CN112457455B - Preparation method of fluorocarbon resin, fluorocarbon resin and application - Google Patents
Preparation method of fluorocarbon resin, fluorocarbon resin and application Download PDFInfo
- Publication number
- CN112457455B CN112457455B CN202011415062.0A CN202011415062A CN112457455B CN 112457455 B CN112457455 B CN 112457455B CN 202011415062 A CN202011415062 A CN 202011415062A CN 112457455 B CN112457455 B CN 112457455B
- Authority
- CN
- China
- Prior art keywords
- methacrylate
- silicon dioxide
- nano silicon
- fluorocarbon resin
- methyl methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 173
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 77
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 46
- 239000011737 fluorine Substances 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- 230000000977 initiatory effect Effects 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 16
- -1 tridecyl octyl Chemical group 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 10
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 9
- YPCMISLZCVOUJB-UHFFFAOYSA-N 4-cyano-4-methyl-5-phenyl-5-sulfanylidenepentanoic acid Chemical compound OC(=O)CCC(C)(C#N)C(=S)C1=CC=CC=C1 YPCMISLZCVOUJB-UHFFFAOYSA-N 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011253 protective coating Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- CLISWDZSTWQFNX-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)F CLISWDZSTWQFNX-UHFFFAOYSA-N 0.000 claims description 2
- PHFBUQLYIAXNEB-UHFFFAOYSA-N 2,4,6-triphenyl-2h-thiopyran Chemical class S1C(C=2C=CC=CC=2)C=C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 PHFBUQLYIAXNEB-UHFFFAOYSA-N 0.000 claims description 2
- RQTKXUGYFLEUJV-UHFFFAOYSA-N 2,4,6-tris(4-methoxyphenyl)-2H-thiopyran Chemical class C1=CC(OC)=CC=C1C1C=C(C=2C=CC(OC)=CC=2)C=C(C=2C=CC(OC)=CC=2)S1 RQTKXUGYFLEUJV-UHFFFAOYSA-N 0.000 claims description 2
- CAVOMBYQSRVLNI-UHFFFAOYSA-N 2,4,6-tris(4-methoxyphenyl)pyrylium Chemical compound C1=CC(OC)=CC=C1C1=CC(C=2C=CC(OC)=CC=2)=[O+]C(C=2C=CC(OC)=CC=2)=C1 CAVOMBYQSRVLNI-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- RNTXYZIABJIFKQ-UHFFFAOYSA-N 4-cyano-4-dodecylsulfanylcarbothioylsulfanylpentanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C#N)CCC(O)=O RNTXYZIABJIFKQ-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- RKHKUHQPRDTHEI-UHFFFAOYSA-N N[S+](CC#N)C(OC1=CC=CC=C1)=S Chemical compound N[S+](CC#N)C(OC1=CC=CC=C1)=S RKHKUHQPRDTHEI-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 15
- 229920000058 polyacrylate Polymers 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000003973 paint Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000007921 spray Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000013467 fragmentation Methods 0.000 description 6
- 238000006062 fragmentation reaction Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000006897 homolysis reaction Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 230000001105 regulatory effect Effects 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
- LDJNCEDHGGKACP-UHFFFAOYSA-N 2-propyl-3H-1,2lambda4-benzodithiole-2-carbonitrile Chemical compound C(#N)S1(SC2=C(C1)C=CC=C2)CCC LDJNCEDHGGKACP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention is suitable for the technical field of materials, and provides a preparation method of fluorocarbon resin, fluorocarbon resin and application, wherein the preparation method comprises the following steps: adding methyl methacrylate monomers with the same mass into the nano silicon dioxide/ethanol dispersion liquid to obtain a modified nano silicon dioxide/methyl methacrylate monomer mixed solution, further placing the modified nano silicon dioxide/methyl methacrylate monomer mixed solution, a fluorine-containing acrylate solution, a photoinitiator, a chain transfer agent and an initiation aid into a transparent closed container, uniformly mixing by rotation, and then stirring for 4-12 hours at room temperature by using an LED lamp source with the wavelength of more than 400 nm. According to the invention, fluorinated polyacrylate is used as a base material, and the modified nano silicon dioxide/methyl methacrylate monomer is added, so that the modified nano silicon dioxide/methyl methacrylate monomer has good dispersibility in fluorinated polyacrylate copolymer paint, and fluorocarbon resin with excellent performance of being initiated by visible light and controllable in reaction is obtained, and the performances of the paint film appearance, water resistance, adhesive force, pencil hardness, salt spray resistance, aging resistance and the like of the coating are effectively improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of fluorocarbon resin, the fluorocarbon resin and application.
Background
With the economic development and the arrival of the intelligent electronic era, the generation, the transmission, the storage and the application of knowledge are rapidly developed, and the informatization plays a vital role in the development of the whole society. Wherein the development of the LED display screen is an important part in the development of informatization. Due to the limitation of LED packaging materials and technologies, an LED screen without special protection treatment is used in some specific scenes, so that the test of the use environment, such as erosion and damage of moisture, humidity, cleaning solvent and the like to the luminescent crystal, is difficult to bear, and the reliability and the service life of the luminescent crystal are greatly reduced. In order to solve the surface protection of high-end LED display products and improve the market competitiveness of the products, it is necessary to develop a protective material suitable for the surface of a screen and improve the reliability of related products, so as to ensure the normal and efficient operation of the products in a severe environment, prolong the service life of the products and further improve the added value of high-order products.
In the prior art, compared with the traditional three-proofing paint with certain requirements on thickness, the coating has good leveling performance and can be more suitable for an LED screen through thin spraying. Protective coating materials applied to spraying are mainly organic coatings, and can be generally classified into epoxy, acrylic acid, polyurethane, organic silicon, alkyd, phenolic aldehyde, vinyl ester resin and the like. The fluorine-containing polyacrylate has many excellent performances, such as low surface energy, weather resistance, heat resistance, corrosion resistance, excellent electrical properties and the like, has wide application market and prospect in the field of outdoor coatings, can be suitable for protection of LED screens, and has poor performances in the aspects of hardness, solvent resistance, scratch resistance and the like.
Therefore, the prior fluorine-containing polyacrylate has the problems of poor hardness, solvent resistance and scratch resistance and limited use.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of fluorocarbon resin, and aims to solve the problems of poor hardness, solvent resistance and scratch resistance and limited use of the existing fluorine-containing polyacrylate.
The embodiment of the invention is realized in such a way that the preparation method of the fluorocarbon resin comprises the following steps:
dispersing the modified nano silicon dioxide in absolute ethyl alcohol to obtain nano silicon dioxide/ethyl alcohol dispersion liquid;
adding methyl methacrylate monomers with the same mass into the nano silicon dioxide/ethanol dispersion liquid, and obtaining a modified nano silicon dioxide/methyl methacrylate monomer mixed solution with the mass fraction of 5-35% after uniform mixing and evaporation treatment;
placing the modified nano silicon dioxide/methyl methacrylate monomer mixed solution, the fluorine-containing acrylate solution, the photoinitiator, the chain transfer agent and the initiation aid in a transparent closed container, uniformly mixing by rotation, and then stirring for 4-12 hours at room temperature by using an LED lamp source with the wavelength of more than 400nm to obtain the modified nano silicon dioxide/methyl methacrylate monomer mixed solution;
the molar ratio of the fluorine-containing acrylate solution to the photoinitiator to the chain transfer agent is 200-400: 0.1-0.5: 1 to 20.
Another object of the embodiments of the present invention is to provide a fluorocarbon resin, which is prepared by the preparation method of the fluorocarbon resin.
The embodiment of the invention also aims to provide an application of the fluorocarbon resin in preparing protective paint for LED display products.
The preparation method of the fluorocarbon resin provided by the embodiment of the invention is simple in process, clean and environment-friendly, realizes that the polymerization reaction is controlled by switching light by utilizing a method of photoinduced electron transfer-reversible addition fragmentation chain transfer radical polymerization (PET-RAFT) with stronger practicability to obtain the fluorocarbon resin with controllable molecular weight and narrow dispersity, and simultaneously adds the modified nano silicon dioxide/methyl methacrylate monomer mixed solution, so that the nano protective coating for the LED screen is good in dispersity in fluorinated polyacrylate copolymer coating, can be cured by visible light in a room temperature environment, and has excellent paint film appearance, water resistance, adhesive force, pencil hardness, salt fog resistance and ageing resistance. Compared with the traditional RAFT (reversible addition-fragmentation chain transfer) method for generating free radicals by a thermal homolysis method, the coating can be initiated by visible light at room temperature, is suitable for various substrate materials, can avoid other influences caused by a heating process, and has wider application scenes without heating and isolating oxygen; meanwhile, the photoinitiation can also control the on and off of polymerization by regulating the on and off of light, can control the polymerization reaction process and the reaction rate, and can obtain a proper nano coating according to the use requirement.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The performance of the fluorine-containing polyacrylate in the aspects of hardness, solvent resistance, scratch resistance and the like is poor, and the fluorine-containing polyacrylate needs to be modified to increase the hardness and scratch resistance of a coating. The fluorine-containing polyacrylate is generally free radical polymerization, but the method has high requirements on polymerization environment, needs oxygen isolation or high-temperature curing, but the temperature tolerance of the LED screen part material is limited, and the LED screen part material cannot be operated for a long time in a high-temperature environment, so that a normal-temperature curable fluorine-containing polyacrylate coating must be adopted. Because of the properties of slow initiation, fast growth and fast termination of common free radical polymerization and the easy chain transfer reaction to monomers, solvents and the like, the prepared fluorine-containing polymer has the defects of difficult control of molecular weight, molecular weight distribution, polymer structure and the like, and more fluorine-containing monomers are usually required to be added when the fluorine-containing polymerization meets certain performances. Since fluoromonomers are expensive, they tend to increase the cost of the polymer, limiting its use in certain applications.
The embodiment of the invention provides a preparation method of fluorocarbon resin for solving the problems of poor hardness, aging resistance and scratch resistance performance and limited use of the existing fluorine-containing polyacrylate, the preparation method is simple in process, clean and environment-friendly, the polymerization reaction is controlled by switching on and off light by utilizing a method of photoinduced electron transfer-reversible addition fragmentation chain transfer radical polymerization (PET-RAFT) with stronger practicability, the fluorocarbon resin with controllable molecular weight and narrow dispersity is obtained, simultaneously adding the modified nano silicon dioxide/methyl methacrylate monomer mixed solution, it has good dispersibility in fluorinated polyacrylate copolymer paint, can be cured by visible light at room temperature, and the LED screen nano protective coating has excellent paint film appearance, water resistance, adhesive force, pencil hardness, salt spray resistance and aging resistance. Compared with the traditional RAFT (reversible addition-fragmentation chain transfer) method for generating free radicals by a thermal homolysis method, the coating can be initiated by visible light at room temperature, is suitable for various substrate materials, can avoid other influences caused by a heating process, and has wider application scenes without heating and isolating oxygen; meanwhile, the photoinitiation can also control the on and off of polymerization by regulating the on and off of light, can control the polymerization reaction process and the reaction rate, and can obtain a proper nano coating according to the use requirement. In addition, the visible light curing fluorocarbon resin is simple in use process, does not need to be cured through thermochemical reaction, and can be cured by visible light after being directly sprayed on the LED screen according to actual conditions; the spraying is convenient, the cost is obviously reduced, the spraying is not influenced by the environment or the volume of the base material, and the manpower and material resources in the spraying process are reduced.
In the embodiment of the invention, the preparation method of the fluorocarbon resin comprises the following steps:
and S101, dispersing the modified nano silicon dioxide in absolute ethyl alcohol to obtain nano silicon dioxide/ethyl alcohol dispersion liquid.
In the embodiment of the invention, the modified nano-silica is dispersed in absolute ethyl alcohol, and a nano-silica/ethyl alcohol dispersion liquid with the mass fraction of 15% is generally obtained.
And S102, adding methyl methacrylate monomers with the same mass into the nano silicon dioxide/ethanol dispersion liquid, and uniformly mixing and evaporating to obtain a modified nano silicon dioxide/methyl methacrylate monomer mixed solution with the mass fraction of 5-35%.
And S103, placing the modified nano silicon dioxide/methyl methacrylate monomer mixed solution, the fluorine-containing acrylate solution, the photoinitiator, the chain transfer agent and the initiation aid in a transparent closed container, uniformly mixing by rotation, and then stirring for 4-12 hours at room temperature by using an LED lamp source with the wavelength of more than 400 nm.
In the embodiment of the invention, the molar ratio of the fluorine-containing acrylate solution to the photoinitiator to the chain transfer agent is 200-400: 0.1-0.5: 1 to 20.
In the embodiment of the invention, the illumination stirring time of the LED lamp source with the wavelength of more than 400nm at room temperature is preferably 4-6h, and the gel permeation chromatography analysis of the product under different illumination stirring times shows that the product molecular weight and the polymerization dispersion degree corresponding to the illumination time of 4-6h have the best effect.
In the embodiment of the invention, the preparation method of the modified nano silicon dioxide comprises the following steps:
adding absolute ethyl alcohol and deionized water into the nano silicon dioxide, adding gamma-methacryloxypropyl trimethoxy silane into an alkaline environment, uniformly dispersing, standing and layering the solution, performing centrifugal separation, cleaning and drying treatment to obtain the nano silicon dioxide.
In the embodiment of the invention, the mass ratio of the nano silicon dioxide to the gamma-methacryloxypropyltrimethoxysilane is 20: 1 to 4.
In the embodiment of the invention, a certain amount of nano silicon dioxide is weighed, absolute ethyl alcohol and deionized water are added, a small amount of triethylamine is added dropwise to adjust the pH value to 8-9, gamma-methacryloxypropyl trimethoxy silane is added, ultrasonic dispersion is carried out for 30min at room temperature, heating and stirring reaction are carried out at 40 ℃, and the solution is stood for layering, and then centrifugal separation, cleaning and drying treatment are carried out, thus obtaining the nano silicon dioxide.
In the embodiment of the invention, the fluorine-containing acrylate solution is prepared from methacrylate, hydroxy methacrylate, fluorine-containing methacrylic acid and a solvent according to a mass ratio of 2-4: 1-1.5: 0.5-2.5: 4, mixing and preparing.
In the embodiment of the invention, the methacrylate is one or a mixture of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, glycidyl methacrylate and ethylene glycol dimethacrylate.
In the embodiment of the invention, the hydroxy methacrylate is one of hydroxyethyl methacrylate and hydroxypropyl methacrylate or a mixture of the two in any proportion.
In the embodiment of the invention, the fluorine-containing methacrylic acid is one of trifluoroethyl methacrylate, pentafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate and tridecafluorooctyl methacrylate or a mixture of two or more of them in any proportion.
In the embodiment of the present invention, the solvent may be one of benzene, xylene, anisole, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, butanone, cyclohexanone, propanol, and butanol, or a mixed solvent of several solvents in any proportion.
In the embodiment of the present invention, the photoinitiator is any one of 2, 4, 6-triphenylpyrane tetrafluoroborate (TPT +), 2, 4, 6-triphenylthiopyrane salt (TTPP +), 2, 4, 6-tris (4-methoxyphenyl) pyrylium tetrafluoroborate (p-MeO-TPT +), 2, 4, 6-tris (4-methoxyphenyl) thiopyrane salt (p-MeO-TTPP +), Fluorescein (FL), rhodamine B, rhodamine 6G, eosin y (ey), and lamp light with a wavelength of more than 400nm is used.
In the embodiment of the present invention, the chain transfer agent is any one of ethyl phenylpropionate disulfide, butyl trithiobutyl propionate, 4-cyano-4- (thiobenzoyl) valeric acid, 2-cyano-2-propylbenzodithiol, 4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanylpentanoic acid, cyanomethyl (phenyl) aminodithiocarbonate, 2-cyano-2-propyl-dodecyltrithiocarbonyl ester, and 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
In the embodiment of the invention, the mass fraction of the initiation aid is 5-15%.
In the embodiment of the invention, the initiation assistant is one of triethylamine, methyldiethanolamine and N-methylpyrrolidone.
The embodiment of the invention also provides the fluorocarbon resin prepared by the preparation method of the fluorocarbon resin.
The embodiment of the invention also provides an application of the fluorocarbon resin in preparing the protective coating of the LED display product; the fluorocarbon resin is modified fluorinated polyacrylate copolymer, and the coating suitable for a spraying mode can be obtained by adding a leveling agent, a dispersing agent and a defoaming agent, and the specific matching method can be realized by referring to the prior art.
The technical effects of the preparation method of fluorocarbon resin of the present invention will be further described with reference to the specific embodiments; however, the specific implementation methods mentioned in these examples are only illustrative of the technical solutions of the present invention, and do not limit the implementation scope of the present invention.
Example 1
(1) Activation modification of nano silicon dioxide
Weighing 10g of nano silicon dioxide, adding 120ml of absolute ethyl alcohol and 6.5ml of deionized water, dropwise adding a small amount of triethylamine to adjust the pH value to 8, adding 2gKH-570 to activate and modify the nano silicon dioxide, ultrasonically dispersing the nano silicon dioxide at room temperature for 30min, heating the nano silicon dioxide at 40 ℃, magnetically stirring the nano silicon dioxide for 24h, standing and layering the solution after the reaction is finished, centrifugally separating the solution, and washing the solution for 3 times by using the absolute ethyl alcohol; the final powder was collected and dried at 80 ℃ for 12 h.
Adding 17g of absolute ethyl alcohol into 3g of modified nano silicon dioxide powder, uniformly stirring and dispersing to obtain nano silicon dioxide/ethyl alcohol dispersion liquid containing 15% of mass fraction, taking the same mass nano silicon dioxide/ethyl alcohol dispersion liquid and methyl methacrylate monomer, mixing and stirring, removing the ethyl alcohol in the mixed solution by using a vacuum rotary evaporator to obtain modified nano silicon dioxide/methyl methacrylate monomer mixed solution, and supplementing a small amount of methyl methacrylate monomer to obtain the modified nano silicon dioxide/methyl methacrylate monomer mixed solution containing 15% of mass fraction.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
100g of a fluorine-containing acrylate solution, 0.75g of eosin y, 7g of 4-cyano-4- (thiobenzoyl) valeric acid, 10g of N-methylpyrrolidone and 10g of a modified silica/methyl methacrylate monomer mixed solution are added into a transparent closed container, the transparent closed container filled with the mixed solution is further mixed for three minutes in a full-automatic rotary mixer in a rotating mode, the solution is mixed uniformly, and then the mixture is stirred for 6 hours at room temperature under the illumination of an LED lamp source with the wavelength of more than 400 nm. Wherein the fluorine-containing acrylate solution is methyl methacrylate: hydroxyethyl methacrylate: dodecafluoroheptyl methacrylate: xylene: butyl acetate is mixed according to the mass ratio of 4: 1.5: 0.5: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 89.3% and the molecular weight was Mn,GPC10150g/mol, polydispersity PDI 1.32.
Example 2
(1) The modified nano-silica/methyl methacrylate monomer mixed solution was obtained in the same manner as in example 1.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
100g of a fluorine-containing acrylate solution, 0.75g of eosin y, 7g of 4-cyano-4- (thiobenzoyl) valeric acid, 10g of N-methylpyrrolidone and 10g of a modified silica/methyl methacrylate monomer mixed solution are added into a transparent closed container, the transparent closed container filled with the mixed solution is further mixed for three minutes in a full-automatic rotary mixer in a rotating mode, the solution is mixed uniformly, and then the mixture is stirred for 6 hours at room temperature under the illumination of an LED lamp source with the wavelength of more than 400 nm. Wherein the fluorine-containing acrylate solution is methyl methacrylate: hydroxyethyl methacrylate: dodecafluoroheptyl methacrylate: xylene: butyl acetate is mixed according to the mass ratio of 4: 1: 1: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 88.5% and the molecular weight was Mn,GPC10400g/mol and a polydispersity PDI of 1.36.
Example 3
(1) The modified nano-silica/methyl methacrylate monomer mixed solution was obtained in the same manner as in example 1.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
100g of fluorine-containing acrylate solution, 0.65g of eosin y, 5.5g of 2-cyano-2-propyl-benzodithio, 15g of triethylamine and 10g of modified silicon dioxide/methyl methacrylate monomer mixed solution are added into a transparent closed container, then the transparent closed container filled with the mixed solution is rotationally mixed for three minutes by a full-automatic rotary mixer, the solution is uniformly mixed, and then the mixture is stirred for 10 hours under the illumination of an LED lamp source with the wavelength of more than 400nm at room temperature. Wherein the fluorine-containing acrylate solution is methyl methacrylate: lauryl methacrylate: hydroxyethyl methacrylate: octafluoropentyl methacrylate: xylene: propylene glycol methyl ether acetate according to a mass ratio of 2: 2: 1.5: 0.5: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 72.3% and the molecular weight was Mn,GPC8200g/mol, polydispersity PDI 1.52.
Example 4
(1) The modified nano-silica/methyl methacrylate monomer mixed solution was obtained in the same manner as in example 1.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
100g of a fluorine-containing acrylate solution, 0.8g of eosin y, 8.5g of 4-cyano-4- (thiobenzoyl) valeric acid, 10g of N-methyl pyrrolidone and 10g of a modified silica/methyl methacrylate monomer mixed solution are added into a transparent closed container, the transparent closed container filled with the mixed solution is further mixed by a full-automatic rotary mixer in a rotating mode for three minutes, the solution is mixed uniformly, and then the mixture is stirred for 5 hours at room temperature under the illumination of an LED lamp source with the wavelength of more than 400 nm. Wherein the fluorine-containing acrylate solution is methyl methacrylate: glycidyl methacrylate; hydroxyethyl methacrylate: dodecafluoroheptyl methacrylate: xylene: butyl acetate according to the mass ratio of 2; 2: 1.5: 0.5: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 81.2% and the molecular weight was Mn,GPC11300g/mol, the polydispersity PDI is 1.42.
Example 5
(1) Activation modification of nano silicon dioxide
Weighing 10g of nano silicon dioxide, adding 120ml of absolute ethyl alcohol and 6.5ml of deionized water, dropwise adding a small amount of triethylamine to adjust the pH value to 8, adding 2gKH-570 to activate and modify the nano silicon dioxide, ultrasonically dispersing the nano silicon dioxide at room temperature for 30min, heating the nano silicon dioxide at 40 ℃, magnetically stirring the nano silicon dioxide for 24h, standing and layering the solution after the reaction is finished, centrifugally separating the solution, and washing the solution for 3 times by using the absolute ethyl alcohol; the final powder was collected and dried at 80 ℃ for 12 h.
Adding 5g of modified nano-silica powder into 15g of absolute ethyl alcohol, uniformly stirring and dispersing to obtain nano-silica/ethyl alcohol dispersion liquid containing 25 mass percent, taking the same mass of nano-silica/ethyl alcohol dispersion liquid and methyl methacrylate monomer, mixing and stirring, removing the ethyl alcohol in the mixed solution by using a vacuum rotary evaporator to obtain modified nano-silica/methyl methacrylate monomer mixed solution, and supplementing a small amount of methyl methacrylate monomer to obtain the modified nano-silica/methyl methacrylate monomer mixed solution containing 25 mass percent.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
100g of fluorine-containing acrylate solution, 0.85g of eosin y, 9g of 4-cyano-4- (thiobenzoyl) valeric acid, 15g of triethylamine and 10g of modified silicon dioxide/methyl methacrylate monomer mixed solution are added into a transparent closed container, then the transparent closed container filled with the mixed solution is rotationally mixed for three minutes by a full-automatic rotary mixer, the solution is uniformly mixed, and then the mixture is stirred for 6 hours under the illumination of an LED lamp source with the wavelength of more than 400nm at room temperature. Wherein the fluorine-containing acrylate solution is lauryl methacrylate: glycidyl methacrylate: hydroxyethyl methacrylate: dodecafluoroheptyl methacrylate: xylene: butyl acetate is mixed according to the mass ratio of 2: 2: 1.5: 0.5: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 68.2% and the molecular weight was Mn,GPC11200g/mol, polydispersity PDI 1.52.
Comparative example 1
(1) Activation modification of nano silicon dioxide
Weighing 10g of nano silicon dioxide, adding 120ml of absolute ethyl alcohol and 6.5ml of deionized water, dropwise adding a small amount of triethylamine to adjust the pH value to 8, adding 2gKH-570 to activate and modify the nano silicon dioxide, ultrasonically dispersing the nano silicon dioxide at room temperature for 30min, heating the nano silicon dioxide at 40 ℃, magnetically stirring the nano silicon dioxide for 24h, standing and layering the solution after the reaction is finished, centrifugally separating the solution, and washing the solution for 3 times by using the absolute ethyl alcohol; the final powder was collected and dried at 80 ℃ for 12 h.
Adding 17g of absolute ethyl alcohol into 3g of modified nano silicon dioxide powder, uniformly stirring and dispersing to obtain nano silicon dioxide/ethyl alcohol dispersion liquid containing 15% of mass fraction, taking the same mass nano silicon dioxide/ethyl alcohol dispersion liquid and methyl methacrylate monomer, mixing and stirring, removing the ethyl alcohol in the mixed solution by using a vacuum rotary evaporator to obtain modified nano silicon dioxide/methyl methacrylate monomer mixed solution, and supplementing a small amount of methyl methacrylate monomer to obtain the modified nano silicon dioxide/methyl methacrylate monomer mixed solution containing 15% of mass fraction.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
10g of modified silicon dioxide/methyl methacrylate monomer mixed solution, 0.07g of eosin y, 0.7g of 4-cyano-4- (thiobenzoyl) valeric acid and 1g of N-methylpyrrolidone are added into a transparent closed container, then the transparent closed container filled with the mixed liquid is rotationally mixed for three minutes by a full-automatic rotary mixer, the solution is uniformly mixed, and then the mixture is stirred for 1 hour under the illumination of an LED lamp source with the wavelength of more than 400nm at room temperature. Then 100g of a fluoroacrylate solution, 0.68g of eosin y, 6.3g of 4-cyano-4- (thiobenzoyl) pentanoic acid, and 9g of N-methylpyrrolidone were added, the above transparent closed container containing the mixed liquid was mixed by rotation for three minutes in a fully automatic rotary mixer to mix the solutions uniformly, and then stirred at room temperature for 6 hours under illumination with an LED lamp source having a wavelength of more than 400 nm. Wherein the fluorine-containing acrylate solution is methyl methacrylate: hydroxyethyl methacrylate: dodecafluoroheptyl methacrylate: xylene: butyl acetate is mixed according to the mass ratio of 4: 1.5: 0.5: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 79.3% and the molecular weight was Mn,GPC8400g/mol, polydispersity PDI 1.85.
Comparative example 2
(1) Activation modification of nano silicon dioxide
Weighing 10g of nano silicon dioxide, adding 120ml of absolute ethyl alcohol and 6.5ml of deionized water, dropwise adding a small amount of triethylamine to adjust the pH value to 8, adding 2gKH-570 to activate and modify the nano silicon dioxide, ultrasonically dispersing the nano silicon dioxide at room temperature for 30min, heating the nano silicon dioxide at 40 ℃, magnetically stirring the nano silicon dioxide for 24h, standing and layering the solution after the reaction is finished, centrifugally separating the solution, and washing the solution for 3 times by using the absolute ethyl alcohol; the final powder was collected and dried at 80 ℃ for 12 h.
(2) PET-RAFT polymerized nano silicon dioxide modified fluorocarbon resin
100g of a fluorine-containing acrylate solution, 0.75g of eosin y, 7g of 4-cyano-4- (thiobenzoyl) valeric acid, 10g of N-methylpyrrolidone, 1.5g of modified silica powder and 8.5g of methyl methacrylate monomer are added into a transparent closed container, and the transparent closed container filled with the mixed liquid is rotationally mixed for three minutes by a full-automatic rotary mixer to uniformly mix the solutions, and then stirred for 6 hours at room temperature under the illumination of an LED lamp source with the wavelength of more than 400 nm. Wherein the fluorine-containing acrylate solution is methyl methacrylate: hydroxyethyl methacrylate: dodecafluoroheptyl methacrylate: toluene: butyl acetate is mixed according to the mass ratio of 4: 1.5: 0.5: 2: 2, preparing the mixture.
The conversion, determined gravimetrically, was 83%, the molecular weight of which was Mn,GPC10200g/mol and a polydispersity PDI of 1.46.
The fluorocarbon resins prepared in the above examples and comparative examples were respectively sprayed on six groups of quartz test pieces, and the six groups of quartz test piece samples were subjected to test analysis of paint film appearance, surface drying, actual drying, water resistance, adhesion, pencil hardness, salt spray resistance, and aging resistance, and the test results are shown in table 1 below.
TABLE 1
In summary, as can be seen from table 1, in the embodiments of the present invention, by using a method of photoinduced electron transfer-reversible addition fragmentation chain transfer radical polymerization (PET-RAFT) with strong practicability, a fluorinated polyacrylate is used as a base material, and a modified nano silica/methyl methacrylate monomer mixed solution is added to obtain a fluorocarbon resin with excellent performance of being initiated by visible light and controllable in reaction, and the modified nano silica/methyl methacrylate monomer mixed solution has good dispersibility in a fluorinated polyacrylate copolymer coating, so that the performances of the coating in the aspects of paint film appearance, water resistance, adhesion, pencil hardness, salt spray resistance, aging resistance, and the like are effectively improved; in addition, compared with the traditional RAFT (reversible addition-fragmentation chain transfer) method for generating free radicals by a thermal homolysis method, the fluorocarbon resin can be initiated by visible light at room temperature, is suitable for various substrate materials, and can avoid other influences caused by a heating process; the application scene of the coating is wider without heating and isolating oxygen, the visible light curing fluorocarbon paint has simple use process, does not need to be cured by a thermochemical reaction, and can be cured by visible light after being directly sprayed on the LED screen according to actual conditions; the spraying is convenient, the cost is obviously reduced, the spraying is not influenced by the environment or the volume of the base material, and the manpower and material resources in the spraying process are reduced.
It is worth noting that the fluorine-containing polymer has the defects of difficult control of molecular weight, molecular weight distribution and polymer structure, etc., when the fluorine-containing polymerization meets certain performances, more fluorine-containing monomers are generally required to be added, and the fluorine-containing monomers are expensive, so the cost of the polymer is often increased, and the application of the fluorine-containing monomers in certain fields is limited. The molecular weight and the molecular weight distribution can be effectively controlled by utilizing the PET-RAFT polymerization reaction, and a good protection effect can be obtained by adding a small amount of fluorine-containing monomer.
Further, on the basis of the example 1, the influence of the illumination stirring time on the conversion rate, the molecular weight and the polymerization dispersion degree of the obtained fluorocarbon resin is researched by changing the illumination stirring time of the LED light source with the wavelength of more than 400nm, the gel permeation chromatography of the obtained fluorocarbon resin is respectively measured, the appearance of the formed paint film is recorded, and the results shown in the following table 2 are obtained.
TABLE 2
In summary, from Table 2, the effect of the molecular weight and the polydispersity obtained by the stirring time of 4-6 hours with the LED light source with the wavelength of more than 400nm is the best; under the condition of the illumination reaction time, the monomer is basically completely converted, the molecular weight is increased due to the continuous illumination reaction, and the appearance of a paint film is influenced by the increase of agglomeration.
Further, the content of modified silica in the modified nano silica/methyl methacrylate monomer mixed solution is adjusted to be 5%, 25%, 35% and 45% by adjusting the addition amount of the modified silica, the modified silica is not added to the control group, and the addition and preparation processes of the other components are the same as those in example 1. The fluorocarbon resin and the comparative example obtained by the preparation method are respectively sprayed on six groups of quartz test pieces, the appearance and the hardness of paint films of the six groups of quartz test piece samples are tested and analyzed, and the test results are shown in the following table 3.
TABLE 3
In summary, as can be seen from table 3, the addition of the modified nano-silica/methyl methacrylate monomer mixed solution with the mass fraction of 5% to 35% can effectively improve the hardness of the fluorocarbon resin, and the amount of the modified silica can be added according to the actual required paint film appearance.
Further, the present invention was made to adjust the amount of the fluorine-containing acrylate monomer to 5%, 15%, 20%, 25% of the content of dodecafluoroheptyl methacrylate in the fluorine-containing acrylate solution, and the control group was made to have no fluorine-containing acrylate monomer and the other components were added in the same manner as in example 2. The prepared fluorocarbon resin and the control group are respectively sprayed on six groups of Q235 steel sheets and quartz test sheets, and the test sheet samples are subjected to salt spray resistance and aging resistance for test analysis, wherein the test results are shown in the following table 4.
TABLE 4
In summary, it can be seen from table 4 that when the content of the dodecafluoroheptyl methacrylate in the fluoroacrylate solution reaches 15% to 25%, the salt spray resistance and the aging resistance of the fluorocarbon resin can be effectively improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A method for preparing fluorocarbon resin is characterized by comprising the following steps:
dispersing the modified nano silicon dioxide in absolute ethyl alcohol to obtain nano silicon dioxide/ethyl alcohol dispersion liquid;
adding methyl methacrylate monomers with the same mass into the nano silicon dioxide/ethanol dispersion liquid, and uniformly mixing and evaporating to obtain a modified nano silicon dioxide/methyl methacrylate monomer mixed solution with the mass fraction of 5-35%;
placing the modified nano silicon dioxide/methyl methacrylate monomer mixed solution, the fluorine-containing acrylate solution, the photoinitiator, the chain transfer agent and the initiation aid in a transparent closed container, uniformly mixing by rotation, and then stirring for 4-6 hours at room temperature by using an LED lamp source with the wavelength of more than 400 nm;
the molar ratio of the fluorine-containing acrylate solution to the photoinitiator to the chain transfer agent is 200-400: 0.1-0.5: 1-20; the fluorine-containing acrylate solution is prepared from methacrylate, hydroxy methacrylate, fluorine-containing methacrylic acid and a solvent according to a mass ratio of 2-4: 1-1.5: 0.5-2.5: 4, mixing and preparing;
the preparation method of the modified nano silicon dioxide comprises the following steps:
adding absolute ethyl alcohol and deionized water into nano silicon dioxide, adding gamma-methacryloxypropyl trimethoxy silane into an alkaline environment, uniformly dispersing, standing and layering the solution, performing centrifugal separation, cleaning and drying treatment to obtain the nano silicon dioxide; the mass ratio of the nano silicon dioxide to the gamma-methacryloxypropyl trimethoxysilane is 20: 1 to 4.
2. A method for preparing fluorocarbon resin according to claim 1, characterized in that said methacrylate is one or a mixture of several of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate;
the hydroxyl methacrylate is one or a mixture of two of hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the fluorine-containing methacrylic acid is one or a mixture of more than two of trifluoroethyl methacrylate, pentafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate and tridecyl octyl methacrylate;
the solvent is one or a mixture of more of benzene, xylene, anisole, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, butanone, cyclohexanone, propanol and butanol.
3. A method for producing a fluorocarbon resin as set forth in claim 1, wherein said photoinitiator is any one of 2, 4, 6-triphenylpyrane tetrafluoroborate, 2, 4, 6-triphenylthiopyrane salt, 2, 4, 6-tris (4-methoxyphenyl) pyrylium tetrafluoroborate, 2, 4, 6-tris (4-methoxyphenyl) thiopyrane salt, fluorescein, rhodamine B, rhodamine 6G, and eosin y.
4. A method for preparing fluorocarbon resin as set forth in claim 1, wherein said chain transfer agent is any one of ethyl phenylpropionate disulfide, butyl trithiopropionate, 4-cyano-4- (thiobenzoyl) pentanoic acid, 2-cyano-2-propylbenzodithio, 4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanylpentanoic acid, cyanomethyl (phenyl) aminodithiocarbonate, 2-cyano-2-propyl-dodecyltrithiocarbonyl ester, 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
5. A method for preparing fluorocarbon resin as claimed in claim 1, wherein said initiation aid is present in a mass fraction of 5% to 15%.
6. A method for preparing fluorocarbon resin as claimed in claim 1 or 5, characterized in that said initiation aid is one of triethylamine, methyldiethanolamine, N-methylpyrrolidone.
7. Fluorocarbon resin, characterized in that, the fluorocarbon resin is prepared by the method of any one of claims 1 to 6.
8. Use of the fluorocarbon resin of claim 7 in the preparation of protective coatings for LED display products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011415062.0A CN112457455B (en) | 2020-12-04 | 2020-12-04 | Preparation method of fluorocarbon resin, fluorocarbon resin and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011415062.0A CN112457455B (en) | 2020-12-04 | 2020-12-04 | Preparation method of fluorocarbon resin, fluorocarbon resin and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112457455A CN112457455A (en) | 2021-03-09 |
| CN112457455B true CN112457455B (en) | 2021-05-25 |
Family
ID=74801148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011415062.0A Active CN112457455B (en) | 2020-12-04 | 2020-12-04 | Preparation method of fluorocarbon resin, fluorocarbon resin and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457455B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717603B (en) * | 2021-10-11 | 2022-07-12 | 广西民族大学 | Modified fluorocarbon anticorrosive paint and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110089271A (en) * | 2008-10-10 | 2011-08-05 | 팀칼 에스에이(팀칼아게)(팀칼리미티드) | Carbon particles coated with polymer films, methods for their production and uses thereof |
| CN101845124B (en) * | 2010-03-23 | 2011-12-21 | 武汉双虎涂料有限公司 | Water-based hydrophobic nano-resin, glass thermal insulating coating and preparation method |
| CN101792639B (en) * | 2010-04-02 | 2012-09-05 | 德莱特恩环保涂料(北京)有限公司 | Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof |
| CN104558449B (en) * | 2014-12-30 | 2019-02-19 | 北京金汇利应用化工制品有限公司 | A kind of preparation method of high patience organo-mineral complexing modified aqueous acrylic acid resin |
| JP2018522999A (en) * | 2015-08-10 | 2018-08-16 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Thiocarbonylthio-free RAFT polymer and process for producing the same |
| CN107523152A (en) * | 2015-12-10 | 2017-12-29 | 吴联凯 | Modified Nano SiO for fluorocarbon coating2Preparation method |
| CN107397959B (en) * | 2017-07-28 | 2020-10-16 | 国家纳米科学中心 | Preparation method and application of nano antagonist with ultrastructure on surface |
| CN109337410B (en) * | 2018-10-12 | 2020-11-06 | 安庆北化大科技园有限公司 | Fluorine-containing nano SiO with photoinitiation activity2Preparation method of microsphere and nano SiO2 |
-
2020
- 2020-12-04 CN CN202011415062.0A patent/CN112457455B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112457455A (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lei et al. | Synthesis and characterization of UV-absorbing fluorine-silicone acrylic resin polymer | |
| CN101348611B (en) | Acroleic acid modified polysiloxane resin and coating thereof | |
| CN102731788B (en) | Organosilicone hybrid and organosilicone composite paint and preparations thereof | |
| CN105585879B (en) | One kind can quick-setting acrylic resin paint | |
| CN108546540B (en) | Preparation method of ultraviolet curing transfer adhesive for glass substrate | |
| CN102827501A (en) | Double-curing varnish paint | |
| CN105368297B (en) | high-temperature-resistant vacuum plating UV coating and preparation method and application thereof | |
| CN107083150B (en) | A kind of UV coating for automobile interiors and its preparation method and application | |
| CN105462468A (en) | Undercoat used for base material with copper film, base material with copper film, manufacturing method for base material with copper film, and conductive film | |
| CN1204170C (en) | Preparation method of nano particles with high refractive index and polymer nano composite film material | |
| CN112457455B (en) | Preparation method of fluorocarbon resin, fluorocarbon resin and application | |
| Ha et al. | UV curing kinetics and properties of polyurethane acrylate/multi-walled carbon nanotube coatings | |
| CN108546485B (en) | High-solid-content organic-inorganic hybrid resin and preparation method thereof | |
| CN108753182A (en) | A kind of OCA optical cements haveing excellent performance, optical adhesive tape and preparation method thereof | |
| JP2001163906A (en) | Low refractive index composition, low refractive index film, optical multilayer film and antireflection film | |
| CN108485452B (en) | Water-based paint suitable for wooden products and preparation method thereof | |
| CN101348679B (en) | Anti-pasting anti-covering coating and preparation thereof | |
| CN113122101A (en) | Ultraviolet-curable fluorosilicone polyacrylate antifouling coating for glass and preparation method thereof | |
| CN116333575B (en) | Green multi-substrate universal rainproof and stain-resistant light-transmitting coating for solar power supply wireless communication system and preparation method thereof | |
| CN110041798B (en) | Preparation method of PVC waterproof coating | |
| KR20040104155A (en) | Organic-inorganic hybrid ultraviolet curable hard coating composition and method for preparing same, and hard coat film manufactured by using same | |
| CN111234686A (en) | Self-crosslinking acrylic polyurethane dispersion stone-like paint and preparation method thereof | |
| CN111777872A (en) | Preparation method of functional film for shielding infrared rays | |
| CN113308178B (en) | Preparation method of polyphenyl ether super-hydrophobic coating | |
| CN114015352B (en) | High-transparency light pollution prevention coating and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |