CN102675524A - Self-polishing antifouling resin and preparation method thereof - Google Patents
Self-polishing antifouling resin and preparation method thereof Download PDFInfo
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- CN102675524A CN102675524A CN2012101606698A CN201210160669A CN102675524A CN 102675524 A CN102675524 A CN 102675524A CN 2012101606698 A CN2012101606698 A CN 2012101606698A CN 201210160669 A CN201210160669 A CN 201210160669A CN 102675524 A CN102675524 A CN 102675524A
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- Prior art keywords
- polishing antifouling
- antifouling resin
- metal ion
- initiator
- polishing
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 116
- 238000005498 polishing Methods 0.000 title claims abstract description 100
- 239000011347 resin Substances 0.000 title claims abstract description 98
- 229920005989 resin Polymers 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 51
- 150000007524 organic acids Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 41
- 239000003513 alkali Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 27
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 23
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 21
- 238000012856 packing Methods 0.000 description 16
- 239000004925 Acrylic resin Substances 0.000 description 10
- -1 isobutyl- Chemical group 0.000 description 10
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 238000010526 radical polymerization reaction Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 4
- BPHLCSXLTFFFBE-UHFFFAOYSA-N barium;prop-2-enoic acid Chemical compound [Ba].OC(=O)C=C BPHLCSXLTFFFBE-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- KCNHXBQWUUIBIG-UHFFFAOYSA-N [Mg].C(C=C)(=O)O Chemical compound [Mg].C(C=C)(=O)O KCNHXBQWUUIBIG-UHFFFAOYSA-N 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 229960005147 calcium acetate Drugs 0.000 description 3
- 235000011092 calcium acetate Nutrition 0.000 description 3
- 239000001639 calcium acetate Substances 0.000 description 3
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 3
- KOBKUSXTVUSJEU-UHFFFAOYSA-N copper;prop-2-enoic acid Chemical compound [Cu].OC(=O)C=C KOBKUSXTVUSJEU-UHFFFAOYSA-N 0.000 description 3
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 3
- DMZUKDRIRUYBIU-UHFFFAOYSA-N manganese;prop-2-enoic acid Chemical compound [Mn].OC(=O)C=C DMZUKDRIRUYBIU-UHFFFAOYSA-N 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 3
- 0 C***(C**(CN)C([U]CCC=**(C)=[I+])=O)C(*)=N Chemical compound C***(C**(CN)C([U]CCC=**(C)=[I+])=O)C(*)=N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229950003143 basic zinc acetate Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- JCPDISNOORFYFA-UHFFFAOYSA-H tetrazinc;oxygen(2-);hexaacetate Chemical compound [O-2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JCPDISNOORFYFA-UHFFFAOYSA-H 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 2
- VPIRJGXSNAKQRB-UHFFFAOYSA-N 2-methylprop-2-enoic acid;tributyltin Chemical compound CC(=C)C(O)=O.CCCC[Sn](CCCC)CCCC VPIRJGXSNAKQRB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000585116 Galba truncatula Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N OC(c1ccccc1)=O Chemical compound OC(c1ccccc1)=O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 208000035844 biological anomaly Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- QMZIDZZDMPWRHM-UHFFFAOYSA-L manganese(2+);dibenzoate Chemical compound [Mn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QMZIDZZDMPWRHM-UHFFFAOYSA-L 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a self-polishing antifouling resin and a preparation method thereof; the self-polishing antifouling resin has good fluidity, adhesive force and a certain self-polishing rate, and can be used as main resin of a ship bottom self-polishing antifouling paint; the preparation method of the self-polishing antifouling resin comprises the steps of reacting unsaturated organic acid with basic divalent metal ion double salt, and then reacting with other acrylic monomers under the action of an initiator to synthesize the self-polishing antifouling resin; the method overcomes the defect of low grafting rate in the synthesis of the tin-free self-polishing resin, shortens the reaction time and ensures that the product is more stable.
Description
Technical field
The invention belongs to the synthetic field of resin, relate to a kind of particularly from polishing antifouling resin and preparation method thereof.
Background technology
As everyone knows, a large amount of sea life that living in the ocean, when ship navigated by water in the ocean, sea life can be adsorbed on the shell surface very soon, and grew in the above, breed, and this just causes shell by marine biofouling.And after shell was by marine denudation or marine biofouling, hull surface roughness increased, and caused flow resistance and frictional force to increase, and caused ship navigation speed obviously to reduce; The increase of hull mass increases fuel consumption, and the frequency of maintenance that lies up also increases thereupon, and fuel oil consumption increases.Have data to show, when hull bottom generates the thick mucous membrane of 1mm, can make the hull surface frictional coefficient increase by 80%, ship's speed reduces by 15%.In addition, the sea life that adhere to (like barnacle) are in the process of growth, and the mobile of its shell can be destroyed the surperficial antifouling and corrosion protection coating of shell, and death of organism and mikrobe have quickened the corrosion of hull to organic effect.The sea life that the while hull bottom adheres to can be brought to each marine site, the world easily with the ocean freighter; This vegeto-animal unrestricted flow is very likely taken alien species to somewhere; Destroy the local eubiosis; Even cause the big area of some disease and pest or fatal epidemic situation to propagate, for the global environment protection, this is a huge hidden danger beyond doubt.
Organotin is applied to antifouling paint as the poison material and starts from the mid-50 in last century, and (TBT Tributyltin) has the wide spectrum high toxicity, can kill the fresh water mud snail to it is found that tributyl tin.Nineteen seventies; A kind of antifouling phase imitates long organotin self polishing copolymer antifouling paint TBT-SPC (self-polishing copolymer paints) self polishing copolymer antifouling paint and is developed, and mainly is to be film forming matter, to be the coating that color stuffings such as poison material and adding zinc oxide are processed with Red copper oxide by water-disintegrable methylacrylic acid tributyl tin multipolymer.In seawater, the organotin propenoate generation hydrolysis on the coatingsurface polymeric linear main chain discharges TBT; It is water-soluble that the hydrophilic radical that the while main polymer chain produces because of hydrolysis has it, and when hydrophilic radical quantity reached a threshold value, main polymer chain just was dissolved in the seawater from disappearing gradually, exposes the surface that makes new advances again.This self polishing copolymer antifouling paint, good antifouling effect uses validity period long, and this kind coating just becomes the main product of antifouling paint very soon once appearance, almost accounts for 70% of global ocean antifouling paint usage quantity, and the antifouling phase imitates and was generally 5 years.
But it is found that afterwards that seashells biological anomalies phenomenon was relevant with the toxicity that organo-tin compound has.The antifouling effect of organo-tin compound is that it has the effect that intensive disturbs biological endocrine system; Promptly disturb the hormone molecule; Influence the most basic biological reproductive function; Cause the adverse consequences of growth and genetic aspect, because organo-tin compound stockpiles, is difficult to decompose also and can in environment, be detained for a long time at the sea life middle and high concentration, cause the distortion of organism simultaneously.For preventing the pollution of the environment; Since the later stage eighties; The U.S., Britain, France, Japan and european community country etc. have successively carried out the restriction to the application of organic tin antifouling paint; Force marine finish manufacturer to set about substituting the research and development of coating, and drawn back the prelude of research nontoxic antifouling paint thus.Because containing the objectionable impurities of the antifouling paint release of organotin poison material, tradition caused serious harm for ecotope and human health; The IMO of International Maritime Organizaton (International Marine Organization) made stipulations in October, 2000: the final time limit of service that contains the organotin antifouling paint is on January 1st, 2003, and the final term that scribbles the boats and ships operation of such coating is on January 1st, 2008.Promptly, no longer allow any boats and ships that contain organotin coating that scribble to move at sea from 2008.Therefore the new Nontoxic Antifouling Paint of developing environmentally safe is imperative to replace traditional toxicity antifouling paint.
The main stream approach of current synthetic tin-free self-polishing antifouling resin is the synthetic earlier vinyl resin that contains carboxyl; Again with the subsalt reaction that contains zinc (or copper); Chinese patent CN200310105495.6 for example, this method technology is complicated, and the time is long; Power consumption is big, and percentage of grafting is difficult to reach 100%.What also have that a kind of method such as Chinese patent CN201110048903.3 propose synthesizes the small molecules that has zinc acrylate resin or copper earlier; With other acrylic monomer radical polymerization, this method is fairly simple again, and it is low to consume energy; Controllability is strong; But when the first step acrylic acid synthesizing zinc or copper, be difficult to guarantee to form single zinc acrylate resin or copper monomer, cause the next stability deficiency of resin.
Summary of the invention
The technical problem that the present invention will solve provides a kind of from the polishing antifouling resin.
The technical problem that the present invention will solve provides a kind of preparation method from the polishing antifouling resin.
For solving the problems of the technologies described above, it is a kind of from the polishing antifouling resin that the present invention provides, and its molecular formula is:
In the formula, M is Zn, Cu, Ca, Mg, Mn, Co or Ba;
R
1, R
2Be respectively carbonatoms and be not more than 6 alkyl;
R
3Be methyl or phenyl;
M, n, k are respectively the integer greater than 1; Should be 7000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
For solving the problems of the technologies described above, the present invention provides a kind of preparation method from the polishing antifouling resin, may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 40 ℃～80 ℃ the condition to solution becomes to clarify; Be incubated 1 ~ 2 hour again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) the unsaturated organic acid divalent-metal ion salt D and other acrylic monomers E that step (1) are generated are blended among the solvent F; Temperature is under 65 ℃～90 ℃ the condition; At first 4/5 initiator G was added drop-wise in the mixed solution through 1～4 hour, initiated polymerization is added drop-wise to remaining 1/5 initiator G in the mixed solution afterwards; Reacted again 2 ~ 3 hours, synthetic from polishing antifouling resin H;
Wherein, the unsaturated organic acid A of said step (1) is one or more mixtures in vinylformic acid, methylacrylic acid, the butenoic acid;
The alkali formula divalent-metal ion double salt B of said step (1) be M (CH3COO) (OH), M (C
6H
5COO) mixture of one or more in (OH);
In the said step (2), each material uses according to following mass fraction proportioning:
Said synthetic from the molecular formula of polishing antifouling resin H is:
In the formula, M is Zn, Cu, Ca, Mg, Mn, Co or Ba;
R
1, R
2Be respectively carbonatoms and be not more than 6 alkyl;
R
3Be methyl or phenyl;
M, n, k are respectively the integer greater than 1; Should be 7000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
The divalent-metal ion M of the said alkali formula divalent-metal ion double salt B of said step (1) is Zn
2+, Cu
2+, Ca
2+, Mg
2+, Mn
2+, Co
2+, Ba
2+
Those skilled in the art can select suitable solvent C of the present invention from known acrylic monomer.Preferably, the solvent C of said step (1) is one or more mixtures in propyl carbinol, Virahol, the n-propyl alcohol.The consumption of the solvent C of step (1) only needs to satisfy the unsaturated organic acid divalent-metal ion salt D that can dissolve generation and gets final product, and does not do particular determination.
Said step (1) reaction is accomplished, and the method for employing 4A level molecular sieve or underpressure distillation dewaters to the solution of unsaturated organic acid divalent-metal ion salt.
Step (2) can obtain of the present invention from polishing resin according to top description; But reaction is steady more in order to make, narrow molecular weight distribution; Preferably, said step (2) is: temperature is under 65 ℃～90 ℃ the condition, at first; Unsaturated organic acid divalent-metal ion salt D, 1/4 other acrylic monomers E and 1/5 initiator G that 1/4 step (1) is generated are blended among the solvent F, react 1～2 hour; Secondly, in the mixed solution of mixed solution before being added drop-wise in 1～4 hour of unsaturated organic acid divalent-metal ion salt D, 3/4 other acrylic monomers E and the 3/5 initiator G that 3/4 step (1) is generated, reacted again 1～3 hour; At last, 1/5 initiator G is added drop-wise in the mixed solution, reacted 2 ~ 3 hours, synthetic from polishing antifouling resin H.
Those skilled in the art can select suitable other acrylic monomers E of the present invention from known acrylic monomer.Preferably, other acrylic monomers E of said step (2) is one or more mixtures in Bing Xisuandingzhi, ethyl propenoate, TEB 3K, methyl acrylate, the NSC 20956.
Those skilled in the art can select from prior art and be fit to solvent F of the present invention.Preferably, the solvent F of said step (2) is one or more mixtures in propyl carbinol, Virahol, the n-propyl alcohol or is the mixture of one or both and YLENE in the propyl carbinol, Virahol, n-propyl alcohol.
Those skilled in the art can select from prior art and be fit to initiator G of the present invention.Preferably, the initiator G of said step (2) is Diisopropyl azodicarboxylate, ABVN, azo-bis-iso-dimethyl, Lucidol, lauroyl peroxide.
The invention has the advantages that:
1, method of the present invention has been improved the synthetic middle low shortcoming of percentage of grafting of tin-free self-polishing resin;
2, synthesis technique of the present invention has shortened the reaction times, makes product more stable, can accurately control the content of divalent-metal ion in the resin;
3, the tin-free self-polishing antifouling resin that makes of the present invention has good mobility, sticking power and certain for polishing speed, can be used as the main resin of hull bottom self-polishing antifouling paint.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Among the embodiment, 1. propyl carbinol is illustrated in the propyl carbinol that the first step is used in the reactions step; 2. propyl carbinol is illustrated in the propyl carbinol that second step used in the reactions step.
Embodiment 1
A kind of from the polishing antifouling resin, molecular formula is:
In the formula, M is Zn; R
1, R
2Be methyl; R
3Be methyl; M, n, k are respectively the integer greater than 1; Should be 7000～9000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 2
A kind of from the polishing antifouling resin, molecular formula is with embodiment 1, and difference is: in the formula, M is Cu; R
1Be ethyl; R
2Be propyl group; R
3Be phenyl; M, n, k are respectively the integer greater than 1; Should be 10000～12000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 3
A kind of from the polishing antifouling resin, molecular formula is:
In the formula, M is Ca; R
1Be n-pentyl; R
2Be butyl; R
3Be phenyl; M, n, k are respectively the integer greater than 1; Should be 30000～35000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 4
A kind of from the polishing antifouling resin, molecular formula is with embodiment 3, and difference is: in the formula, M is Mg; R
1Be n-hexyl; R
2Be isobutyl-; R
3Be methyl; M, n, k are respectively the integer greater than 1; Should be 45000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 5
A kind of from the polishing antifouling resin, molecular formula is:
In the formula, M is Mn; R
1Be n-pentyl; R
2Be butyl; R
3Be methyl; M, n, k are respectively the integer greater than 1; Should be 7000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 6
A kind of from the polishing antifouling resin, molecular formula is with embodiment 5, and difference is: in the formula, M is Co; R
1Be isobutyl-; R
2Be butyl, R
3Be phenyl; M, n, k are respectively the integer greater than 1; Should be 10000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 7
A kind of from the polishing antifouling resin, molecular formula is with embodiment 5, and difference is: in the formula, M is Ba; R
1Be n-pentyl; R
2Be butyl, R
3Be methyl; M, n, k are respectively the integer greater than 1; Should be 30000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
Embodiment 8
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: Zinc acetate, basic 14.1g, vinylformic acid 7.2g, propyl carbinol be 45.5g, 4A level molecular sieve 20g 1.;
Bing Xisuandingzhi 40g, TEB 3K 42g, Diisopropyl azodicarboxylate 3.75g, propyl carbinol be 33g, YLENE 75g 2..
The first step: acrylic acid synthesizing zinc monomer
14.1g Zinc acetate, basic mixes with the 35.5g propyl carbinol, stirs, the there-necked flask of packing into places 70 ℃ oil bath; 7.2g vinylformic acid and 10g propyl carbinol mix, and in the constant pressure funnel of packing into, splash in the there-necked flask through 2 hours with constant speed, are incubated 1 hour, promptly obtain the zinc acrylate resin solution of clear.At last, add the 4A level molecular sieve dehydration of 20g, filter.The zinc acrylate resin strength of solution that finally obtains is 30%.Reaction formula is:
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is that the initiator of 10g Bing Xisuandingzhi, 10.5g TEB 3K, 15g zinc acrylate resin solution and 1/5 is the 0.75g Diisopropyl azodicarboxylate, and 55g YLENE, 20g propyl carbinol mix; Pack in the four-hole boiling flask, at 80 ℃ of following stirring reaction 1h; Secondly; Initiator with 3/5 is that the 2.25g Diisopropyl azodicarboxylate is dissolved in (being 30g Bing Xisuandingzhi, 31.5g TEB 3K, 45g zinc acrylate resin solution) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 2 hours, keep the constant stir speed (S.S.) down and be incubated 1h again at 80 ℃ simultaneously; To remain 1/5 initiator 0.75g at last and be dissolved in 20g YLENE and the 13g propyl carbinol, be contained in a constant pressure funnel, be added drop-wise in the four-hole bottle in 10 minutes, 80 ℃ of insulations 2 hours down, obtain at last from the polishing antifouling resin.
Detecting through nuclear-magnetism of present embodiment preparation from the polishing antifouling resin; Percentage of grafting reaches 100%, and number-average molecular weight is 11500, and polydispersity coefficient Mw/Mn is 3.5; Second-order transition temperature is 46.5 ℃; Sticking power reaches zero level, fits over other fillers to prepare antifouling varnish and have from polishability, and the antifouling phase imitates and can reach more than 3 years.The molecular formula from the polishing antifouling resin of present embodiment preparation is:
Wherein, m, n, k are the integer greater than 1.
Embodiment 9
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: alkali formula Zinc dibenzoate 20.3g, vinylformic acid 7.2g, propyl carbinol be 67.4g, 4A level molecular sieve 20g 1.;
Ethyl propenoate 40g, TEB 3K 36g, Diisopropyl azodicarboxylate 5g, propyl carbinol be 16g, YLENE 50g 2..
The first step: acrylic acid synthesizing zinc monomer
20.3g alkali formula Zinc dibenzoate and 57.4g propyl carbinol mixing and stirring, the there-necked flask of packing into places 70 ℃ oil bath; 7.2g vinylformic acid and 10g propyl carbinol mix, and in the constant pressure funnel of packing into, with constant speed, splash in the there-necked flask in 2 hours, are incubated 1 hour, promptly obtain the zinc acrylate resin solution of clear.The 4A level molecular sieve dehydration that adds 20g at last filters.The zinc acrylate resin strength of solution that finally obtains is 30%.Reaction formula is:
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is that the initiator of 10g ethyl propenoate, 9g TEB 3K, 30g zinc acrylate resin solution and 1/5 is the 1g Diisopropyl azodicarboxylate, and 40g YLENE, 6g propyl carbinol mix; Pack in the four-hole boiling flask, at 70 ℃ of following stirring reaction 1h; Secondly; Initiator with 3/5 is that the 3g Diisopropyl azodicarboxylate is dissolved in (being 30g ethyl propenoate, 27g TEB 3K, 90g zinc acrylate resin solution) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 2 hours, keep the constant stir speed (S.S.) down and be incubated 1h again at 70 ℃ simultaneously; At last, the initiator 1g with remaining 1/5 is dissolved in 10g YLENE and the 10g propyl carbinol, is contained in a constant pressure funnel, is added drop-wise in the four-hole bottle in 10 minutes, is incubated 2 hours down at 70 ℃ at last, obtains from the polishing antifouling resin.
Detecting through nuclear-magnetism of present embodiment preparation from the polishing antifouling resin; Percentage of grafting reaches 100%, and number-average molecular weight is 8500, and polydispersity coefficient Mw/Mn is 4.1; Second-order transition temperature is 54.2 ℃; Sticking power reaches zero level, fits over other fillers to prepare antifouling varnish and have from polishability, and the antifouling phase imitates and can reach more than 3 years.The molecular formula from the polishing antifouling resin of present embodiment preparation is:
Wherein, m, n, k are the integer greater than 1.
Embodiment 10
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: basic copper acetate 14g, vinylformic acid 7.2g, propyl carbinol be 45.3g, 4A level molecular sieve 20g 1.;
Ethyl propenoate 40g, TEB 3K 48g, Diisopropyl azodicarboxylate 5g, propyl carbinol be 22g, YLENE 75g 2..
The first step: acrylic acid synthesizing copper monomer
14g basic copper acetate and 35.3g propyl carbinol mixing and stirring, the there-necked flask of packing into places 70 ℃ oil bath; 7.2g vinylformic acid and 10g propyl carbinol mix, and in the constant pressure funnel of packing into, with constant speed, splash in the there-necked flask in 2 hours, are incubated 1 hour, promptly obtain the vinylformic acid copper solutions of clear.The 4A level molecular sieve dehydration that adds 20g at last filters.The vinylformic acid copper solutions concentration that finally obtains is 30%.
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is that the initiator of 10g ethyl propenoate, 12g TEB 3K, 10g vinylformic acid copper butanol solution and 1/5 is the 1g Diisopropyl azodicarboxylate, and 55g YLENE, 12g propyl carbinol mix; Pack in the four-hole boiling flask, at 80 ℃ of following stirring reaction 1h; Secondly; Initiator with 3/5 is that the 3g Diisopropyl azodicarboxylate is dissolved in (being 30g ethyl propenoate, 36g TEB 3K, 30g vinylformic acid copper solutions) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 2 hours, keep the constant stir speed (S.S.) down and be incubated 1h again at 80 ℃ simultaneously; At last, the initiator 1g with remaining 1/5 is dissolved in 20g YLENE and the 10g propyl carbinol, is contained in a constant pressure funnel, is added drop-wise in the four-hole bottle in 10 minutes, is incubated 2 hours down at 80 ℃ at last, obtains from the polishing antifouling resin.
Detecting through nuclear-magnetism of present embodiment preparation from the polishing antifouling resin; Percentage of grafting reaches 100%, and number-average molecular weight is 9700, and polydispersity coefficient Mw/Mn is 3.9; Second-order transition temperature is 41.3 ℃; Sticking power reaches zero level, fits over other fillers to prepare antifouling varnish and have from polishability, and the antifouling phase imitates and can reach more than 3 years.The molecular formula from the polishing antifouling resin of present embodiment preparation is:
Wherein, m, n, k are the integer greater than 1.
Embodiment 11
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: alkali formula magnesium benzoate 16.2g, vinylformic acid 7.2g, propyl carbinol be 57.8g, 4A level molecular sieve 20g 1.;
Bing Xisuandingzhi 40g, TEB 3K 48g, Diisopropyl azodicarboxylate 3.75g, propyl carbinol be 53g, YLENE 75g 2..
The first step: acrylic acid synthesizing magnesium monomer
16.2g alkali formula magnesium benzoate and 47.8g propyl carbinol mixing and stirring, the there-necked flask of packing into places 70 ℃ oil bath; 7.2g vinylformic acid and 10g propyl carbinol mix, and in the constant pressure funnel of packing into, with constant speed, splash in the there-necked flask in 2 hours, are incubated 1 hour, promptly obtain the vinylformic acid magnesium solution of clear.The 4A level molecular sieve dehydration that adds 20g at last filters.The vinylformic acid magnesium solution concentration that finally obtains is 30%.
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is that the initiator of 10g Bing Xisuandingzhi, 12g TEB 3K, 8g vinylformic acid magnesium butanol solution and 1/5 is the 0.75g Diisopropyl azodicarboxylate, and 55g YLENE, 40g propyl carbinol mix; Pack in the four-hole boiling flask, at 80 ℃ of following stirring reaction 1h; Secondly; Initiator with 3/5 is that the 2.25g Diisopropyl azodicarboxylate is dissolved in (being 30g Bing Xisuandingzhi, 36g TEB 3K, 24g vinylformic acid magnesium solution) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 2 hours, keep the constant stir speed (S.S.) down and be incubated 1h again at 80 ℃ simultaneously; At last, the initiator 0.75g that remains 1/5 is dissolved in 20g YLENE and the 13g propyl carbinol, is contained in a constant pressure funnel, be added drop-wise in the four-hole bottle in 10 minutes, be incubated 2 hours down at 80 ℃ at last, obtain from the polishing antifouling resin.
Detecting through nuclear-magnetism of present embodiment preparation from the polishing antifouling resin; Percentage of grafting reaches 100%, and number-average molecular weight is 10700, and polydispersity coefficient Mw/Mn is 3.61; Second-order transition temperature is 40.5 ℃; Sticking power reaches zero level, fits over other fillers to prepare antifouling varnish and have from polishability, and the antifouling phase imitates and can reach more than 3 years.The molecular formula from the polishing antifouling resin of present embodiment preparation is:
Wherein, m, n, k are the integer greater than 1.
Embodiment 12
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: alkali formula barium acetate 21.3g, vinylformic acid 7.2g, Virahol 62.3g, 4A level molecular sieve 20g;
Ethyl propenoate 40g, TEB 3K 48g, Diisopropyl azodicarboxylate 5g, propyl carbinol 22g, YLENE 75g.
The first step: acrylic acid synthesizing barium monomer
21.3g alkali formula barium acetate and 52.3g Virahol mixing and stirring, the there-necked flask of packing into places 70 ℃ oil bath; 7.2g vinylformic acid and 10g Virahol mix, and in the constant pressure funnel of packing into, with constant speed, splash in the there-necked flask in 2 hours, are incubated 1 hour, promptly obtain the vinylformic acid barium solution of clear.The 4A level molecular sieve dehydration that adds 20g at last filters.The vinylformic acid barium strength of solution that finally obtains is 30%.
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is that the initiator of 10g ethyl propenoate, 12g TEB 3K, 10g vinylformic acid barium aqueous isopropanol and 1/5 is the 1g Diisopropyl azodicarboxylate; And 55g YLENE, 12g propyl carbinol mixes, in the four-hole boiling flask of packing into, 80 ℃ of following stirring reactions 1 hour; Secondly; Initiator with 3/5 is that the 3g Diisopropyl azodicarboxylate is dissolved in (being 30g ethyl propenoate, 36g TEB 3K, 30g vinylformic acid barium solution) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 1 hour, keep the constant stir speed (S.S.) and be incubated 1 hour down at 80 ℃ simultaneously; At last, the initiator 1g that remains 1/5 is dissolved in 20g YLENE and the 10g propyl carbinol, is contained in a constant pressure funnel, be added drop-wise in the four-hole bottle in 10 minutes, be incubated 2 hours down at 80 ℃ at last, obtain from the polishing antifouling resin.
Embodiment 13
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: alkali formula manganese benzoate 19.3g, methylacrylic acid 8.6g, propyl carbinol be 65.1g, 4A level molecular sieve 20g 1.;
Bing Xisuandingzhi 40g, TEB 3K 48g, propyl carbinol be 47g, YLENE 75g, Diisopropyl azodicarboxylate 3.75g 2..
The first step: acrylic acid synthesizing manganese monomer
19.3g alkali formula cupric benzoate and 55.1g propyl carbinol mixing and stirring, the there-necked flask of packing into places 70 ℃ oil bath.8.6g methylacrylic acid and 10g propyl carbinol mix, and in the constant pressure funnel of packing into, with constant speed, splash in the there-necked flask in 2 hours, are incubated 1 hour, promptly obtain the vinylformic acid manganese solution of clear.The 4A level molecular sieve dehydration that adds 20g at last filters.The concentration of the vinylformic acid manganese solution that finally obtains is 30%.
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is that the initiator of 10g Bing Xisuandingzhi, 12g TEB 3K, 10g vinylformic acid manganese butanol solution and 1/5 is the 0.75g Diisopropyl azodicarboxylate, and 55g YLENE, 34g propyl carbinol mix; Pack in the four-hole boiling flask, 80 ℃ of following stirring reactions 2 hours; Secondly; Initiator with 3/5 is that the 2.25g Diisopropyl azodicarboxylate is dissolved in (being 30g Bing Xisuandingzhi, 36g TEB 3K, 30g vinylformic acid manganese solution) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 4 hours, keep the constant stir speed (S.S.) and be incubated 3 hours down at 80 ℃ simultaneously; At last, the initiator 0.75g that remains 1/5 is dissolved in 20g YLENE and the 13g propyl carbinol, is contained in a constant pressure funnel, be added drop-wise in the four-hole bottle in 10 minutes, be incubated 3 hours down at 80 ℃ at last, obtain from the polishing antifouling resin.
Embodiment 14
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
Raw material: alkali formula calcium acetate 11.6g, vinylformic acid 7.2g, propyl carbinol 1. 39.7g,, 4A level molecular sieve 20g;
Bing Xisuandingzhi 40g, TEB 3K 42g, propyl carbinol be 33g, YLENE 75g, Diisopropyl azodicarboxylate 3.75g 2..
The first step: acrylic acid synthesizing calcium monomer
11.6g alkali formula calcium acetate and 29.7g propyl carbinol mixing and stirring, the there-necked flask of packing into places 70 ℃ oil bath; 7.2g vinylformic acid and 10g propyl carbinol mix, and in the constant pressure funnel of packing into, with constant speed, splash in the there-necked flask in 2 hours, are incubated 1 hour, promptly obtain the calcium acrylate solution of clear.The 4A level molecular sieve dehydration that adds 20g at last filters.The calcium acrylate strength of solution that finally obtains is 30%.
Second step: radical polymerization is synthetic from the polishing antifouling resin
At first; Monomer with 1/4 is 10g Bing Xisuandingzhi, 10.5g TEB 3K, 15g calcium acrylate butanol solution; With 1/5 initiator be the 0.75g Diisopropyl azodicarboxylate; And 55g YLENE, 20g propyl carbinol mixes, in the four-hole boiling flask of packing into, 80 ℃ of following stirring reactions 1.5 hours; Secondly; Initiator with 3/5 is that the 2.25g Diisopropyl azodicarboxylate is dissolved in (being 30g Bing Xisuandingzhi, 31.5g TEB 3K, 45g calcium acrylate solution) in the residual monomers; Be contained in the constant pressure funnel; Be added drop-wise in the four-hole bottle with constant speed in 3 hours, keep the constant stir speed (S.S.) and be incubated 2 hours down at 80 ℃ simultaneously; At last, the initiator 0.75g that remains 1/5 is dissolved in 20g YLENE and the 13g propyl carbinol, is contained in a constant pressure funnel, be added drop-wise in the four-hole bottle in 10 minutes, be incubated 2.5 hours down at 80 ℃ at last, obtain from the polishing antifouling resin.
Embodiment 15
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 40 ℃ the condition to solution becomes to clarify; Be incubated 1 hour again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) 2 parts of unsaturated organic acid divalent-metal ion salt D that step (1) is generated and 1 part of other acrylic monomers E are blended among 45 parts of the solvent F; Temperature is under 65 ℃ the condition; At first 4/5 initiator G promptly was added drop-wise in the mixed solution through 2 hours, initiated polymerization is added drop-wise to remaining 1/5 initiator G in the mixed solution afterwards; Reacted again 2 hours, synthetic from polishing antifouling resin H;
Wherein, unsaturated organic acid A is the mixture (both mol ratios are 1:1) of vinylformic acid and methylacrylic acid; Alkali formula divalent-metal ion double salt B is an alkali formula calcium acetate; Solvent C is the mixture of Virahol and n-propyl alcohol; Other acrylic monomers E is the mixture of 0.5 part of Bing Xisuandingzhi, 0.5 part of ethyl propenoate; Solvent F is a Virahol; Initiator G is 5 parts of ABVNs;
Embodiment 16
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 80 ℃ the condition to solution becomes to clarify; Be incubated 2 hours again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) 40 parts of unsaturated organic acid divalent-metal ion salt D that step (1) is generated and 120 parts of other acrylic monomers E are blended among 125 parts of the solvent F; Temperature is under 90 ℃ the condition; At first 4/5 initiator G was added drop-wise in the mixed solution through 3 hours, initiated polymerization is added drop-wise to remaining 1/5 initiator G in the mixed solution afterwards; Reacted again 3 hours, synthetic from polishing antifouling resin H;
Wherein, unsaturated organic acid A is a butenoic acid; Alkali formula divalent-metal ion double salt B is the mixture (both mol ratios are 5:1) of alkali formula Cobaltous diacetate and alkali formula barium acetate; Solvent C is the mixture of propyl carbinol, Virahol and n-propyl alcohol; Other acrylic monomers E is the mixture of 70 parts of 30 parts of TEB 3Ks, 20 parts of methyl acrylates and NSC 20956s; Solvent F is the mixture of 50 parts of 25 parts of propyl carbinols, 50 parts of Virahols and n-propyl alcohols; Initiator G is 0.5 part of a Lucidol.
Embodiment 17
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 60 ℃ the condition to solution becomes to clarify; Be incubated 1.5 hours again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) 8 parts of unsaturated organic acid divalent-metal ion salt D that step (1) is generated and 30 parts of other acrylic monomers E are blended among 80 parts of the solvent F; Temperature is under 78 ℃ the condition; At first 4/5 initiator G was added drop-wise in the mixed solution through 4 hours, initiated polymerization is added drop-wise to remaining 1/5 initiator G in the mixed solution afterwards; Reacted again 2.5 hours, synthetic from polishing antifouling resin H;
Wherein, unsaturated organic acid A is the mixture (three's mol ratio is 1:1:2) of vinylformic acid, methylacrylic acid and butenoic acid; Alkali formula divalent-metal ion double salt B is the mixture (both mol ratios are 2:3) of alkali formula manganese acetate and alkali formula Zinc dibenzoate; Solvent C is a Virahol; Other acrylic monomers E is the mixture of 10 parts of Bing Xisuandingzhis and 20 parts of methyl acrylates; Solvent F is the mixture of 20 parts of Virahols and 60 parts of YLENE; Initiator G is 3 parts of azo-bis-iso-dimethyls.
Embodiment 18
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 65 ℃ the condition to solution becomes to clarify; Be incubated 1.2 hours again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) at first, unsaturated organic acid divalent-metal ion salt D, 1/4 other acrylic monomers E and 1/5 initiator G that 1/4 step (1) is generated are blended among the solvent F, react 1 hour; Secondly, in the mixed solution of mixed solution before being added drop-wise in 2 hours of unsaturated organic acid divalent-metal ion salt D, 3/4 other acrylic monomers E and the 3/5 initiator G that 3/4 step (1) is generated, reacted again 1 hour; At last, 1/5 initiator G is added drop-wise in the mixed solution, reacted 2 hours, synthetic from polishing antifouling resin H; Wherein, the temperature of reaction of above-mentioned reaction is 65 ℃;
Wherein, unsaturated organic acid A is a vinylformic acid; Alkali formula divalent-metal ion double salt B is an alkali formula cupric benzoate; Solvent C is a n-propyl alcohol; 10 parts of unsaturated organic acid divalent-metal ion salt D; Other acrylic monomers E is 50 parts of NSC 20956s; Solvent F is the mixture of 30 parts of 50 parts of n-propyl alcohols, 50 parts of Virahols and YLENE; Initiator G is 2.5 parts of lauroyl peroxides.
Embodiment 19
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 50 ℃ the condition to solution becomes to clarify; Be incubated 2 hours again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) at first, unsaturated organic acid divalent-metal ion salt D, 1/4 other acrylic monomers E and 1/5 initiator G that 1/4 step (1) is generated are blended among the solvent F, react 1 hour; Secondly, in the mixed solution of mixed solution before being added drop-wise in 2 hours of unsaturated organic acid divalent-metal ion salt D, 3/4 other acrylic monomers E and the 3/5 initiator G that 3/4 step (1) is generated, reacted again 1 hour; At last, 1/5 initiator G is added drop-wise in the mixed solution, reacted 3 hours, synthetic from polishing antifouling resin H; Wherein, the temperature of reaction of above-mentioned reaction is 90 ℃;
Wherein, unsaturated organic acid A is the mixture (both mol ratios are 2:1) of methylacrylic acid and butenoic acid; Alkali formula divalent-metal ion double salt B is an alkali formula magnesium benzoate; Solvent C is a Virahol; 15 parts of unsaturated organic acid divalent-metal ion salt D; Other acrylic monomers E is 50 parts of 10 parts of Bing Xisuandingzhis, 20 parts of methyl acrylates and NSC 20956s; Solvent F is the mixture of 10 parts of n-propyl alcohols, 60 parts of Virahols; Initiator G is 5 parts of azo-bis-iso-dimethyls.
Embodiment 20
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 75 ℃ the condition to solution becomes to clarify; Be incubated 1.5 hours again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) at first, unsaturated organic acid divalent-metal ion salt D, 1/4 other acrylic monomers E and 1/5 initiator G that 1/4 step (1) is generated are blended among the solvent F, react 1 hour; Secondly, in the mixed solution of mixed solution before being added drop-wise in 2 hours of unsaturated organic acid divalent-metal ion salt D, 3/4 other acrylic monomers E and the 3/5 initiator G that 3/4 step (1) is generated, reacted again 1 hour; At last, 1/5 initiator G is added drop-wise in the mixed solution, reacted 2 hours, synthetic from polishing antifouling resin H; Wherein, the temperature of reaction of above-mentioned reaction is 75 ℃;
Wherein, unsaturated organic acid A is a vinylformic acid; Alkali formula divalent-metal ion double salt B is an alkali formula cupric benzoate; Solvent C is a n-propyl alcohol; 40 parts of unsaturated organic acid divalent-metal ion salt D; Other acrylic monomers E is 120 parts of NSC 20956s; Solvent F is the mixture of 35 parts of 10 parts of n-propyl alcohols, 20 parts of Virahols and YLENE; Initiator G is 5 parts of lauroyl peroxides.
Embodiment 21
A kind of preparation method from the polishing antifouling resin may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 70 ℃ the condition to solution becomes to clarify; Be incubated 2 hours again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) 2 parts of unsaturated organic acid divalent-metal ion salt D that step (1) is generated and 1 part of other acrylic monomers E are blended among 45 parts of the solvent F; Temperature is under 70 ℃ the condition; At first 4/5 initiator G was added drop-wise in the mixed solution through 2 hours, initiated polymerization is added drop-wise to remaining 1/5 initiator G in the mixed solution afterwards; Reacted again 3 hours, synthetic from polishing antifouling resin H; Wherein, the temperature of reaction of above-mentioned reaction is 70 ℃;
Wherein, unsaturated organic acid A is a butenoic acid; Alkali formula divalent-metal ion double salt B is the mixture (both mol ratios are 1:2) of alkali formula Cobaltous diacetate and alkali formula barium acetate; Solvent C is the mixture of propyl carbinol, Virahol and n-propyl alcohol; Other acrylic monomers E is 1 part of a TEB 3K; Solvent F is the mixture of 25 parts of propyl carbinols, 20 parts of Virahols; Initiator G is 0.5 part of a Lucidol.
Obviously, the above embodiment of the present invention only be for clearly the present invention is described and is done for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (9)
1. one kind from the polishing antifouling resin, it is characterized in that its molecular formula is:
In the formula, M is Zn, Cu, Ca, Mg, Mn, Co or Ba;
R
1, R
2Be respectively carbonatoms and be not more than 6 alkyl;
R
3Be methyl or phenyl;
M, n, k are respectively the integer greater than 1; Should be 7000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
2. the preparation method from the polishing antifouling resin as claimed in claim 1 is characterized in that, may further comprise the steps:
(1) unsaturated organic acid A and alkali formula divalent-metal ion double salt B are reacted in solvent C according to mol ratio 1:1; Temperature is to react under 40 ℃～80 ℃ the condition to solution becomes to clarify; Be incubated 1 ~ 2 hour again, generate unsaturated organic acid divalent-metal ion salt D, remove the water of generation;
(2) the unsaturated organic acid divalent-metal ion salt D and other acrylic monomers E that step (1) are generated are blended among the solvent F; Temperature is under 65 ℃～90 ℃ the condition; At first 4/5 initiator G was added drop-wise in the mixed solution through 1～4 hour, initiated polymerization is added drop-wise to remaining 1/5 initiator G in the mixed solution afterwards; Reaction, synthetic from polishing antifouling resin H;
The unsaturated organic acid A of said step (1) is one or more mixtures in vinylformic acid, methylacrylic acid, the butenoic acid;
The alkali formula divalent-metal ion double salt B of said step (1) be M (CH3COO) (OH), M (C
6H
5COO) mixture of one or more in (OH);
In the said step (2), each material uses according to following mass fraction proportioning:
Said synthetic from the molecular formula of polishing antifouling resin H is:
In the formula, M is Zn, Cu, Ca, Mg, Mn, Co or Ba;
R
1, R
2Be respectively carbonatoms and be not more than 6 alkyl;
R
3Be methyl or phenyl;
M, n, k are respectively the integer greater than 1; Should be 7000～50000 from the number-average molecular weight of polishing antifouling resin, polydispersity coefficient≤5.
3. the preparation method from the polishing antifouling resin according to claim 2 is characterized in that, the divalent-metal ion M of the said alkali formula divalent-metal ion double salt B of said step (1) is Zn
2+, Cu
2+, Ca
2+, Mg
2+, Mn
2+, Co
2+, Ba
2+
4. the preparation method from the polishing antifouling resin according to claim 2 is characterized in that, the solvent C of said step (1) is one or more mixtures in propyl carbinol, Virahol, the n-propyl alcohol.
5. the preparation method from the polishing antifouling resin according to claim 2; It is characterized in that; Said step (2) is: temperature is under 65 ℃～90 ℃ the condition; At first, unsaturated organic acid divalent-metal ion salt D, 1/4 other acrylic monomers E and 1/5 initiator G that 1/4 step (1) is generated are blended among the solvent F, react 1～2 hour; Secondly, in the mixed solution of mixed solution before being added drop-wise in 1～4 hour of unsaturated organic acid divalent-metal ion salt D, 3/4 other acrylic monomers E and the 3/5 initiator G that 3/4 step (1) is generated, reacted again 1～3 hour; At last, 1/5 initiator G is added drop-wise in the mixed solution, reacted 2 ~ 3 hours, synthetic from polishing antifouling resin H.
6. according to claim 2 or 4 described preparing methods from the polishing antifouling resin; It is characterized in that other acrylic monomers E of said step (2) is one or more mixtures in Bing Xisuandingzhi, ethyl propenoate, TEB 3K, methyl acrylate, the NSC 20956.
7. according to claim 2 or 4 described preparing methods from the polishing antifouling resin; It is characterized in that the solvent F of said step (2) is one or more mixtures in propyl carbinol, Virahol, the n-propyl alcohol or is the mixture of one or both and YLENE in the propyl carbinol, Virahol, n-propyl alcohol.
8. according to claim 2 or 4 described preparing methods from the polishing antifouling resin; It is characterized in that the initiator G of said step (2) is Diisopropyl azodicarboxylate, ABVN, azo-bis-iso-dimethyl, Lucidol, lauroyl peroxide.
9. the preparation method from the polishing antifouling resin according to claim 2 is characterized in that, adopts the method for 4A level molecular sieve or underpressure distillation that solution is dewatered in the said step (1).
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Cited By (7)
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| CN103709318A (en) * | 2013-12-25 | 2014-04-09 | 浙江海洋学院 | Polyacrylic acid metal salt resin antifouling material and coating structure |
| CN104177970A (en) * | 2014-08-20 | 2014-12-03 | 海南大学 | Antifouling coating material and preparation method thereof |
| CN108017969A (en) * | 2017-12-13 | 2018-05-11 | 王葱芽 | Abietyl modified acrylate paint |
| CN108609672A (en) * | 2018-04-23 | 2018-10-02 | 福建省蓝深环保技术股份有限公司 | A kind of environment protection sewage inorganic agent |
| CN106317346B (en) * | 2016-08-17 | 2019-02-01 | 厦门双瑞船舶涂料有限公司 | A kind of preparation method and its usage of degradable antifouling resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
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2012
- 2012-05-22 CN CN 201210160669 patent/CN102675524B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
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| CN103709318A (en) * | 2013-12-25 | 2014-04-09 | 浙江海洋学院 | Polyacrylic acid metal salt resin antifouling material and coating structure |
| CN103709318B (en) * | 2013-12-25 | 2016-05-04 | 浙江海洋学院 | Polyacrylic acid slaine resin anti-fouling material and coating structure |
| CN104177970A (en) * | 2014-08-20 | 2014-12-03 | 海南大学 | Antifouling coating material and preparation method thereof |
| CN106317346B (en) * | 2016-08-17 | 2019-02-01 | 厦门双瑞船舶涂料有限公司 | A kind of preparation method and its usage of degradable antifouling resin |
| CN108017969A (en) * | 2017-12-13 | 2018-05-11 | 王葱芽 | Abietyl modified acrylate paint |
| CN108609672A (en) * | 2018-04-23 | 2018-10-02 | 福建省蓝深环保技术股份有限公司 | A kind of environment protection sewage inorganic agent |
| CN110183597A (en) * | 2019-06-17 | 2019-08-30 | 中国科学院理化技术研究所 | It is a kind of containing grafted graphene oxide from polishing antifouling resin and preparation method thereof |
| CN115197360A (en) * | 2022-07-08 | 2022-10-18 | 哈尔滨工程大学 | Eugenol ester-based fluorine methacrylate self-polishing antifouling resin and preparation method thereof |
| CN115197360B (en) * | 2022-07-08 | 2023-08-01 | 哈尔滨工程大学 | Eugenol ester methacrylic acid fluorine self-polishing anti-fouling resin and preparation method thereof |
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| CN102675524B (en) | 2013-10-16 |
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