CN107868182A - A kind of polynary collaboration antifouling paint resin and preparation method thereof - Google Patents
A kind of polynary collaboration antifouling paint resin and preparation method thereof Download PDFInfo
- Publication number
- CN107868182A CN107868182A CN201711241195.9A CN201711241195A CN107868182A CN 107868182 A CN107868182 A CN 107868182A CN 201711241195 A CN201711241195 A CN 201711241195A CN 107868182 A CN107868182 A CN 107868182A
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- Prior art keywords
- monomer
- initiator
- acrylic acid
- esters
- functional group
- Prior art date
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 70
- 239000011347 resin Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003973 paint Substances 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 91
- 238000000576 coating method Methods 0.000 claims abstract description 67
- 239000011248 coating agent Substances 0.000 claims abstract description 58
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical group COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 claims abstract description 41
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 polyethylene Polymers 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000013256 coordination polymer Substances 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract 8
- 239000003999 initiator Substances 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229960002504 capsaicin Drugs 0.000 claims description 9
- 235000017663 capsaicin Nutrition 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- LPNLASIEYTWMBC-UHFFFAOYSA-N [tert-butyl(dimethyl)silyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[Si](C)(C)C(C)(C)C LPNLASIEYTWMBC-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- UGKLJUIMKCCNGS-UHFFFAOYSA-N triethylsilyl prop-2-enoate Chemical compound CC[Si](CC)(CC)OC(=O)C=C UGKLJUIMKCCNGS-UHFFFAOYSA-N 0.000 claims description 2
- PIQIWPDMOYYEBV-UHFFFAOYSA-N triphenylsilyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PIQIWPDMOYYEBV-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 6
- MWGMEGAYPPQWFG-UHFFFAOYSA-N [SiH4].OC(=O)C=C Chemical class [SiH4].OC(=O)C=C MWGMEGAYPPQWFG-UHFFFAOYSA-N 0.000 claims 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- NBKXIQAGLFPJCA-UHFFFAOYSA-N 1-butoxypropyl acetate Chemical compound CCCCOC(CC)OC(C)=O NBKXIQAGLFPJCA-UHFFFAOYSA-N 0.000 claims 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 35
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical group [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 abstract description 27
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 241000894006 Bacteria Species 0.000 abstract description 7
- 238000005498 polishing Methods 0.000 abstract description 7
- 102000004169 proteins and genes Human genes 0.000 abstract description 5
- 108090000623 proteins and genes Proteins 0.000 abstract description 5
- 229920000178 Acrylic resin Polymers 0.000 abstract description 3
- 239000004925 Acrylic resin Substances 0.000 abstract description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 3
- 230000012010 growth Effects 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 66
- 239000004342 Benzoyl peroxide Substances 0.000 description 19
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 19
- 235000019400 benzoyl peroxide Nutrition 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 239000008096 xylene Substances 0.000 description 10
- 238000007664 blowing Methods 0.000 description 8
- 239000002954 polymerization reaction product Substances 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000206761 Bacillariophyta Species 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 2
- 0 CC(CC(C)=*[C@]1(*)C(O[Si](C)(*)*)=S(C)CCC(C)(C)C1(C)C)N(CCC1)C1=O Chemical compound CC(CC(C)=*[C@]1(*)C(O[Si](C)(*)*)=S(C)CCC(C)(C)C1(C)C)N(CCC1)C1=O 0.000 description 2
- 241000502321 Navicula Species 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 2
- APNSJCGUSTXBLE-UHFFFAOYSA-N C=CC(NCc(cc1Cl)ccc1O)=O Chemical compound C=CC(NCc(cc1Cl)ccc1O)=O APNSJCGUSTXBLE-UHFFFAOYSA-N 0.000 description 1
- IYLKBLLCOUKITR-UHFFFAOYSA-N CC(CC1(C)C(O)=NCCC1(C)C)N(CCC1)C1=O Chemical compound CC(CC1(C)C(O)=NCCC1(C)C)N(CCC1)C1=O IYLKBLLCOUKITR-UHFFFAOYSA-N 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 240000008574 Capsicum frutescens Species 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LCAOFKNDEPERSU-UHFFFAOYSA-N propan-2-ylsilyl 2-methylprop-2-enoate Chemical compound CC(C)[SiH2]OC(=O)C(C)=C LCAOFKNDEPERSU-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- PWVJTRQTFFVDEU-UHFFFAOYSA-N triethylsilyl 2-methylprop-2-enoate Chemical compound CC[Si](CC)(CC)OC(=O)C(C)=C PWVJTRQTFFVDEU-UHFFFAOYSA-N 0.000 description 1
- PGQNYIRJCLTTOJ-UHFFFAOYSA-N trimethylsilyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)O[Si](C)(C)C PGQNYIRJCLTTOJ-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 238000005406 washing Methods 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- 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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- 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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种多元协同防污涂料树脂及其制备方法；其通式P(AA‑SiA‑PVP‑CP)；其AA结构单体为丙烯酸酯类单体，CP结构单体为含辣素官能团的单体，SiA结构单体为丙烯酸甲硅烷酯类单体，NVP结构单体为N‑乙烯吡咯烷酮。采用自由基溶液聚合将N‑乙烯吡咯烷酮和辣素官能团以及丙烯酸甲硅烷酯类官能团引入到丙烯酸树脂上，得到一种多元协同防污涂料树脂，既可以具有辣素官能团的抗菌功能又具有聚乙烯吡咯烷酮结构的抗蛋白吸附功能，同时还具有丙烯酸甲硅烷酯的低表面能与自抛光的功能，可以抑制细菌的黏附与蛋白的吸附以及及时清除表面的污损物，阻断其他大型生物继续在船舶表面生长；可以很好的保护海洋环境。
The invention discloses a multi-component synergistic antifouling coating resin and a preparation method thereof; its general formula is P(AA‑SiA‑PVP‑CP); its AA structural monomer is an acrylate monomer, and its CP structural monomer is a The monomer of the prime functional group, the SiA structural monomer is a silyl acrylate monomer, and the NVP structural monomer is N-vinylpyrrolidone. Using free radical solution polymerization to introduce N-vinylpyrrolidone and capsaicin functional groups and silyl acrylate functional groups into acrylic resin to obtain a multi-component synergistic antifouling coating resin, which can not only have the antibacterial function of capsaicin functional groups but also have polyethylene The anti-protein adsorption function of the pyrrolidone structure also has the low surface energy and self-polishing function of silyl acrylate, which can inhibit the adhesion of bacteria and the adsorption of proteins and timely remove the contamination on the surface, blocking other large organisms from continuing to Growth on the surface of ships; it can protect the marine environment very well.
Description
技术领域technical field
本发明涉及一种防污涂料树脂及其制备方法和应用，尤其是涉及一种既具有抗菌功能、抗蛋白吸附功能又同时具有侧链可降解功能的防污涂料树脂及其制备方法。The invention relates to an antifouling coating resin and its preparation method and application, in particular to an antifouling coating resin with antibacterial function, anti-protein adsorption function and side chain degradable function and its preparation method.
背景技术Background technique
众所周知，海洋生物污损对海洋里的人工设施腐蚀污损严重。海洋生物污损是指具有附着特性的海洋生物(海洋细菌，绿藻，硅藻和藤壶等)附着在海水中的固体表面进行生长繁殖，从而造成船舶、海洋工程及水下设施表面产生污损破坏事故的现象。其中受损失最为严重的是船舶，海洋生物的附着会增加船舶自身重量和航行阻力，增加燃油消耗，并且严重影响船舶航行性能。据统计，当船舶生物污损率达到5％时，船舶与海水之间的摩擦系数增加50％，燃油消耗量增加40-50％，资金花费增加77％。解决海洋生物污染的方法有机械清除、水下清理、海水淡水转换、涂覆海洋防污涂料等，其中最有效、最便捷的方法为涂覆海洋防污涂料。It is well known that marine biofouling has caused serious corrosion and pollution to artificial facilities in the ocean. Marine biofouling refers to the growth and reproduction of marine organisms (marine bacteria, green algae, diatoms and barnacles, etc.) damage to accidents. Among them, the most serious loss is the ship. The attachment of marine organisms will increase the ship's own weight and navigation resistance, increase fuel consumption, and seriously affect the ship's navigation performance. According to statistics, when the biofouling rate of a ship reaches 5%, the friction coefficient between the ship and seawater increases by 50%, fuel consumption increases by 40-50%, and capital expenditure increases by 77%. The methods to solve marine biological pollution include mechanical removal, underwater cleaning, conversion of seawater and freshwater, and coating of marine antifouling coatings, among which the most effective and convenient method is coating marine antifouling coatings.
传统的海洋防污涂料以自抛光型防污涂料的使用最为广泛，该类涂料含有毒性杀生剂(biocide)成分，当涂料浸于海水中时，通过基质的水解释放出毒料，杀死靠近涂层周围的海洋生物，并且在水流的作用下基质不断水解，继续露出新的光滑表面，降低航行阻力。其中以含有机锡化合物(如三丁基锡TBT)的自抛光防污涂料应用效果最好，但TBT毒性很强，对非目标性海洋生物致死或致畸，严重破坏生态平衡，已被国际海事组织完全禁止。近年来，低表面能型防污涂层因不易附着污损生物而成为研究热点，包括有机硅和有机氟两大类，但低表面能涂层静态防污效果较差，一旦海洋生物吸附在船底，则需要施加一定的外力才能够脱离，所以目前只能应用在高速船体上。因此，必须将多种有效防污技术协同作用，方能更好地实现高效、无毒、节能的防污目标。The traditional marine antifouling paint is the most widely used self-polishing antifouling paint. This type of paint contains toxic biocide components. The marine organisms around the coating, and the matrix is continuously hydrolyzed under the action of the water flow, continuing to reveal a new smooth surface, reducing navigation resistance. Among them, self-polishing antifouling coatings containing organotin compounds (such as tributyltin TBT) have the best application effect, but TBT is very toxic, causing death or teratogenicity to non-target marine organisms, seriously destroying the ecological balance, and has been approved by the International Maritime Organization. Totally prohibited. In recent years, low surface energy antifouling coatings have become a research hotspot because they are not easy to attach fouling organisms, including organic silicon and organic fluorine. However, low surface energy coatings have poor static antifouling effects. Once marine organisms are adsorbed on For the bottom of the ship, a certain external force needs to be applied to be able to break away, so it can only be applied to high-speed hulls at present. Therefore, a variety of effective anti-fouling technologies must be synergistic in order to better achieve the goal of high-efficiency, non-toxic, and energy-saving anti-fouling.
本发明选用的辣椒素是从辣椒等天然产物中提取出来的一种绿色环保、具有良好的杀菌、趋避活性的物质。在海洋防污中，它可有效防止细菌吸附，趋避污损生物，是一种天然高效防污剂；本发明选用的PVP具有很低的聚合物-水界面能，对于蛋白质吸附和细菌粘附的具有优良耐性。另外，由于PVP具有优异的水结合性能，与水结合形成一层紧密的水化层，为蛋白、细菌、细胞等的粘附设置了壁垒。本发明选用的丙烯酸甲硅烷酯聚合物，具有低表面能以及可水解的特性，使涂层不但不易粘附污损物，而且在水中可以定期的脱除表面层，以及时清洗表面污染物。因此将这三种单体结合到一起，有望提供一种兼具抗菌、抗蛋白、趋避污损生物、自抛光功能的多元协同改性环境友好型防污涂料树脂，在环境友好型海洋防污领域有很大的应用前景。The capsaicin selected in the present invention is a kind of green and environment-friendly substance extracted from natural products such as capsicum, and has good bactericidal and repellent activities. In marine antifouling, it can effectively prevent bacterial adsorption and tend to avoid fouling organisms. It is a natural and efficient antifouling agent; the PVP selected in the present invention has a very low polymer-water interface energy, which is good for protein adsorption and bacterial adhesion. has excellent endurance. In addition, because PVP has excellent water-binding properties, it combines with water to form a tight hydration layer, which sets up barriers for the adhesion of proteins, bacteria, cells, etc. The silyl acrylate polymer selected in the present invention has low surface energy and hydrolyzable characteristics, so that the coating is not only difficult to adhere to dirt, but also can regularly remove the surface layer in water, so as to clean the surface pollutants in time. Therefore, the combination of these three monomers is expected to provide a multi-component synergistically modified environment-friendly antifouling coating resin with antibacterial, anti-protein, anti-fouling organisms, and self-polishing functions. The field has great application prospects.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种兼具抗菌、抗蛋白、趋避污损生物、自抛光功能的多元协同改性环境友好型防污涂料树脂及其制备方法和应用。The technical problem to be solved by the present invention is to provide a multi-component synergistically modified environment-friendly antifouling coating resin with the functions of antibacterial, anti-protein, anti-fouling organisms and self-polishing functions, as well as its preparation method and application.
本发明提供了一种多元协同改性防污涂料树脂，其通式P(AA-SiA-PVP-CP)结构如下：The invention provides a multi-element synergistically modified antifouling coating resin, whose general formula P(AA-SiA-PVP-CP) structure is as follows:
式中：In the formula:
R2，R3为H或CH3；R 2 , R 3 is H or CH 3 ;
R1为H，CH3，CH2CH3，CH2CH2CH3，CH2CH2CH2CH3，CH2CH(CH3)2或C(CH3)3；R 1 is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 CH 3 , CH 2 CH(CH 3 ) 2 or C(CH 3 ) 3 ;
R4，R6为CH3，CH2CH3，C(CH3)3，CH(CH3)2，C6H5，Si(CH3)3；R 4 and R 6 are CH 3 , CH 2 CH 3 , C(CH 3 ) 3 , CH(CH 3 ) 2 , C 6 H 5 , Si(CH 3 ) 3 ;
R5为CH3，CH2CH3，C(CH3)3，CH(CH3)2，C6H5，Si(CH3)3；R 5 is CH 3 , CH 2 CH 3 , C(CH 3 ) 3 , CH(CH 3 ) 2 , C 6 H 5 , Si(CH 3 ) 3 ;
R7，R8，R9为F，Cl，Br，OH，OCH3,H或OCH2CH3。R7, R8, R9 are F, Cl, Br, OH, OCH 3 , H or OCH 2 CH 3 .
通式中，包括4个结构单元，其中AA结构单体为丙烯酸酯类单体，CP结构单体为含辣素官能团的单体，SiA结构单体为丙烯酸甲硅烷酯类单体，NVP结构单体为N-乙烯吡咯烷酮。In the general formula, it includes 4 structural units, among which the AA structural monomer is an acrylate monomer, the CP structural monomer is a monomer containing capsaicin functional group, the SiA structural monomer is a silyl acrylate monomer, and the NVP structure The monomer is N-vinylpyrrolidone.
优选的，所述的一种多元协同防污涂料树脂的含辣素官能团的单体为N-(5-乙酰基-4-羟基-2-甲氧基苄基)丙烯酰胺、N-(3-羟基-4-甲氧基苄基)丙烯酰胺、N-(4-氯-3-羟基苄基)丙烯酰胺、N-(4-氟-3-羟基苄基)丙烯酰胺、N-(4-溴-3-羟基苄基)丙烯酰胺或N-(4-乙氧基-3-羟基苄基)丙烯酰胺；Preferably, the monomer containing capsaicin functional group of the described multi-component synergistic antifouling paint resin is N-(5-acetyl-4-hydroxyl-2-methoxybenzyl)acrylamide, N-(3 -Hydroxy-4-methoxybenzyl)acrylamide, N-(4-chloro-3-hydroxybenzyl)acrylamide, N-(4-fluoro-3-hydroxybenzyl)acrylamide, N-(4 - bromo-3-hydroxybenzyl)acrylamide or N-(4-ethoxy-3-hydroxybenzyl)acrylamide;
所述的丙烯酸酯类的单体为甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸异丁酯或甲基丙烯酸叔丁酯；The acrylate monomer is methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl methacrylate or tert-butyl methacrylate;
所述的丙烯酸甲硅烷酯类的单体为甲基丙烯酸三甲基硅酯、甲基丙烯酸三乙基甲硅烷基酯、叔丁基二甲基甲硅烷基甲基丙烯酸酯、甲基丙烯酸三异丙基甲硅烷酯、1,1,1,3,3,3-六甲基-2-(三甲基甲硅烷基)三硅烷-2-基甲基丙烯酸酯、三苯基甲硅烷基甲基丙烯酸酯、丙烯酸三乙基甲硅烷基酯或丙烯酸三异丙基甲硅烷酯；The silyl acrylate monomers are trimethylsilyl methacrylate, triethylsilyl methacrylate, tert-butyldimethylsilyl methacrylate, trimethyl methacrylate Isopropylsilyl ester, 1,1,1,3,3,3-hexamethyl-2-(trimethylsilyl)trisilan-2-ylmethacrylate, triphenylsilyl Methacrylate, triethylsilyl acrylate, or triisopropylsilyl acrylate;
所述的结构通式中a＝30-70，b＝30-100，c＝30-70，d＝30-80。In the general structural formula, a=30-70, b=30-100, c=30-70, d=30-80.
本发明还提供了一种多元协同防污涂料树脂的制备方法，该方法包括如下步骤：The present invention also provides a method for preparing a multi-component synergistic antifouling coating resin, the method comprising the following steps:
(1)准备下列反应物：含辣素官能团的单体、N-乙烯吡咯烷酮(NVP)、丙烯酸酯类单体、丙烯酸甲硅烷酯类单体、引发剂、有机溶剂、沉降剂；首先将引发剂分为三份，第一份为引发剂总质量15％-24％，第二份为引发剂总质量的53％-71％，剩余为第三份引发剂；有机溶剂分为两份，第一份为有机溶剂总质量30％-40％，第二份为有机溶剂总质量的60％-70％；(1) Prepare the following reactants: monomers containing capsaicin functional groups, N-vinylpyrrolidone (NVP), acrylate monomers, silyl acrylate monomers, initiators, organic solvents, sedimentation agents; The agent is divided into three parts, the first part is 15%-24% of the total mass of the initiator, the second part is 53%-71% of the total mass of the initiator, and the rest is the third part of the initiator; the organic solvent is divided into two parts, The first part is 30%-40% of the total mass of organic solvent, and the second part is 60%-70% of the total mass of organic solvent;
(2)将第一份引发剂溶于第一份有机溶剂中，放入容器中并预热至50-80℃；(2) Dissolve the first part of initiator in the first part of organic solvent, put it into a container and preheat to 50-80°C;
(3)将含辣素官能团的单体、NVP、丙烯酸酯类单体、丙烯酸甲硅烷酯类单体和第二份引发剂溶于第二份有机溶剂中，均匀滴加到步骤(2)的容器中；聚合反应在氮气保护下进行；之后，加入第三份引发剂将温度升高至80-90℃，保温；反应得到聚合反应溶液；(3) The monomer containing capsaicin functional group, NVP, acrylate monomer, silyl acrylate monomer and the second part of initiator are dissolved in the second part of organic solvent, and evenly added dropwise to step (2) In a container; the polymerization reaction is carried out under the protection of nitrogen; after that, a third part of initiator is added to raise the temperature to 80-90°C, and the temperature is kept; the reaction obtains a polymerization reaction solution;
(4)将步骤(3)得到的聚合反应溶液滴加到沉降剂中析出固体，过滤，干燥，得到多元协同防污涂料树脂。(4) The polymerization reaction solution obtained in step (3) is added dropwise to a sedimentation agent to precipitate solids, filtered, and dried to obtain a multi-component synergistic antifouling coating resin.
优选的，所述含辣素官能团的单体、NVP、丙烯酸酯类单体和丙烯酸甲硅烷酯类单体的用量按摩尔比计，为30-80：30-70：30-70：30-100；所述引发剂的用量为含辣素官能团的单体、NVP、丙烯酸酯类单体和丙烯酸甲硅烷酯类单体总质量的2％-4％；有机溶剂用量为含辣素官能团的单体、NVP、丙烯酸酯类单体和丙烯酸甲硅烷酯类单体总质量的100％-300％。Preferably, the amount of the monomer containing capsaicin functional group, NVP, acrylate monomer and silyl acrylate monomer is 30-80:30-70:30-70:30- 100; the amount of the initiator is 2%-4% of the total mass of monomers containing capsaicin functional groups, NVP, acrylate monomers and silyl acrylate monomers; 100%-300% of the total mass of monomers, NVP, acrylate monomers and silyl acrylate monomers.
优选的，所述的含辣素官能团的单体结构式为：Preferably, the structural formula of the monomer containing capsaicin functional group is:
式中R7，R8，R9为F，Cl，Br，OH，OCH3,H或OCH2CH3。In the formula, R7, R8, R9 are F, Cl, Br, OH, OCH 3 , H or OCH 2 CH 3 .
优选的，所述的多元协同防污涂料树脂的制备方法，其特征在于，所述的丙烯酸酯类的单体结构式为：Preferably, the preparation method of the multi-component synergistic antifouling coating resin is characterized in that the structural formula of the monomer of the acrylate is:
式中R2，为H或CH3；R1为H，CH3，CH2CH3，CH2CH2CH3，CH2CH2CH2CH3，CH2CH(CH3)2或C(CH3)3。In the formula, R2 is H or CH 3 ; R1 is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 CH 3 , CH 2 CH(CH 3 ) 2 or C(CH 3 ) 3 .
优选的，所述的丙烯酸甲硅烷酯类的单体结构式为：Preferably, the monomer structural formula of the described silyl acrylate is:
式中R3为H或CH3；R4，R6为CH3，CH2CH3，C(CH3)3，CH(CH3)2，C6H5，Si(CH3)3；R5为CH3，CH2CH3，C(CH3)3，CH(CH3)2，C6H5，Si(CH3)3。In the formula, R3 is H or CH 3 ; R4, R6 are CH 3 , CH 2 CH 3 , C(CH 3 ) 3 , CH(CH 3 ) 2 , C 6 H 5 , Si(CH 3 ) 3 ; R5 is CH 3 , CH 2 CH 3 , C(CH 3 ) 3 , CH(CH 3 ) 2 , C 6 H 5 , Si(CH 3 ) 3 .
优选的，所述的引发剂为2,2-偶氮二异丁睛或过氧化苯甲酰。Preferably, the initiator is 2,2-azobisisobutyronitrile or benzoyl peroxide.
优选的，所述的有机溶剂选自酯类、酮类或醚酯类等；所述酯类为乙酸丁酯或乙酸乙酯或其任意比例的混合溶液；所述酮类为丙酮或甲基乙基酮或其任意比例混合溶剂；所述醚酯类为乙二醇乙醚醋酸酯、乙二醇丁醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇丁醚醋酸酯中的一种或多种任意比例混合溶液；其他溶剂包括N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、二甲苯等一种或多种的混合溶剂，沉降剂选用乙醚、石油醚、正己烷或甲醇。Preferably, the organic solvent is selected from esters, ketones or ether esters, etc.; the esters are butyl acetate or ethyl acetate or a mixed solution in any proportion thereof; the ketones are acetone or methyl Ethyl ketone or its mixed solvent in any proportion; the ether esters are one or more of ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate Proportional mixed solution; other solvents include one or more mixed solvents such as N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, xylene, etc., and the settling agent is selected from diethyl ether, petroleum ether, n-hexane or methanol.
本发明还提供了一种多元协同防污涂料树脂的应用，该应用为：将所述多元协同防污涂料树脂应用于海洋防污。The present invention also provides an application of a multi-component synergistic anti-fouling coating resin, the application being: applying the multi-component synergistic anti-fouling coating resin to marine anti-fouling.
相对于现有的技术本发明的有益效果是：Compared with prior art, the beneficial effects of the present invention are:
(1)本发明采用自由基溶液聚合将N-乙烯吡咯烷酮结构和辣素官能团以及丙烯酸甲硅烷酯类官能团引入到丙烯酸树脂上，得到一种多元协同防污涂料树脂，既可以具有辣素官能团的抗菌功能又具有聚乙烯吡咯烷酮结构的抗蛋白吸附功能，同时还具有丙烯酸甲硅烷酯的低表面能与自抛光的功能，可以抑制细菌的黏附与蛋白的吸附以及及时清除表面的污损物，从而阻断其他大型生物继续在船舶表面生长；同时，由于不释放毒杀剂，可以很好的保护海洋环境。(1) The present invention adopts free radical solution polymerization to introduce N-vinylpyrrolidone structure, capsaicin functional group and silyl acrylate functional group into acrylic resin to obtain a multi-component synergistic antifouling coating resin, which can have capsaicin functional group The antibacterial function also has the anti-protein adsorption function of polyvinylpyrrolidone structure, and also has the low surface energy and self-polishing function of silyl acrylate, which can inhibit the adhesion of bacteria and protein adsorption and timely remove the dirt on the surface, thereby Block other large organisms from continuing to grow on the surface of the ship; at the same time, because no poisonous chemicals are released, the marine environment can be well protected.
(2)本发明采用的是常规自由基聚合，相比于原子转移自由基聚合，操作更简单，对反应本身的要求也比较低；且由于无需采用金属作催化剂，因此反应的成本也降低。(2) The present invention adopts conventional free radical polymerization. Compared with atom transfer radical polymerization, the operation is simpler and the requirements for the reaction itself are relatively low; and since no metal is used as a catalyst, the cost of the reaction is also reduced.
(3)本发明合成的多元协同防污涂料树脂具有湿气固化的特性，可以提供室温下可控的交联固化方式，可以在室温下很好的固化成膜，形成机械性能优异的功能涂层。(3) The multi-component synergistic antifouling coating resin synthesized by the present invention has the characteristics of moisture curing, can provide a controllable cross-linking and curing method at room temperature, and can be well cured to form a film at room temperature to form a functional coating with excellent mechanical properties. Floor.
(4)本发明合成的多元协同防污涂料树脂成膜后经测定，与丙烯酸涂层相比，对大肠杆菌的抗粘附率达76.37％以上，说明具有了良好的抗菌功能。(4) Compared with the acrylic coating, the multi-component synergistic antifouling coating resin synthesized by the present invention has an anti-adhesion rate of 76.37% or more, indicating that it has a good antibacterial function.
(5)本合成方法简单、方便、成膜快，能够在玻璃、板材和金属板材等多种表面使用，在环境友好型海洋防污涂料领域有很大的应用前景。(5) The synthesis method is simple, convenient, and fast in film formation, and can be used on various surfaces such as glass, plates, and metal plates, and has great application prospects in the field of environment-friendly marine antifouling coatings.
(6)本发明合成的多元协同防污涂料树脂成膜后经测定其对硅藻(小舟藻)的吸附情况，与丙烯酸涂层相比，对硅藻的抗粘附率达98.73％以上，因此，在海洋防污涂料领域有很好的应用前景。(6) After the multi-component synergistic antifouling coating resin of the present invention forms a film, it is measured to the adsorption situation of diatom (navicula), compared with acrylic acid coating, the anti-adhesion rate to diatom reaches more than 98.73%, Therefore, it has a good application prospect in the field of marine antifouling coatings.
本发明已获得青岛海洋科学与技术国家实验室开放基金项目(项目编号：QNLM2016ORP0407)的支持。This invention has been supported by the Qingdao National Laboratory of Marine Science and Technology Open Fund Project (project number: QNLM2016ORP0407).
附图说明Description of drawings
图1多功能改性防污涂料树脂抗大肠杆菌粘附效果图；Fig. 1 Multifunctional modified antifouling paint resin anti-Escherichia coli adhesion effect diagram;
图2多功能改性防污涂料树脂抗硅藻粘附效果如图。Figure 2 The anti-diatom adhesion effect of the multifunctional modified antifouling coating resin is shown in the figure.
具体实施方式Detailed ways
本发明采用自由基溶液聚合将N-乙烯吡咯烷酮结构和辣素官能团以及丙烯酸甲硅烷酯类官能团引入到丙烯酸树脂上，得到一种多元协同防污涂料树脂，既可以具有辣素官能团的抗菌趋避功能又具有聚乙烯吡咯烷酮结构的抗蛋白吸附功能，同时还具有丙烯酸甲硅烷酯的低表面能与自抛光的功能，可以抑制细菌的黏附与蛋白的吸附以及及时清除表面的污损物，从而阻断其他大型生物继续在船舶表面生长；同时，由于不释放毒杀剂，可以很好的保护海洋环境。The present invention adopts free radical solution polymerization to introduce N-vinylpyrrolidone structure, capsaicin functional group and silyl acrylate functional group into acrylic resin to obtain a multi-component synergistic antifouling coating resin, which can not only have the antibacterial and repellent function of capsaicin functional group It also has the anti-protein adsorption function of polyvinylpyrrolidone structure, and also has the low surface energy and self-polishing function of silyl acrylate, which can inhibit the adhesion of bacteria and the adsorption of proteins and timely remove the contamination on the surface, thereby blocking Other large organisms continue to grow on the surface of the ship; at the same time, since no poisonous chemicals are released, the marine environment can be well protected.
具体的，本发明的多元协同防污涂层树脂的制备如下步骤：Concretely, the preparation of multivariate synergistic antifouling coating resin of the present invention is as follows:
(1)准备下列反应物：含辣素官能团的单体、N-乙烯吡咯烷酮(NVP)、丙烯酸酯类单体、丙烯酸甲硅烷酯类单体、引发剂、沉降剂和有机溶剂；首先将引发剂分为三份，第一份为引发剂总质量15％-24％，第二份为引发剂总质量的53％-71％，剩余为第三份引发剂；有机溶剂分为两份，第一份为有机溶剂总质量30％-40％，第二份为有机溶剂总质量的60％-70％；(1) Prepare the following reactants: monomers containing capsaicin functional groups, N-vinylpyrrolidone (NVP), acrylate monomers, silyl acrylate monomers, initiators, sedimentation agents and organic solvents; The agent is divided into three parts, the first part is 15%-24% of the total mass of the initiator, the second part is 53%-71% of the total mass of the initiator, and the rest is the third part of the initiator; the organic solvent is divided into two parts, The first part is 30%-40% of the total mass of organic solvent, and the second part is 60%-70% of the total mass of organic solvent;
(2)将第一份引发剂溶于第一份有机溶剂中，放入容器中并预热至50-80℃；(2) Dissolve the first part of initiator in the first part of organic solvent, put it into a container and preheat to 50-80°C;
(3)将含辣素官能团的单体、NVP、丙烯酸酯类单体、丙烯酸甲硅烷酯类单体和第二份引发剂溶于第二份有机溶剂中，均匀滴加到步骤(2)的容器中；聚合反应在氮气保护下进行；之后，加入第三份引发剂，将温度升高至80-90℃，保温；反应得到聚合反应溶液；(3) The monomer containing capsaicin functional group, NVP, acrylate monomer, silyl acrylate monomer and the second part of initiator are dissolved in the second part of organic solvent, and evenly added dropwise to step (2) In a container; the polymerization reaction is carried out under the protection of nitrogen; after that, a third portion of initiator is added, the temperature is raised to 80-90° C., and the temperature is kept; the reaction obtains a polymerization reaction solution;
(4)将步骤(3)得到的聚合反应溶液滴加到沉降剂中析出固体，过滤，干燥，得到多元协同防污涂料树脂。(4) The polymerization reaction solution obtained in step (3) is added dropwise to a sedimentation agent to precipitate solids, filtered, and dried to obtain a multi-component synergistic antifouling coating resin.
制备过程中，优选的含辣素官能团的单体结构式为：In the preparation process, the preferred monomeric structural formula containing capsaicin functional group is:
式中R7，R8，R9为F，Cl，Br，OH，OCH3,H或OCH2CH3。In the formula, R7, R8, R9 are F, Cl, Br, OH, OCH 3 , H or OCH 2 CH 3 .
制备过程中，优选的多元协同防污涂料树脂的制备方法，其特征在于，所述的丙烯酸酯类的单体结构式为：In the preparation process, the preparation method of the preferred multi-component synergistic antifouling coating resin is characterized in that the structural formula of the monomer of the acrylate is:
式中R2，为H或CH3；R1为H，CH3，CH2CH3，CH2CH2CH3，CH2CH2CH2CH3，CH2CH(CH3)2或C(CH3)3。In the formula, R2 is H or CH 3 ; R1 is H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 CH 3 , CH 2 CH(CH 3 ) 2 or C(CH 3 ) 3 .
制备过程中，优选的丙烯酸甲硅烷酯类的单体结构式为：In the preparation process, the monomer structural formula of preferred silyl acrylates is:
式中R3为H或CH3；R4，R6为CH3，CH2CH3，C(CH3)3，CH(CH3)2，C6H5，Si(CH3)3；R5为CH3，CH2CH3，C(CH3)3，CH(CH3)2，C6H5，Si(CH3)3。In the formula, R3 is H or CH 3 ; R4, R6 are CH 3 , CH 2 CH 3 , C(CH 3 ) 3 , CH(CH 3 ) 2 , C 6 H 5 , Si(CH 3 ) 3 ; R5 is CH 3 , CH 2 CH 3 , C(CH 3 ) 3 , CH(CH 3 ) 2 , C 6 H 5 , Si(CH 3 ) 3 .
制备过程中，优选的引发剂为2,2-偶氮二异丁睛或过氧化苯甲酰。In the preparation process, the preferred initiator is 2,2-azobisisobutyronitrile or benzoyl peroxide.
制备过程中，优选的有机溶剂选自酯类、酮类或醚酯类等；所述酯类为乙酸丁酯或乙酸乙酯或其任意比例的混合溶液；所述酮类为丙酮或甲基乙基酮或其任意比例混合溶剂；所述醚酯类为乙二醇乙醚醋酸酯、乙二醇丁醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇丁醚醋酸酯中的一种或多种任意比例混合溶液；其他溶剂包括N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、二甲苯等一种或多种的混合溶剂，沉降剂选用乙醚、石油醚、正己烷或甲醇。In the preparation process, the preferred organic solvent is selected from esters, ketones or ether esters, etc.; the esters are butyl acetate or ethyl acetate or a mixed solution of any proportion thereof; the ketones are acetone or methyl Ethyl ketone or its mixed solvent in any proportion; the ether esters are one or more of ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate Proportional mixed solution; other solvents include one or more mixed solvents such as N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, xylene, etc., and the settling agent is selected from diethyl ether, petroleum ether, n-hexane or methanol.
最后，本发明多元协同防污涂料树脂P(AA-SiA-PVP-CP)的结构通式为：Finally, the general structural formula of the multi-component synergistic antifouling coating resin P (AA-SiA-PVP-CP) of the present invention is:
本发明采用的是常规自由基聚合，相比于原子转移自由基聚合，操作更简单，对反应本身的要求也比较低；且由于无需采用金属作催化剂，因此反应的成本也降低。The present invention adopts conventional radical polymerization, and compared with atom transfer radical polymerization, the operation is simpler and the requirements for the reaction itself are relatively low; and since no metal is used as a catalyst, the cost of the reaction is also reduced.
本发明合成的多元协同防污涂料树脂具有湿气固化的特性，可以提供室温下可控的交联固化方式，可以在室温下很好的固化成膜，形成机械性能优异的功能涂层。The multi-component synergistic antifouling coating resin synthesized by the invention has the characteristic of moisture curing, can provide a controllable cross-linking and curing mode at room temperature, can be well cured and formed into a film at room temperature, and forms a functional coating with excellent mechanical properties.
为了更清楚的理解本发明，下面结合实施例对本发明做进一步描述，但本发明的实施方式不限于此。In order to understand the present invention more clearly, the present invention will be further described below in conjunction with examples, but the embodiments of the present invention are not limited thereto.
实例1Example 1
1)取1.0g的含辣素官能团单体0.4g的NVP单体，0.4g的丙烯酸丁酯，2.0g的丙烯酸甲硅烷酯50mg的2，2-偶氮二异丁腈，6g的N,N-二甲基甲酰胺。将2，2-偶氮二异丁腈分为三份，第一份8mg，第二份34mg，第三份8mg。将N,N-二甲基甲酰胺分为两份，第一份2g，第二份4g。1) Take 1.0g of monomer containing capsaicin functional group 0.4g NVP monomer, 0.4g butyl acrylate, 2.0g silyl acrylate 50 mg of 2,2-azobisisobutyronitrile, 6 g of N,N-dimethylformamide. Divide 2,2-azobisisobutyronitrile into three parts, the first part is 8 mg, the second part is 34 mg, and the third part is 8 mg. Divide N,N-dimethylformamide into two parts, the first part is 2g, and the second part is 4g.
2)将第一份2,2-偶氮二异丁腈溶于第一份N,N-二甲基甲酰胺中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of 2,2-azobisisobutyronitrile in the first part of N,N-dimethylformamide, put it into a two-necked flask connected with a condenser tube and N gas blowing device, and preheat to 70 ℃.
3)将所有的单体和引发剂加入到第二份N,N-二甲基甲酰胺中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份2,2-偶氮二异丁腈，升温至80℃，保温12h。3) Add all the monomers and initiators to the second part of N,N-dimethylformamide, put them into a constant pressure dropping funnel, and add them dropwise to the two-necked bottle with the initiator, And control the dropping within 2 hours, under the protection of nitrogen, after the polymerization reaction for 12 hours, add the third part of 2,2-azobisisobutyronitrile, raise the temperature to 80°C, and keep the temperature for 12 hours.
4)采用乙醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Diethyl ether is used to precipitate the polymerization reaction product, filter, and vacuum-dry to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例2Example 2
1)取0.7g的含辣素官能团单体0.4g的NVP单体，0.5g的丙烯酸丁酯，0.8g的丙烯酸甲硅烷酯50mg的2,2-偶氮二异丁腈，6g的四氢呋喃。将2,2-偶氮二异丁腈分为三份，第一份8mg，第二份34mg，第三份8mg。将四氢呋喃分为两份，第一份2g，第二份4g。1) Take 0.7g of monomer containing capsaicin functional group 0.4g NVP monomer, 0.5g butyl acrylate, 0.8g silyl acrylate 50 mg of 2,2-azobisisobutyronitrile, 6 g of tetrahydrofuran. Divide 2,2-azobisisobutyronitrile into three parts, the first part is 8 mg, the second part is 34 mg, and the third part is 8 mg. Tetrahydrofuran was divided into two portions, the first 2g and the second 4g.
2)将第一份2,2-偶氮二异丁腈溶于第一份四氢呋喃中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of 2,2-azobisisobutyronitrile in the first part of tetrahydrofuran, put it into a two-necked flask connected with a condenser tube and N 2 blowing device, and preheat to 70°C.
3)将所有的单体和引发剂加入到第二份四氢呋喃中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份2,2-偶氮二异丁腈，升温至80℃，保温12h。3) Add all the monomers and initiators to the second part of tetrahydrofuran, put them into the constant pressure dropping funnel, add them dropwise into the two-necked bottle with the initiator, and control the dripping within 2 hours , under the protection of nitrogen, after the polymerization reaction for 12 hours, a third part of 2,2-azobisisobutyronitrile was added, the temperature was raised to 80° C., and the temperature was kept for 12 hours.
4)采用石油醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) The polymerization reaction product is precipitated by petroleum ether, filtered, and vacuum-dried to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例3Example 3
1)取0.8g的含辣素官能团单体0.2g的NVP单体，0.4g甲基丙烯酸甲酯，1) Take 0.8g of monomer containing capsaicin functional group 0.2g NVP monomer, 0.4g methyl methacrylate,
0.4g的丙烯酸甲硅烷酯36mg的过氧化苯甲酰，5g的N,N-二甲基甲酰胺。将过氧化苯甲酰为三份，第一份6mg，第二份24mg，第三份6mg。将N,N-二甲基甲酰胺分为两份，第一份2g，第二份3g。0.4g of silyl acrylate 36mg of benzoyl peroxide, 5g of N,N-dimethylformamide. Take benzoyl peroxide in three parts, the first 6mg, the second 24mg, and the third 6mg. Divide N,N-dimethylformamide into two parts, the first part is 2g, and the second part is 3g.
2)将第一份过氧化苯甲酰溶于第一份N,N-二甲基甲酰胺中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of benzoyl peroxide in the first part of N,N-dimethylformamide, put it into a two-necked flask connected with a condenser tube and a N2 blowing device, and preheat to 70°C.
3)将所有的单体和引发剂加入到第二份N,N-二甲基甲酰胺中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份过氧化苯甲酰，升温至80℃，保温12h。3) Add all the monomers and initiators to the second part of N,N-dimethylformamide, put them into a constant pressure dropping funnel, and add them dropwise to the two-necked bottle with the initiator, And control the dropping within 2 hours, under the protection of nitrogen, after the polymerization reaction for 12 hours, add the third part of benzoyl peroxide, raise the temperature to 80°C, and keep the temperature for 12 hours.
4)采用乙醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Diethyl ether is used to precipitate the polymerization reaction product, filter, and vacuum-dry to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例4Example 4
1)取0.6g的含辣素官能团单体0.7g的NVP单体，0.45g丙烯酸乙酯，1.5g的丙烯酸甲硅烷酯60mg的2，2-偶氮二异丁腈，8g的二甲苯和乙酸丁酯混合溶液。将2，2-偶氮二异丁腈分为三份，第一份10mg，第二份38mg，第三份12mg。将二甲苯和乙酸丁酯混合溶液分为两份，第一份4g，第二份6g。1) Take 0.6g of monomer containing capsaicin functional group 0.7g NVP monomer, 0.45g ethyl acrylate, 1.5g silyl acrylate 60mg of 2,2-azobisisobutyronitrile, 8g of xylene and butyl acetate mixed solution. Divide 2,2-azobisisobutyronitrile into three parts, the first part is 10 mg, the second part is 38 mg, and the third part is 12 mg. The mixed solution of xylene and butyl acetate was divided into two parts, the first part was 4g, and the second part was 6g.
2)将第一份2,2-偶氮二异丁腈溶于第一份二甲苯和乙酸丁酯混合溶液中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of 2,2-azobisisobutyronitrile in the first part of the mixed solution of xylene and butyl acetate, put it into a two-necked flask connected with a condenser tube and N2 blowing device, and preheat it to 70°C .
3)将所有的单体和引发剂加入到第二份二甲苯和乙酸丁酯混合溶液中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份2,2-偶氮二异丁腈，升温至80℃，保温12h。3) All the monomers and the initiator are added to the second part of xylene and butyl acetate mixed solution, put into a constant pressure dropping funnel, added dropwise to the two-necked bottle with the initiator, and Control the dropping within 2 hours. Under the protection of nitrogen, after the polymerization reaction for 12 hours, add the third part of 2,2-azobisisobutyronitrile, raise the temperature to 80° C., and keep the temperature for 12 hours.
4)采用乙醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Diethyl ether is used to precipitate the polymerization reaction product, filter, and vacuum-dry to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例5Example 5
1)取1.0g的含辣素官能团单体0.5g的NVP单体，0.5g的丙烯酸丁酯，0.8g的丙烯酸甲硅烷酯60mg的过氧化苯甲酰，6g的乙二醇乙醚醋酸酯和二甲苯的混合溶液。将过氧化苯甲酰分为三份，第一份12mg，第二份40mg，第三份8mg。将乙二醇乙醚醋酸酯和二甲苯的混合溶液两份，第一份2g，第二份4g。1) Take 1.0g of monomer containing capsaicin functional group 0.5g NVP monomer, 0.5g butyl acrylate, 0.8g silyl acrylate A mixed solution of 60mg of benzoyl peroxide, 6g of ethylene glycol ether acetate and xylene. The benzoyl peroxide is divided into three parts, the first part is 12mg, the second part is 40mg, and the third part is 8mg. The mixed solution of ethylene glycol ether acetate and xylene is two parts, the first part is 2g, and the second part is 4g.
2)将第一份过氧化苯甲酰溶于第一份乙二醇乙醚醋酸酯和二甲苯的混合溶液中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) the first part of benzoyl peroxide is dissolved in the mixed solution of the first part of ethylene glycol ethyl ether acetate and xylene, put into the two-necked flask that is connected with condenser and N gas blowing device, preheat to 70 ℃.
3)将所有的单体和引发剂加入到第二份乙二醇乙醚醋酸酯和二甲苯的混合溶液中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份过氧化苯甲酰，升温至85℃，保温12h。3) Add all the monomers and initiators to the second part of the mixed solution of ethylene glycol ether acetate and xylene, put it into a constant pressure dropping funnel, and add it dropwise to the two ports with the initiator. bottle, and control the dripping within 2 hours, under the protection of nitrogen, after the polymerization reaction for 12 hours, add the third part of benzoyl peroxide, raise the temperature to 85°C, and keep the temperature for 12 hours.
4)采用正己烷将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Precipitate the polymerization product by using n-hexane, filter it, and dry it in vacuum to obtain the multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例6Example 6
1)取1.46g的含辣素官能团单体0.34g的NVP单体，0.9g的丙烯酸丁酯，0.6g的丙烯酸甲硅烷酯60mg的过氧化苯甲酰，7g的丙二醇甲醚醋酸酯和N,N-二甲基甲酰胺。将过氧化苯甲酰分为三份，第一份12mg，第二份39mg，第三份9mg。将丙二醇甲醚醋酸酯和N,N-二甲基甲酰胺分为两份，第一份3g，第二份4g。1) Take 1.46g of monomer containing capsaicin functional group 0.34g NVP monomer, 0.9g butyl acrylate, 0.6g silyl acrylate 60mg of benzoyl peroxide, 7g of propylene glycol methyl ether acetate and N,N-dimethylformamide. The benzoyl peroxide is divided into three parts, the first part is 12mg, the second part is 39mg, and the third part is 9mg. Divide propylene glycol methyl ether acetate and N,N-dimethylformamide into two parts, the first part is 3g, and the second part is 4g.
2)将第一份过氧化苯甲酰溶于第一份丙二醇甲醚醋酸酯和N,N-二甲基甲酰胺中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of benzoyl peroxide in the first part of propylene glycol methyl ether acetate and N,N-dimethylformamide, put it into a two-necked flask connected with a condenser tube and N gas blowing device, pre- Heat to 70°C.
3)将所有的单体和引发剂加入到第二份丙二醇甲醚醋酸酯和N,N-二甲基甲酰胺中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份过氧化苯甲酰，升温至85℃，保温12h。3) Add all monomers and initiators to the second part of propylene glycol methyl ether acetate and N,N-dimethylformamide, put them into a constant pressure dropping funnel, and add them dropwise to the In the two-necked bottle of benzoyl peroxide, the dripping was controlled within 2 hours. Under the protection of nitrogen, after 12 hours of polymerization reaction, the third part of benzoyl peroxide was added, the temperature was raised to 85°C, and the temperature was kept for 12 hours.
4)采用乙醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Diethyl ether is used to precipitate the polymerization reaction product, filter, and vacuum-dry to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例7Example 7
1)取0.63g的含辣素官能团单体0.8g的NVP单体，0.4g的丙烯酸丁酯，0.6g的丙烯酸甲硅烷酯50mg的过氧化苯甲酰，6g的N,N-二甲基甲酰胺。将过氧化苯甲酰分为三份，第一份12mg，第二份30mg，第三份8mg。将N,N-二甲基甲酰胺分为两份，第一份2g，第二份4g。1) Take 0.63g of monomer containing capsaicin functional group 0.8g NVP monomer, 0.4g butyl acrylate, 0.6g silyl acrylate 50mg of benzoyl peroxide, 6g of N,N-dimethylformamide. The benzoyl peroxide is divided into three parts, the first part is 12mg, the second part is 30mg, and the third part is 8mg. Divide N,N-dimethylformamide into two parts, the first part is 2g, and the second part is 4g.
2)将第一份过氧化苯甲酰溶于第一份N,N-二甲基甲酰胺中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of benzoyl peroxide in the first part of N,N-dimethylformamide, put it into a two-necked flask connected with a condenser tube and a N2 blowing device, and preheat to 70°C.
3)将所有的单体和引发剂加入到第二份N,N-二甲基甲酰胺中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份过氧化苯甲酰，升温至80℃，保温12h。3) Add all the monomers and initiators to the second part of N,N-dimethylformamide, put them into a constant pressure dropping funnel, and add them dropwise to the two-necked bottle with the initiator, And control the dropping within 2 hours, under the protection of nitrogen, after the polymerization reaction for 12 hours, add the third part of benzoyl peroxide, raise the temperature to 80°C, and keep the temperature for 12 hours.
4)采用乙醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Diethyl ether is used to precipitate the polymerization reaction product, filter, and vacuum-dry to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
实例8Example 8
1)取0.63g的含辣素官能团单体0.4g的NVP单体，0.4g的丙烯酸丁酯，2.0g的丙烯酸甲硅烷酯80mg的2，2-偶氮二异丁腈，10g的N,N-二甲基甲酰胺。将2，2-偶氮二异丁腈分为三份，第一份20mg，第二份45mg，第三份15mg。将N,N-二甲基甲酰胺分为两份，第一份4g，第二份6g。1) Take 0.63g of monomer containing capsaicin functional group 0.4g NVP monomer, 0.4g butyl acrylate, 2.0g silyl acrylate 80 mg of 2,2-azobisisobutyronitrile, 10 g of N,N-dimethylformamide. Divide 2,2-azobisisobutyronitrile into three parts, the first part is 20 mg, the second part is 45 mg, and the third part is 15 mg. Divide N,N-dimethylformamide into two parts, the first part is 4g, and the second part is 6g.
2)将第一份2,2-偶氮二异丁腈溶于第一份N,N-二甲基甲酰胺中，放入连有冷凝管和N2鼓气装置的两口烧瓶，预热至70℃。2) Dissolve the first part of 2,2-azobisisobutyronitrile in the first part of N,N-dimethylformamide, put it into a two-necked flask connected with a condenser tube and N gas blowing device, and preheat to 70 ℃.
3)将所有的单体和引发剂加入到第二份N,N-二甲基甲酰胺中，放入恒压滴液漏斗，采用滴加的方式加入到带有引发剂的两口瓶中，并控制在2小时内滴完，氮气保护下，聚合反应12h后，加入第三份2,2-偶氮二异丁腈，升温至90℃，保温12h。3) Add all the monomers and initiators to the second part of N,N-dimethylformamide, put them into a constant pressure dropping funnel, and add them dropwise to the two-necked bottle with the initiator, And control the dropping within 2 hours, under the protection of nitrogen, after the polymerization reaction for 12 hours, add the third part of 2,2-azobisisobutyronitrile, raise the temperature to 90°C, and keep the temperature for 12 hours.
4)采用乙醚将聚合反应产物沉出，过滤，真空干燥，即得到多元协同防污涂料树脂。4) Diethyl ether is used to precipitate the polymerization reaction product, filter, and vacuum-dry to obtain a multi-component synergistic antifouling coating resin.
本实施例制得的多元协同防污涂料树脂的结构通式如下。The general structural formula of the multi-component synergistic antifouling coating resin prepared in this embodiment is as follows.
性能测试Performance Testing
抗大肠杆菌粘附测试Anti-E. coli Adhesion Test
将实施实例1、2制备的涂料树脂以及丙烯酸清漆(对照)各10mg分别涂在1cm2钢片上，在烘箱和真空干燥箱除去全部溶剂，待测。将大肠杆菌培养至OD为1.0(此时细菌增长速度最快)后，稀释10倍，用作测试菌液。将待测样品分别放入24孔板，每孔加入1ml测试菌液，摇床孵育1.5h(100rpm，37℃)后，将待测样品转移到新孔中，每孔加入1ml无菌PBS，摇床200rpm清洗10min，之后换新鲜无菌PBS重复清洗操作，共洗3次，以去除涂层表面粘附不牢固的大肠杆菌。清洗完毕后，再将样品转移至新孔中，每孔加入1ml无菌PBS，50％功率超声30s，停30s，重复4次，以将涂层表面粘附的大肠杆菌全部洗脱下来。每个样品孔取50μL洗脱液涂板，于37℃在固体培养基上培养12h，对平板做活菌计数(即菌落形成数，CFU)，计算得样品单位面积大肠杆菌粘附量(AE)，计算公式如下：Each 10 mg of coating resin prepared by implementing examples 1 and 2 and acrylic varnish (contrast) are coated on 1 cm steel sheet respectively, and all solvents are removed in an oven and a vacuum oven, to be tested. After culturing Escherichia coli to an OD of 1.0 (at this time, the bacterial growth rate is the fastest), dilute it 10 times and use it as a test bacterial solution. Put the samples to be tested into 24-well plates, add 1ml of test bacteria solution to each well, incubate on a shaking table for 1.5h (100rpm, 37°C), transfer the samples to be tested into new wells, add 1ml of sterile PBS to each well, Shake at 200rpm for 10 minutes, then replace with fresh sterile PBS and repeat the washing operation for a total of 3 times to remove Escherichia coli that is not firmly adhered to the coating surface. After cleaning, transfer the sample to a new well, add 1ml of sterile PBS to each well, sonicate at 50% power for 30s, stop for 30s, repeat 4 times to elute all E. coli adhered to the coating surface. Take 50 μL of the eluate from each sample well and spread it on the plate, culture it on solid medium at 37°C for 12 hours, count the viable bacteria on the plate (that is, the number of colonies formed, CFU), and calculate the adhesion amount of Escherichia coli per unit area of the sample (AE) ,Calculated as follows:
AE(CFU/cm2)＝(菌落形成数(CFU)*1/0.05)/1cm2 AE (CFU/cm 2 )=(colony forming number (CFU)*1/0.05)/1cm 2
抗大肠杆菌粘附率按下式计算：The anti-Escherichia coli adhesion rate was calculated according to the following formula:
抗大肠杆菌粘附率(％)＝(AE清漆-AE样品)/AE清漆 Anti-E. coli adhesion rate (%) = (AE varnish -AE sample )/AE varnish
多功能改性防污涂料树脂抗大肠杆菌粘附率测试结果如表1。Table 1 shows the test results of the anti-Escherichia coli adhesion rate of the multifunctional modified antifouling coating resin.
表1：多动能改性防污涂料的抗大肠杆菌粘附率测试结果Table 1: Test results of anti-E. coli adhesion rate of multi-kinetic energy modified antifouling coatings
多功能改性防污涂料树脂抗大肠杆菌粘附效果如图1。The anti-adhesion effect of Escherichia coli with multifunctional modified antifouling coating resin is shown in Figure 1.
抗硅藻粘附测试Anti-diatom adhesion test
按实施实例3的步骤将样品及对照清漆涂在1cm2玻璃片上，待测。所用的藻类购自中国船舶重工集团公司第七二五研究所青岛分所，利用指数生长期的附着来评价涂层的抗污性能。在无菌锥形瓶中装入硅藻细胞，并在25℃条件下进行20天连续常规光照(12小时明亮，12小时黑暗)培养。并通过细胞计数池直接对细胞计数来估计细胞的生长。经过三周的培养，细胞浓度达到测试数量级。再将部分细胞悬浮液从锥形瓶中移走，用于防污性能的测试藻液。将待测样品分别放入24孔板，每孔加入1ml测试藻液，避光条件下静止孵育3h(室温)后，将待测样品转移到新孔中，每孔加入1ml无菌人工海水，摇床200rpm清洗10min，之后换新鲜无菌人工海水重复清洗操作，共洗3次，以去除涂层表面粘附不牢固的小舟藻。清洗完毕后，再将样品转移至新孔中，并且将涂层面朝下放置，倒置显微镜(放大倍数200X)下在不同的区域观察、拍照。随机取5张照片对粘附的硅藻进行计数，计算得到单位面积硅藻粘附量(AD)，计算公式如下：Sample and contrast varnish are coated on 1cm by the step of implementing example 3 on the glass slide, to be tested. The algae used were purchased from the Qingdao Branch of the 725th Research Institute of China Shipbuilding Industry Corporation, and the antifouling performance of the coating was evaluated by the attachment in the exponential growth phase. Diatom cells were placed in a sterile Erlenmeyer flask, and cultured under 25°C for 20 days under continuous conventional light (12 hours bright, 12 hours dark). And the cell growth is estimated directly by counting the cells through the cell counting pool. After three weeks of culture, the cell concentration reached the test order of magnitude. Then part of the cell suspension was removed from the Erlenmeyer flask to test the algae liquid for antifouling performance. Put the samples to be tested into 24-well plates, add 1ml of test algae solution to each well, and incubate statically for 3 hours (room temperature) in the dark, then transfer the samples to be tested to new wells, add 1ml of sterile artificial seawater to each well, Wash on a shaking table at 200rpm for 10 minutes, then replace with fresh sterile artificial seawater and repeat the cleaning operation for a total of 3 times to remove navicula that is not firmly adhered to the surface of the coating. After cleaning, the sample was transferred to a new hole, and the coating was placed facing down, and observed and photographed in different areas under an inverted microscope (200X magnification). Randomly take 5 photos to count the adhered diatoms, and calculate the adhesion amount of diatoms per unit area (AD), the calculation formula is as follows:
AD(个细胞/cm2)＝硅藻粘附数(个)/面积(cm2)AD (cell/cm 2 ) = number of diatoms adhered (unit)/area (cm 2 )
抗硅藻粘附率按下式计算：The anti-diatom adhesion rate is calculated according to the following formula:
抗硅藻粘附率(％)＝(AD清漆-AD样品)/AD清漆 Anti-diatom adhesion rate (%) = (AD varnish - AD sample ) / AD varnish
多功能改性防污涂料树脂抗硅藻粘附率测试结果如表2。Table 2 shows the test results of the anti-diatom adhesion rate of the multifunctional modified antifouling coating resin.
表2：多动能改性防污涂料的抗硅藻粘附率测试结果Table 2: Test results of anti-diatom adhesion rate of multi-kinetic energy modified antifouling coatings
多功能改性防污涂料树脂抗硅藻粘附效果如图2。The anti-diatom adhesion effect of multifunctional modified antifouling coating resin is shown in Figure 2.
以上所述，仅是对本发明比较好的实施例，并非对本发明其他形式的限制，。其它的任何未背离本发明的精神实质与原理下所做的改变、修饰、替代、组合、简化等,均应为等效的置换方式,都包含在本发明的保护范围之内。The foregoing descriptions are only preferred embodiments of the present invention, and are not intended to limit other forms of the present invention. Any other changes, modifications, substitutions, combinations, simplifications, etc. that do not deviate from the spirit and principle of the present invention shall be equivalent replacement methods, and shall be included in the protection scope of the present invention.
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| CN109251621A (en) * | 2018-09-17 | 2019-01-22 | 山东陆邦涂料有限公司 | A kind of antifouling paint and preparation method thereof |
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