the reaction time is 12-24 h.
Preferably, the carboxyl-terminated acrylic resin and the aminated TiO in the step (4)2The mass ratio of the nanoflower, the dicyclohexylcarbodiimide and the catalyst 4-dimethylaminopyridine is 100:0.5-1.5:2-5: 10-30.
Preferably, the nano TiO in the step (5)2The mass ratio of the modified acrylic resin to the organic silicon defoaming agent to the acrylate leveling agent is 100:0.05-0.1:0.2-0.8。
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the anti-aging nano TiO2The modified acrylic resin composite material is prepared into TiO by regulating a solvothermal reaction system2Nano-flower, compared with traditional nano-TiO2The unique nanoflower structure has higher specific surface area and is more beneficial to TiO2The nanometer flower absorbs ultraviolet light, reflects and scatters the ultraviolet light, and is further modified by amino silane coupling agent to obtain aminated TiO2Nanometer flower for realizing nanometer TiO2The functional modification of the nano TiO widens2The practical application of (1).
The anti-aging nano TiO2The modified acrylic resin composite material is prepared by taking perfluorooctyl ethyl methacrylate as a fluorine-containing monomer and S, S ' -di (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate with carboxyl at two ends as a RAFT chain transfer agent through reversible addition-fragmentation chain transfer polymerization to obtain carboxyl-terminated acrylic resin, so that a fluorine-containing group is introduced into a molecular chain of the acrylic resin, a carboxyl group is introduced into a molecular chain end, and further under the catalytic action of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, the carboxyl at the chain end and TiO2Carrying out amidation reaction on amino on the surface of the nanoflower to obtain nano TiO2Modifying the acrylic resin to bind the TiO by chemical covalent bonds2The nanoflower is organically combined with the acrylic resin chain end, so that the acrylic resin and TiO are obviously enhanced2The interfacial binding force and acting force of the nanoflower improve the compatibility between the nanoflower and the nanoflower, and avoid TiO2Agglomeration of nanoflower, highly dispersed TiO2The nanoflower endows the acrylic resin with the advantages of excellent ultraviolet shielding, ultraviolet aging resistance and the like.
The anti-aging nano TiO2Modified acrylic resin composite, uniformly dispersed TiO2The nanometer flowers form micro-nanometer protruding and concave structures on the surface of the acrylic resin coating, so that the roughness of the surface of the coating is increasedThe structure is adopted, and the perfluorooctyl ethyl methacrylate as the fluorine-containing monomer has lower surface energy, so that the water contact angle of the surface of the coating is increased, the composite material shows good hydrophobicity and water resistance, and the stability of the acrylic resin in an aqueous dispersion medium is improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: anti-aging nano TiO2The preparation method of the modified acrylic resin composite material is as follows:
(1) adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:2-4 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 10-20min, pouring the solution into a high-pressure reaction kettle, heating to 20-30h, cooling to room temperature, centrifugally separating to remove the solvent, washing the precipitate product with distilled water and ethanol, placing the product into a muffle furnace, and calcining at 380-420 ℃ for 2-4h to obtain TiO2And (4) nano flowers.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanometer flower uniformly, adding amino silane coupling agent, wherein the amino silane coupling agent is any one of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-aminopropyl methyl diethoxy silane, and TiO2Placing the nanoflower in a water bath kettle at a mass ratio of 5-15:100, heating to 50-80 ℃, reacting for 6-12h, cooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol to obtain the aminated TiO2And (4) nano flower.
(3) Adding 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctyl ethyl methacrylate, RAFT chain transfer agent S, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and initiator azobisisobutyronitrile into a sealed reaction bottle according to the mass ratio of 20-28:40-60:100:30-40:5-6:0.35-0.45, introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction at 60-80 ℃ in a nitrogen atmosphere for 12-24h, then placing the obtained product in an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Feeding flaskAdding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO in the mass ratio of 100:0.5-1.5:2-5:10-302Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylamino pyridine, reacting for 18-36h at 20-40 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO with the mass ratio of 100:0.05-0.1:0.2-0.82Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Example 1
(1) Adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:2 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 10min, pouring the solution into a high-pressure reaction kettle, heating to 20h, cooling to room temperature, centrifugally separating to remove the solvent, washing the precipitate with distilled water and ethanol, placing the precipitate in a muffle furnace, and calcining at 380 ℃ for 2h to obtain TiO2And (4) nano flower.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanoflower uniformly, adding aminosilane coupling agent, wherein the aminosilane coupling agent is any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-aminopropylmethyldiethoxysilane, and mixing with TiO2Placing the nanoflower into a water bath kettle with the mass ratio of 5:100, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol to obtain the aminated TiO2And (4) nano flowers.
(3) Adding a 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctyl ethyl methacrylate, a RAFT chain transfer agent S, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and an initiator azobisisobutyronitrile in a mass ratio of 20:40:100:30:5:0.35 into a sealed reaction bottle, then introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction for 12 hours at 60 ℃ in a nitrogen atmosphere, then placing in an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO into a flask according to the mass ratio of 100:0.5:2:102Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylamino pyridine, reacting for 18h at 20 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO with the mass ratio of 100:0.05:0.22Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Example 2
(1) Adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:2 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 20min, pouring the solution into a high-pressure reaction kettle, heating to 30h, cooling to room temperature, centrifugally separating to remove the solvent, washing a precipitate product with distilled water and ethanol, placing the precipitate product into a muffle furnace, and calcining at 400 ℃ for 3h to obtain TiO2And (4) nano flowers.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanometer flower uniformly, adding amino silane coupling agent, wherein the amino silane coupling agent is any one of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-aminopropyl methyl diethoxy silane, and TiO2Placing the nanoflower into a water bath kettle with the mass ratio of 8:100, heating to 80 ℃, reacting for 6 hours, cooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol to obtain the aminated TiO2And (4) nano flowers.
(3) Adding 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluoro octyl ethyl methacrylate, RAFT chain transfer agent S, S ' -di (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and initiator azobisisobutyronitrile into a sealed reaction bottle in a mass ratio of 22:45:100:32:5.2:0.38, introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction for 24h at 60 ℃ in a nitrogen atmosphere, then placing the mixture into an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO in the mass ratio of 100:0.7:3:15 into a flask2Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting for 24 hours at 40 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO with the mass ratio of 100:0.081:0.42Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Example 3
(1) Adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:3 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 15min, pouring the solution into a high-pressure reaction kettle, heating to 24h, cooling to room temperature, centrifugally separating to remove the solvent, washing a precipitate product with distilled water and ethanol, placing the precipitate product into a muffle furnace, and calcining at 400 ℃ for 3h to obtain TiO2And (4) nano flowers.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanometer flower uniformly, adding amino silane coupling agent, wherein the amino silane coupling agent is any one of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-aminopropyl methyl diethoxy silane, and TiO2Placing the nanoflower into a water bath kettle according to the mass ratio of 12:100, heating to 60 ℃, reacting for 8 hours, cooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol to obtain the aminated TiO2And (4) nano flowers.
(3) Adding 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluoro octyl ethyl methacrylate, RAFT chain transfer agent S, S ' -di (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and initiator azobisisobutyronitrile into a sealed reaction bottle according to the mass ratio of 26:55:100:38:5.7:0.4, introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction for 18h at 70 ℃ in a nitrogen atmosphere, then placing the mixture into an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO in the mass ratio of 100:1.2:4:22 into a flask2Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting for 24 hours at 30 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO with the mass ratio of 100:0.08:0.62Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Example 4
(1) Adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:4 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 20min, pouring the solution into a high-pressure reaction kettle, heating to 30h, cooling to room temperature, centrifugally separating to remove the solvent, washing the precipitate with distilled water and ethanol, placing the precipitate in a muffle furnace, and calcining at 420 ℃ for 4h to obtain TiO2And (4) nano flowers.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanometer flower uniformly, adding amino silane coupling agent, wherein the amino silane coupling agent is any one of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-aminopropyl methyl diethoxy silane, and TiO2Placing into water bath kettle at a mass ratio of 15:100, heating to 80 deg.C, reacting for 12 hr, cooling to room temperature, filtering to remove solvent, washing solid product with distilled water and ethanolThen, aminated TiO is obtained2And (4) nano flowers.
(3) Adding a 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctyl ethyl methacrylate, a RAFT chain transfer agent S, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and an initiator azobisisobutyronitrile into a sealed reaction bottle according to the mass ratio of 28:60:100:40:6:0.45, introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction for 24 hours at 80 ℃ in a nitrogen atmosphere, then placing the mixture into an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO into a flask according to the mass ratio of 100:1.5:5:302Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting for 36h at 40 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO with the mass ratio of 100:0.1:0.82Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Comparative example 1
(1) Adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:1.5 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 10min, pouring the solution into a high-pressure reaction kettle, heating to 30h, cooling to room temperature, centrifugally separating to remove the solvent, washing a precipitate product with distilled water and ethanol, placing the precipitate product into a muffle furnace, and calcining at 420 ℃ for 3h to obtain TiO2And (4) nano flower.
(2) Adding toluene solvent and TiO into a flask2Dispersing nanometer flower uniformly, adding amino silane coupling agent, wherein the amino silane coupling agent is any one of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-aminopropyl methyl diethoxy silane, and TiO2Placing the nanoflower into a water bath kettle with the mass ratio of 2:100, heating to 60 ℃, reacting for 12 hours, cooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol to obtain the aminated TiO2And (4) nano flowers.
(3) Adding a 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctyl ethyl methacrylate, a RAFT chain transfer agent S, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and an initiator azobisisobutyronitrile in a mass ratio of 15:35:100:26:4.7:0.32 into a sealed reaction bottle, introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction at 70 ℃ in a nitrogen atmosphere for 24 hours, then placing in an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO in the mass ratio of 100:0.2:1:5 into a flask2Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting for 24 hours at 40 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding acetone solvent into a flask, and adding nano TiO with the mass ratio of 100:0.035:0.12Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Comparative example 2
(1) Adding a mixed solvent of glycerol and ethanol with a volume ratio of 1:6 into a flask, dropwise adding tetra-n-butyl titanate, stirring for 15min, pouring the solution into a high-pressure reaction kettle, heating to 30h, cooling to room temperature, centrifugally separating to remove the solvent, washing a precipitate product with distilled water and ethanol, placing the precipitate product into a muffle furnace, and calcining at 400 ℃ for 3h to obtain TiO2And (4) nano flower.
(2) Adding toluene solvent and TiO into a flask2Nano flower, adding amino silane coupling agent after dispersing uniformly, wherein amino silane is coupledThe agent is any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-aminopropylmethyldiethoxysilane, and TiO2Placing the nanoflower into a water bath kettle with the mass ratio of 18:100, heating to 50 ℃, reacting for 12 hours, cooling to room temperature, filtering to remove the solvent, washing the solid product with distilled water and ethanol to obtain the aminated TiO2And (4) nano flower.
(3) Adding 1, 4-dioxane solvent, methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluoro octyl ethyl methacrylate, RAFT chain transfer agent S, S ' -di (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and initiator azobisisobutyronitrile into a sealed reaction bottle in a mass ratio of 30:68:100:43:6.4:0.5, introducing nitrogen to remove oxygen, carrying out RAFT polymerization reaction for 24h at 70 ℃ in a nitrogen atmosphere, then placing the mixture into an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain the carboxyl-terminated acrylic resin.
(4) Adding anhydrous dichloromethane solvent, carboxyl-terminated acrylic resin and aminated TiO into a flask according to the mass ratio of 100:2:6:402Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting for 24 hours at 30 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin.
(5) Adding nano TiO with the mass ratio of 100:0.10:0.1 into an acetone solvent in a flask2Modified acrylic resin, organic silicon defoamer and acrylate flatting agent, emulsifying at high speed, pouring the solution into a mould, curing and forming a film to obtain the anti-aging nano TiO2A modified acrylic resin composite material.
Anti-aging nano TiO2The modified acrylic resin composite material is placed under a 200W ultraviolet lamp to be irradiated for an accelerated aging test for 360h, the wavelength of the ultraviolet lamp is composite light, the wavelength band is 254-380nm, the irradiation distance is 10cm, a WDW-100 electronic universal tester is used for testing the tensile strength and the elongation at break of the composite material, and the test standard is GB/T1040.1-2018.
Testing anti-aging nano TiO by using SDC-500 contact angle tester2The water contact angle of the modified acrylic resin composite material is tested according to the national standard GB/T30693-2014.
Claims (2)
1. Anti-aging nano TiO2The modified acrylic resin composite material is characterized in that: the anti-aging nano TiO2The preparation method of the modified acrylic resin composite material is as follows:
(1) dropping tetra-n-butyl titanate into a mixed solvent of glycerol and ethanol with the volume ratio of 1:2-4, stirring, pouring the solution into a high-pressure reaction kettle, heating for 20-30h, cooling to room temperature, centrifugally separating to remove the solvent, washing the precipitate product with distilled water and ethanol, placing the product into a muffle furnace, calcining for 2-4h at the temperature of 380-420 ℃ to obtain TiO2Nano flower;
(2) adding TiO into toluene solvent2Dispersing nanoflower, adding aminosilane coupling agent, placing in water bath, heating to 50-80 deg.C, reacting for 6-12h, cooling to room temperature, filtering to remove solvent, washing solid product with distilled water and ethanol to obtain aminated TiO2Nano flower;
(3) adding methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctyl ethyl methacrylate, RAFT chain transfer agent S, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and initiator azobisisobutyronitrile into a 1, 4-dioxane solvent, then introducing nitrogen to remove oxygen, carrying out RAFT polymerization in a nitrogen atmosphere, then placing in an ice water bath for cooling, carrying out reduced pressure distillation, and carrying out diethyl ether centrifugal washing and purification to obtain carboxyl-terminated acrylic resin;
(4) adding carboxyl acrylic resin and aminated TiO into anhydrous dichloromethane solvent2Dispersing the nanometer flower evenly, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst 4-dimethylamino pyridine, reacting for 18-36h at 20-40 ℃, decompressing and distilling to remove the solvent after the reaction, and centrifugally washing and purifying diethyl ether to obtain the nanometer TiO2Modified acrylic resin;
(5) adding nano TiO into acetone solvent2Modified acrylic resin, an organic silicon defoamer and an acrylate flatting agent, emulsifying at a high speed, pouring the solution into a mold, and curing to form a film to obtain the anti-aging nano TiO2Modified acrylic resin composite materials;
wherein the aminosilane coupling agent in the step (2) is any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-aminopropylmethyldiethoxysilane, and TiO2The mass ratio of the nano flowers is 5-15: 100;
wherein the mass ratio of methyl acrylate, methyl methacrylate, n-butyl acrylate, perfluorooctylethyl methacrylate, S ' -bis (alpha, alpha ' -methyl-alpha ' -acetic acid) trithiocarbonate and azobisisobutyronitrile in the step (3) is 20-28:40-60:100:30-40:5-6: 0.35-0.45;
wherein the RART polymerization reaction in the step (3) is carried out at the temperature of 60-80 ℃ for 12-24 h;
wherein, the carboxyl-terminated acrylic resin and the aminated TiO in the step (4)2The mass ratio of the nanoflower, the dicyclohexylcarbodiimide and the catalyst 4-dimethylaminopyridine is 100:0.5-1.5:2-5: 10-30.
2. The anti-aging nano TiO of claim 12The modified acrylic resin composite material is characterized in that: the nano TiO in the step (5)2The mass ratio of the modified acrylic resin to the organic silicon defoaming agent to the acrylate leveling agent is 100:0.05-0.1: 0.2-0.8.
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