CN104725551A - Synthetic method of copper/zinc acrylate self-polishing antifouling resin - Google Patents
Synthetic method of copper/zinc acrylate self-polishing antifouling resin Download PDFInfo
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- CN104725551A CN104725551A CN201310717620.2A CN201310717620A CN104725551A CN 104725551 A CN104725551 A CN 104725551A CN 201310717620 A CN201310717620 A CN 201310717620A CN 104725551 A CN104725551 A CN 104725551A
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Abstract
The invention relates to a synthetic method of copper/zinc acrylate self-polishing antifouling resin. According to the method, organic acid and copper/zinc hydroxide are used to synthesize a basic organic acid copper/zinc low molecular weight monomer; then, an acrylic monomer mixture is used to synthesize an acrylic resin prepolymer under the action of an initiator; and finally, the basic organic acid copper/zinc low molecular weight monomer and the acrylic resin prepolymer are used to synthesize the copper/zinc acrylate self-polishing antifouling resin. In comparison with the prior art, the method is simple to operate and can be adopted to effectively reduce conversion rate of by-products, enhance intake quantity of copper ions and overcome the cementation problem during the synthesis process of copper/zinc acrylate.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to the synthetic method of a kind of vinylformic acid copper/zinc from polishing antifouling resin.
Background technology
Marine fouling organism primary growth is on shell waterline lower part, buoy, coastal factory cooling water pipeline, coastal facility, undersea cable, pontoon bridge, fishery netting gear surface, Bio-ontology and secretory product thereof not only can cause burn into shorten its work-ing life but also significantly can increase hull mass to hull structure, boats and ships actual load ability is caused to decline, in addition, the apposition growth of marine fouling organism can make the frictional coefficient of hull surface become large, thus has a strong impact on ship's speed, increase fuel consumption.
Rise in the mid-1970s in last century from polishing antifouling technology, enter the eighties in last century according to statistics, the whole world has the boats and ships of 60% ~ 70% to use organotin self polishing copolymer antifouling paint, this self polishing copolymer antifouling paint can be hull provide as long as five years without stained performance, and the resistance that hull bottom keeps smooth and low can be made, but this organotin self polishing copolymer antifouling paint constantly discharges organotin poison material in mechanism, and this poison expects that accumulation in the seawater can cause biological teratogenesis.The self polishing copolymer antifouling paint of environment amity had a kind ofly both had good didirtresistance and economy, can meet again a kind of antifouling paint of current environment requirement simultaneously.
Vinylformic acid copper/zinc resin is a kind of resin conventional in the self polishing copolymer antifouling paint of environment amity; the method that current acrylic acid synthesizing copper/zinc antifouling resin is conventional is prepolymer method; namely first preparation contains the acrylic resin prepolymer of carboxyl functional group, and then is incorporated in acrylic resin systems by copper/zine ion by the method such as ion exchange reaction, substitution reaction with copper/zinc compounds.But, adopt this method synthetic resins, its salient features is determined by resin prepolymer, and its structure Modulatory character is poor, simultaneously, because side reaction (carboxyl and organic acid permutoid reaction) is wayward, the viscosity of polymkeric substance can constantly raise so that cementing, cause the synthesis difficulty of resin larger, and the introduction volume of this method copper/zine ion is lower, general about 2%, not obvious from polishing effect.
Summary of the invention
Technical problem to be solved by this invention provides a kind of product yield is high, copper/zine ion introduction volume is high vinylformic acid copper/zinc from the synthetic method of polishing antifouling resin.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of vinylformic acid copper/zinc, from the synthetic method of polishing antifouling resin, is characterized in that comprising the following steps:
(1) at reflux temperature T
1under, by 15 ~ 30% organic acids, 10 ~ 25% copper hydroxides or zinc hydroxide, under 45 ~ 75% solvents exist, react 5-10 hour obtained alkali formula copper organic acid/zinc small molecule monomer, each composition press percent mass relation participate in reaction, and in this step each composition mass percent and be 100%;
(2) at reflux temperature T
2under, by 36 ~ 59% Acrylic Acid Monomer mixtures, under 0.6 ~ 4% initiator effect and 40 ~ 60% mixed solvent existence conditions, react and within 3-10 hour, aggregate into carboxylic acrylic resin performed polymer, each composition press percent mass relation participate in reaction, and in this step each composition mass percent and be 100%;
(3) at reflux temperature T
3under, by 10 ~ 15% alkali formula copper organic acid/zinc small molecule monomers and 85 ~ 90% acrylic resin performed polymers, reacting 5-15 hour obtained number-average molecular weight is in the presence of solvent that the vinylformic acid copper/zinc of 10,000-4 ten thousand is from polishing antifouling resin, each composition press percent mass relation participate in reaction, and in this step each composition mass percent and be 100%.
Organic acid in described step (1) is sylvic acid, hydroabietic acid, indolic acid, naphthenic acid or containing the one in benzene organic acid.
Solvent in described step (1) and step (3) is respectively the one in dimethylbenzene, propylene glycol monomethyl ether, propyl carbinol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, 200# solvent oil, methyl-2-pyrrolidone, butylacetate; And the mixed solvent in described step (2) is at least one in dimethylbenzene, propylene glycol monomethyl ether, propyl carbinol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, 200# solvent oil, methyl-2-pyrrolidone, butylacetate.
Described Acrylic Acid Monomer comprises basic monomer and selects monomer, wherein basic monomer comprises vinylformic acid, ethyl propenoate and n-butyl acrylate, and selects monomer to be one in methyl methacrylate, methoxyethyl acrylate, cyclohexyl acrylate, β-dimethyl-aminoethylmethacrylate or at least one.
Described initiator is azo-initiator, and conventional as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), such initiator reacts without induced decomposition, and reaction products therefrom production rate is higher.
Described T
1be 80 ~ 120 DEG C, described T
2be 100 ~ 120 DEG C, described T
3it is 60 ~ 80 DEG C.
In above-mentioned each scheme, described organic acid is phenylformic acid; Solvent in described step (1) is propylene glycol monomethyl ether, and the mixed solvent in described step (2) is propyl carbinol and xylene mixture solvent, and the solvent in described step (3) is dimethylbenzene; Described azo-initiator is Diisopropyl azodicarboxylate.
Further again, in described Acrylic Acid Monomer mixture, the ratio of vinylformic acid, ethyl propenoate, butyl acrylate and selection monomer is: 5 ~ 15:60 ~ 90:10 ~ 30:20 ~ 45.
Further again, in described mixed solvent, the ratio of propyl carbinol and dimethylbenzene is: 1:3 ~ 6
Compared with prior art, the invention has the advantages that: in the present invention, first synthesize copper hydroxybenzoate/zinc small molecule monomer, then acrylic acid synthesizing resin prepolymer, last by copper hydroxybenzoate/zinc small molecule monomer and acrylic resin performed polymer acrylic acid synthesizing copper/zinc antifouling resin, the method is simple to operate, can effectively reduce by product transformation efficiency, improve the introduction volume of copper/zine ion, overcome the cementing problem in vinylformic acid copper/zinc building-up process.
Embodiment
Second-order transition temperature (Tg) reflects that amorphous polymer is the transition temperature of elastomeric state by the glassy transition of fragility, the coating of different purposes, the second-order transition temperature of its resin differs greatly, below by four kinds of different vinylformic acid copper/zinc antifouling resin synthetic methods, the present invention is described in further detail, wherein vinylformic acid copper/zinc antifouling resin is the shorthand of vinylformic acid copper antifouling resin or zinc acrylate resin antifouling resin, low Tg:Tg < 0 DEG C, middle Tg:0≤T
g≤ 30 DEG C, high Tg:T
g> 30 DEG C.
Embodiment 1: the preparation of low Tg vinylformic acid copper antifouling resin
The preparation of a, copper hydroxybenzoate small molecule monomer
97g copper hydroxide and 150g propylene glycol monomethyl ether is added in the 1L four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 120 DEG C, then 122g phenylformic acid is weighed, fully be dissolved in 250g propylene glycol monomethyl ether solution, dropwised by a constant pressure funnel 5-6 hour constant speed, continue reaction and complete reaction after 0.5 hour.Reaction product is filtered, and separates filtrate, and gained filtering solids absolute ethanol washing three times, 30 DEG C of vacuum-drying 48h, obtain sky blue solid 181g, i.e. copper hydroxybenzoate, productive rate 90%.
The preparation of b, vinylformic acid copper antifouling resin
80g propyl carbinol and 270g dimethylbenzene is added in the four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 110 DEG C, then the mixed solution comprising 24g vinylformic acid, 180g ethyl propenoate, the positive fourth vinegar of 40g vinylformic acid, 36g methoxyethyl acrylate, 4g Diisopropyl azodicarboxylate is weighed, dropwised through 3 hours constant speed by constant pressure funnel, add 1g Diisopropyl azodicarboxylate, continue reaction and be warming up to 120 DEG C after 2 hours, obtained acrylic resin performed polymer after insulation 1h.
C, acrylic resin performed polymer obtained for b step is cooled to 80 DEG C, then adds 53g copper hydroxybenzoate, continue reaction 12h, obtain vinylformic acid copper antifouling resin.
The low Tg vinylformic acid copper antifouling resin prepared in the present embodiment is analyzed after tested, and its number-average molecular weight Mn is 31432, polydispersity coefficient Mw Mn be 2.87, second-order transition temperature is-24 DEG C, sticking power reaches zero level, and marine link plate 6 months, film has almost no change.
Embodiment 2: the preparation of middle Tg vinylformic acid copper antifouling resin
The preparation of a, copper hydroxybenzoate small molecule monomer
97g copper hydroxide and 150g propylene glycol monomethyl ether is added in the 1L four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 120 DEG C, then 122g phenylformic acid is weighed, fully be dissolved in 250g propylene glycol monomethyl ether solution, dropwised by a constant pressure funnel 5-6 hour constant speed, continue reaction and complete reaction after 0.5 hour.Reaction product is filtered, and separates filtrate, and gained filtering solids absolute ethanol washing three times, 30 DEG C of vacuum-drying 48h, obtain sky blue solid 181g, i.e. copper hydroxybenzoate, productive rate 90%.
The preparation of b, acrylic resin performed polymer
80g propyl carbinol and 270g dimethylbenzene is added in the four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 110 DEG C, then the mixed solution comprising 24g vinylformic acid, 120g ethyl propenoate, the positive fourth vinegar of 50g vinylformic acid, 86g methyl methacrylate, 4g Diisopropyl azodicarboxylate is weighed, dropwised through 3 hours constant speed by constant pressure funnel, add 1g Diisopropyl azodicarboxylate, continue reaction and be warming up to 120 DEG C after 2 hours, obtained acrylic resin performed polymer after insulation 1h.
The preparation of c, vinylformic acid copper antifouling resin
The acrylic resin performed polymer that b step is obtained is cooled to 80 DEG C, then adds 53g copper hydroxybenzoate and continues reaction 12h, obtain vinylformic acid copper antifouling resin.
The middle Tg vinylformic acid copper antifouling resin prepared in the present embodiment is analyzed after tested, and its number-average molecular weight Mn is 37823, polydispersity coefficient Mw Mn be 3.13, second-order transition temperature is 19 DEG C, and film pencil hardness reaches 2H, and sticking power reaches zero level, marine link plate 6 months, film has almost no change.
Embodiment 3: the preparation of high Tg vinylformic acid copper antifouling resin
The preparation of a, copper hydroxybenzoate small molecule monomer
97g copper hydroxide and 150g propylene glycol monomethyl ether is added in the 1L four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 120 DEG C, then 122g phenylformic acid is weighed, fully be dissolved in 250g propylene glycol monomethyl ether solution, dropwised by a constant pressure funnel 5-6 hour constant speed, continue reaction and complete reaction after 0.5 hour.Reaction product is filtered, and separates filtrate, and gained filtering solids absolute ethanol washing three times, 30 DEG C of vacuum-drying 48h, obtain sky blue solid 181g, i.e. copper hydroxybenzoate, productive rate 90%.
The preparation of b, acrylic resin performed polymer
80g propyl carbinol and 360g dimethylbenzene is added in the four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 110 DEG C, then the mixed solution comprising 24g vinylformic acid, 166g methyl methacrylate, 26g ethyl propenoate, the positive fourth vinegar of 40g vinylformic acid, 4g Diisopropyl azodicarboxylate is weighed, dropwised through 3 hours constant speed by constant pressure funnel, add 1g Diisopropyl azodicarboxylate, continue reaction and be warming up to 120 DEG C after 2 hours, obtained acrylic resin performed polymer after insulation 1h.
The preparation of c, vinylformic acid copper antifouling resin
The acrylic resin performed polymer that b step is obtained is cooled to 80 DEG C, then adds 53g copper hydroxybenzoate and continues reaction 12h, obtain vinylformic acid copper antifouling resin.
The low Tg vinylformic acid copper antifouling resin prepared in the present embodiment is analyzed after tested, and its number-average molecular weight Mn is 32634, polydispersity coefficient Mw Mn be 3.13, second-order transition temperature is 63 DEG C, and film pencil hardness reaches 4H, and sticking power reaches zero level, marine link plate 6 months, film has almost no change.
Embodiment 4: the preparation of high Tg zinc acrylate resin antifouling resin
The preparation of a, alkali formula Zinc dibenzoate small molecule monomer
99g zinc hydroxide and 150g propylene glycol monomethyl ether is added in the 1L four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 120 DEG C, then 122g phenylformic acid is weighed, fully be dissolved in 250g propylene glycol monomethyl ether solution, dropwised through 5-6 hour constant speed by constant pressure funnel, continue reaction and complete reaction after 0.5 hour.Reaction product is filtered, and separates filtrate, and gained filtering solids absolute ethanol washing three times, 30 DEG C of vacuum-drying 48h, obtain white solid 162g, i.e. alkali formula Zinc dibenzoate, productive rate 79%.
The preparation of b, acrylic resin performed polymer
80g propyl carbinol and 270g dimethylbenzene is added in the four-hole boiling flask that agitator, reflux condensing tube, constant pressure funnel, thermometer are housed, stir and be warming up to 110 DEG C, then the mixed solution comprising 24g vinylformic acid, 166g methyl methacrylate, 26g ethyl propenoate, 40g n-butyl acrylate, 4g Diisopropyl azodicarboxylate is weighed, dropwised through 3 hours constant speed by constant pressure funnel, add 1g Diisopropyl azodicarboxylate, continue reaction and be warming up to 120 DEG C after 2 hours, obtained acrylic resin performed polymer after insulation 1h.
The preparation of c, vinylformic acid copper antifouling resin
The acrylic resin performed polymer that b step is obtained is cooled to 80 DEG C, then adds 54g alkali formula Zinc dibenzoate and continues reaction 12h, obtain zinc acrylate resin antifouling resin.
The high Tg zinc acrylate resin antifouling resin prepared in the present embodiment is analyzed after tested, and its number-average molecular weight Mn is 36991, polydispersity coefficient Mw Mn be 3.35, second-order transition temperature is 54 DEG C, and film pencil hardness reaches 3H, and sticking power reaches zero level, marine link plate 6 months, film has almost no change.
Claims (9)
1. vinylformic acid copper/zinc is from a synthetic method for polishing antifouling resin, it is characterized in that comprising the following steps:
(1) at reflux temperature T
1under, by 15 ~ 30% organic acids, 10 ~ 25% copper hydroxides or zinc hydroxide, under 45 ~ 75% solvents exist, react 5-10 hour obtained alkali formula copper organic acid/zinc small molecule monomer, each composition press percent mass relation participate in reaction, and in this step each composition mass percent and be 100%;
(2) at reflux temperature T
2under, by 36 ~ 59% Acrylic Acid Monomer mixtures, under 0.6 ~ 4% initiator effect and 40 ~ 60% mixed solvent existence conditions, react and within 3-10 hour, aggregate into carboxylic acrylic resin performed polymer, each composition press percent mass relation participate in reaction, and in this step each composition mass percent and be 100%;
(3) at reflux temperature T
3under, by 10 ~ 15% alkali formula copper organic acid/zinc small molecule monomers and 85 ~ 90% acrylic resin performed polymers, reacting 5-15 hour obtained number-average molecular weight is in the presence of solvent that the vinylformic acid copper/zinc of 10,000-4 ten thousand is from polishing antifouling resin, each composition press percent mass relation participate in reaction, and in this step each composition mass percent and be 100%.
2. vinylformic acid copper/zinc as claimed in claim 1 is from the synthetic method of polishing antifouling resin, it is characterized in that: the organic acid in described step (1) is sylvic acid, hydroabietic acid, indolic acid, naphthenic acid or containing the one in benzene organic acid.
3. vinylformic acid copper/zinc as claimed in claim 1 is from the synthetic method of polishing antifouling resin, it is characterized in that: the solvent in described step (1) and step (3) is respectively the one in dimethylbenzene, propylene glycol monomethyl ether, propyl carbinol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, 200# solvent oil, methyl-2-pyrrolidone, butylacetate; And the mixed solvent in described step (2) is at least one in dimethylbenzene, propylene glycol monomethyl ether, propyl carbinol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene Glycol Dimethyl Ether, 200# solvent oil, methyl-2-pyrrolidone, butylacetate.
4. vinylformic acid copper/zinc as claimed in claim 1 is from the synthetic method of polishing antifouling resin, it is characterized in that: described Acrylic Acid Monomer comprises basic monomer and selects monomer, wherein basic monomer comprises vinylformic acid, ethyl propenoate and n-butyl acrylate, and selects monomer to be one in methyl methacrylate, methoxyethyl acrylate, cyclohexyl acrylate, β-dimethyl-aminoethylmethacrylate or at least one.
5. vinylformic acid copper/zinc as claimed in claim 1 is from the synthetic method of polishing antifouling resin, it is characterized in that: described initiator is azo-initiator.
6. vinylformic acid copper/zinc as claimed in claim 1 is from the synthetic method of polishing antifouling resin, it is characterized in that: described T
1be 80 ~ 120 DEG C, described T
2be 100 ~ 120 DEG C, described T
3it is 60 ~ 80 DEG C.
7. the vinylformic acid copper/zinc as described in as arbitrary in claim 1 ~ 6, from the synthetic method of polishing antifouling resin, is characterized in that: in described step (1), organic acid is phenylformic acid; Solvent in described step (1) is propylene glycol monomethyl ether, and the mixed solvent in described step (2) is propyl carbinol and xylene mixture solvent, and the solvent in described step (3) is dimethylbenzene; Described azo-initiator is Diisopropyl azodicarboxylate.
8. vinylformic acid copper/zinc as claimed in claim 7 is from the synthetic method of polishing antifouling resin, it is characterized in that: in described Acrylic Acid Monomer mixture, the ratio of vinylformic acid, ethyl propenoate, butyl acrylate and selection monomer is: 5 ~ 15:60 ~ 90:10 ~ 30:20 ~ 45.
9. vinylformic acid copper/zinc as claimed in claim 7 is from the synthetic method of polishing antifouling resin, it is characterized in that: in described mixed solvent, the ratio of propyl carbinol and dimethylbenzene is: 1:3 ~ 6.
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|---|---|---|---|
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| CN201310717620.2A CN104725551A (en) | 2013-12-23 | 2013-12-23 | Synthetic method of copper/zinc acrylate self-polishing antifouling resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880996A (en) * | 2021-10-27 | 2022-01-04 | 大连理工大学 | Multifunctional marine antifouling coating resin and preparation method thereof |
| CN117701090A (en) * | 2023-12-14 | 2024-03-15 | 威海佳美化工有限公司 | Long-acting tin-free self-polishing antifouling paint and preparation method thereof |
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| 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 |
| CN103012664A (en) * | 2012-12-14 | 2013-04-03 | 上海涂料有限公司技术中心 | Method for preparing copper (zinc) acrylate resin |
| CN103289007A (en) * | 2013-04-12 | 2013-09-11 | 中国科学院烟台海岸带研究所 | Improved preparation method for zinc/copper acrylate resin |
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Patent Citations (4)
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| CN1544488A (en) * | 2003-11-10 | 2004-11-10 | 中国海洋大学 | Method for preparation of zinc or copper containing acrylic acid resin |
| 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 |
| CN103012664A (en) * | 2012-12-14 | 2013-04-03 | 上海涂料有限公司技术中心 | Method for preparing copper (zinc) acrylate resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880996A (en) * | 2021-10-27 | 2022-01-04 | 大连理工大学 | Multifunctional marine antifouling coating resin and preparation method thereof |
| CN113880996B (en) * | 2021-10-27 | 2024-02-13 | 大连理工大学 | Multifunctional marine antifouling paint resin and preparation method thereof |
| CN117701090A (en) * | 2023-12-14 | 2024-03-15 | 威海佳美化工有限公司 | Long-acting tin-free self-polishing antifouling paint and preparation method thereof |
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