CN105399903A - Biodegradable macromolecule antifouling composition as well as preparation method and application thereof - Google Patents
Biodegradable macromolecule antifouling composition as well as preparation method and application thereof Download PDFInfo
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- CN105399903A CN105399903A CN201510735861.9A CN201510735861A CN105399903A CN 105399903 A CN105399903 A CN 105399903A CN 201510735861 A CN201510735861 A CN 201510735861A CN 105399903 A CN105399903 A CN 105399903A
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- control agent
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- stain control
- antifouling
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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Abstract
The invention belongs to the technical field of marine antifouling coatings, and discloses a biodegradable macromolecule antifouling composition as well as a preparation method and application thereof. The biodegradable macromolecule antifouling composition is prepared from a cyclic ester monomer, a double-bond antifouling monomer, an initiator and an organic solvent. The biodegradable macromolecule antifouling composition disclosed by the invention is good in environmental friendliness, high in antifouling reagent load rate, good in controllable release property, good in solubility in an ordinary ship coating solvent, simple in synthesis process, relatively low in cost, applicable to industrial production, and good in application prospect in the field of preparation of marine antifouling coatings.
Description
Technical field
The invention belongs to marine antifouling coating technical field, relate to a kind of marine antifoulant, particularly relate to a kind of biodegradable macromole stain control agent and preparation method thereof and application.
Background technology
Marime fouling (MarineBiofouling) refers to the biofouling that marine microorganism and animals and plants are formed at hull or the growth of maritime facilities surface adsorption, and it brings many disadvantageous effects to the exploration of ocean shipping and oceanic resources, exploitation, utilization.Application antifouling paint is current most convenient, effective and economic method.In fact, from the development of current anti-fouling material, adopt the anti-pollution measure of stain control agent that essence can not occur and change, but have toxic action to settled organism due to conventional antifouling agents, cause expendable damage, and pollute the environment, destroy marine ecology balance.Therefore, nontoxic environmental friendliness stain control agent is used to be the important directions of future development.
Although current many environmental friendliness stain control agents can reach validity, broad spectrum and hypotoxicity, mostly can not be applied because antifouling phase effect is too short.Its main restricting factor needs to solve the controllable release of stain control agent in macromolecule resin.Existing stain control agent mostly with small molecules form physical mixed in macromolecule resin, stain control agent is caused to spread to coatingsurface owing to being separated, make stain control agent there is burst release phenomenon at the release initial stage, discharge fast with the amount far exceeding effective concentration, cause stain control agent luxus consumption at short notice; And to the release later stage, because the stain control agent concentration in coating reduces, cause the burst size of stain control agent can not meet the concentration suppressing biodeterioration needs." low after front height " phenomenon in this stain control agent dispose procedure, makes stain control agent not to be utilized effectively, and substantially reduces effect of antifouling phase.In fact, the Co ntrolled release of stain control agent is an important channel of improving environmental friendliness stain control agent utilization ratio and effect of antifouling phase.Under the prerequisite reaching anti-fouling effect, stain control agent is optimal state with constant speed, minimum release, to ecological, economy is all very useful.
Summary of the invention
In order to overcome the deficiency of current material and technology, the object of the present invention is to provide a kind of biodegradable macromole stain control agent.Macromole stain control agent of the present invention is prepared by hydridization copolymerization or radical micellar copolymerization by cyclic ester shape monomer and the antifouling monomer of double bond class, the random copolymers that its structure is made up of polyester segment and the antifouling unit of vinyl.In antifouling paint, stain control agent of the present invention can make it not easily spread loss by chemical bonds in the polymer; Simultaneously it again can by the fracture of ester bond in main (side) chain slow releasing.Under ocean environment, the release of stain control agent continous-stable by the degraded along with polymkeric substance, thus while raising stain control agent and macromolecule resin consistency, realize the slow/controlled release of stain control agent.Particularly, this Degradation does not rely on the speed of a ship or plane, not by the impact of time in port, can improve the utilization ratio of stain control agent.In addition, introduce stain control agent molecule in the polyester, while imparting polymkeric substance didirtresistance, its crystallinity, parent/hydrophobicity can also be improved, thus be expected to carry out Effective Regulation to its degradation speed and mechanical property.Macromole stain control agent of the present invention has the feature of environmental friendliness, high stain control agent load factor and controllable release, can meet the application needs of marine anti-pollution.
Another object of the present invention is the preparation method providing above-mentioned biodegradable macromole stain control agent.
Another object of the present invention is the application providing above-mentioned biodegradable macromole stain control agent.The application of described biodegradable macromole stain control agent in marine antifouling coating.
Object of the present invention is achieved through the following technical solutions:
A kind of biodegradable macromole stain control agent, is prepared from by cyclic ester shape monomer, the antifouling monomer of double bond class, initiator and organic solvent constituent.Described cyclic ester shape monomer and the antifouling monomer mass proportioning of double bond class are: (1:99) ~ (80:20); The consumption of described initiator is 0.01 ~ 10% of monomer total mass.The volume ratio of monomer total mass and organic solvent is 100g:(10-1000mL).
Described cyclic monomer is rac-Lactide, glycollide, 6-caprolactone, 2-methyl-epsilon-caprolactone, the chloro-6-caprolactone of 2-, gamma-butyrolactone, δ-valerolactone, γ-valerolactone, 2-methylene radical-1, one or more in 3-Dioxepane, NSC 11801, propylene carbonate, TMC, 2,2-dimethyltrimethylene cyclic carbonate esters, dimethylamino TMC, 2-ethyl-2-oxazoline, 2-methyl-2-oxazoline, oxyethane, propylene oxide, epoxy chloropropane and γ-glycidyl ether oxygen propyl trimethoxy silicane;
The antifouling monomer of described double bond class is more than one in acrylic ester monomer or 1-vinyl imidazole, described acrylic ester monomer be preferably in N-acryloyloxymethyl isothiazolinone, 3-(acryloyloxymethyl) substituted indole or 3-(N-methyl-N-acryloyl-oxy Ethylaminomethyl) substituted indole more than one.Described acrylic ester monomer at 0-60 DEG C, reacts 0.5-48h by antifouling Summing Factor acrylate chloride to prepare, and the described antifouling factor is methylol/ethylisothiazol quinoline ketone, 3-indole-alcohol or 3-(N-methyl-N-hydroxyethylamino methyl) substituted indole.
Described initiator is low mass molecule alcohol, low molecule amine, mercaptan, more than one in phosphonitrile, phosphonitrile salt (comprising inorganic phosphonitrile salt and organic phosphonitrile salt), phosphine oxide, Diisopropyl azodicarboxylate or benzoyl peroxide.
Described low molecule amine is at least one in the fatty amine of carbon atoms 2 ~ 10.Described low mass molecule alcohol is at least one in the fatty alcohol of carbon atoms 2 ~ 10.
Described organic solvent is more than one in tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene, dimethylbenzene, acetone and propyl carbinol.
The preparation method of described biodegradable macromole stain control agent is:
Under protection of inert gas, cyclic ester shape monomer and the antifouling monomer of double bond class are added in organic solvent, then adds initiator, react in 25 ~ 150 DEG C, precipitation, dry, obtain biodegradable macromole stain control agent.
The described reaction times is 0.5-48h; The precipitation agent of described precipitation is methyl alcohol, water or normal hexane, and described sedimentation time is 4 ~ 24h.The temperature of described drying is 25 ~ 120 DEG C, and time of drying is 6 ~ 48h.
The application of described biodegradable macromole stain control agent in marine antifouling coating.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention is by being incorporated into antifouling functional group in degradation property polyester, prepares biodegradable macromole stain control agent.Because stain control agent makes it not easily spread loss in the polymer by chemical bonds, simultaneously it again can the release of continous-stable along with the degraded of polymkeric substance, thus stain control agent is efficiently utilized.
(2) introduce stain control agent molecule in the polyester, while imparting polymkeric substance didirtresistance, its crystallinity, parent/hydrophobicity can also be improved, thus be expected to carry out Effective Regulation to its degradation speed and mechanical property.
(3) the macromole stain control agent that the present invention obtains has environmental friendliness, high stain control agent load factor and controllable release.
(4) solvability of macromole stain control agent of the present invention in marine finish Conventional solvents is good, and synthesis technique is simple, and cost is lower, is applicable to suitability for industrialized production, and this material has good application prospect preparing marine anti-pollution coatings art.
Embodiment
Describe the present invention in detail below by specific embodiment, but the present invention is not limited only to following examples.
Embodiment 1
Under the condition of rare gas element, add 10g 6-caprolactone, 90gN-acryloyloxymethyl isothiazolinone, 0.1g methyl alcohol and 100mL dimethylbenzene to 250mL with in the there-necked flask of agitator and thermometer, add 100 μ L phosphonitrile (t-BuP
4) normal hexane solution (0.8mol/L), react 6h under 25 DEG C of conditions after, in methyl alcohol, precipitate 12h, in 60 DEG C of vacuum-drying 24h, obtain biodegradable macromole stain control agent, its productive rate is 95%, and the number-average molecular weight of stain control agent is 15000g/mol.
By 3g macromole stain control agent and 10g acrylic resin, 6g rosin, 30g Red copper oxide, 7g zinc oxide and 4ml dimethylbenzene are uniformly mixed, and make marine antifouling coating.According to GB/T5370-2007 " antifouling varnish model shallow sea soak test method ", shallow sea panel experiment (2014.4-2015.4) has been carried out in Xiamen sea area, within 12 months, without marine organism growth, illustrate that the antifouling paint prepared based on this stain control agent has good anti-fouling effect.
Embodiment 2
Under the condition of rare gas element, 5g2-methylene radical-1 is added in 250mL there-necked flask, 3-Dioxepane, 95g3-(acryloyloxymethyl) substituted indole, 0.5g Diisopropyl azodicarboxylate and 100mL toluene, 70 DEG C of reaction 12h, reaction terminates rear normal hexane and precipitates 4h, filters, in 60 DEG C of vacuum-drying 12h, productive rate is 90%, and detecting its number-average molecular weight by gel permeation chromatograph is 1.3 × 10
4g/mol.
By 5g macromole stain control agent and 16g urethane resin, 20g Red copper oxide, 12g zinc oxide and 5g dimethylbenzene are uniformly mixed, and make marine antifouling coating.By the mode of brushing, film forming on epoxy resin board, carried out shallow sea panel experiment (2014.4-2015.4) in Xiamen sea area, 12 months without marine organism growth.
Embodiment 3
Under the condition of rare gas element, 50g2-methyl-epsilon-caprolactone is added in 100mL there-necked flask, 50g3-(N-methyl-N-acryloyl-oxy Ethylaminomethyl) substituted indole, 0.1g benzoyl peroxide and the mixing of 100mL dimethylbenzene, 70 DEG C of reaction 24h, reaction terminates rear water precipitation 24 hours, filter, 60 DEG C of vacuum-drying 12h, productive rate is 80%, and detecting its number-average molecular weight by gel permeation chromatograph is 2.3 × 10
4g/mol.
Embodiment 4
Under the condition of rare gas element, add the chloro-6-caprolactone of 80g2-, 20g4-vinyl pyridine in 250mL there-necked flask, 0.1g ethanol and 100mL toluene, mixing, adds the t-BuP of 7 μ L
4hexane solution (0.8mol/L), 25 DEG C of reaction 12h, then precipitate 12h, filter, 60 DEG C of vacuum-drying 24h, productive rate 90% in methyl alcohol.
Embodiment 5
Under the condition of rare gas element, 50g2-methylene radical-1 is added in 250mL there-necked flask, 3-Dioxepane, 50g1-vinyl imidazole, 0.5g Diisopropyl azodicarboxylate and 100mL xylene solution, 70 DEG C of reaction 24h, reaction terminates rear normal hexane and precipitates 12h, filters, 60 DEG C of vacuum-drying 12h, productive rate is 94%, and detecting its number-average molecular weight by gel permeation chromatograph is 1.0 × 10
4g/mol.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a biodegradable macromole stain control agent, is characterized in that: be prepared from by cyclic ester shape monomer, the antifouling monomer of double bond class, initiator and organic solvent constituent.
2. biodegradable macromole stain control agent according to claim 1, it is characterized in that: described cyclic monomer is rac-Lactide, glycollide, 6-caprolactone, 2-methyl-epsilon-caprolactone, the chloro-6-caprolactone of 2-, gamma-butyrolactone, δ-valerolactone, γ-valerolactone, 2-methylene radical-1, 3-Dioxepane, NSC 11801, propylene carbonate, TMC, 2, 2-dimethyltrimethylene cyclic carbonate ester, dimethylamino TMC, 2-ethyl-2-oxazoline, 2-methyl-2-oxazoline, oxyethane, propylene oxide, one or more in epoxy chloropropane and γ-glycidyl ether oxygen propyl trimethoxy silicane.
3. biodegradable macromole stain control agent according to claim 1, is characterized in that: the antifouling monomer of described double bond class is more than one in acrylic ester monomer or 1-vinyl imidazole;
Described initiator is low mass molecule alcohol, low molecule amine, mercaptan, more than one in phosphonitrile, phosphonitrile salt, phosphine oxide, Diisopropyl azodicarboxylate or benzoyl peroxide.
4. biodegradable macromole stain control agent according to claim 3, is characterized in that: described acrylic ester monomer is more than one in N-acryloyloxymethyl isothiazolinone, 3-(acryloyloxymethyl) substituted indole or 3-(N-methyl-N-acryloyl-oxy Ethylaminomethyl) substituted indole;
Described low molecule amine is at least one in the fatty amine of carbon atoms 2 ~ 10; Described low mass molecule alcohol is at least one in the fatty alcohol of carbon atoms 2 ~ 10.
5. biodegradable macromole stain control agent according to claim 4, it is characterized in that: described acrylic ester monomer is prepared by antifouling Summing Factor acrylate chloride reaction, and the described antifouling factor is methylol/ethylisothiazol quinoline ketone, 3-indole-alcohol or 3-(N-methyl-N-hydroxyethylamino methyl) substituted indole.
6. biodegradable macromole stain control agent according to claim 1, is characterized in that: described cyclic ester shape monomer and the antifouling monomer mass proportioning of double bond class are: (1:99) ~ (80:20); The consumption of described initiator is 0.01 ~ 10% of monomer total mass;
The volume ratio of monomer total mass and organic solvent is 100g:(10 ~ 1000mL).
7. biodegradable macromole stain control agent according to claim 1, is characterized in that: described organic solvent is more than one in tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene, dimethylbenzene, acetone and propyl carbinol.
8. the preparation method of biodegradable macromole stain control agent according to any one of claim 1 ~ 7, is characterized in that: concrete steps are:
Under protection of inert gas, cyclic ester shape monomer and the antifouling monomer of double bond class are added in organic solvent, then adds initiator, react in 25 ~ 150 DEG C, precipitation, dry, obtain biodegradable macromole stain control agent.
9. the preparation method of biodegradable macromole stain control agent according to claim 8, is characterized in that: the described reaction times is 0.5 ~ 48h; The precipitation agent of described precipitation is methyl alcohol, water or normal hexane, and described sedimentation time is 4 ~ 24h;
The temperature of described drying is 25 ~ 120 DEG C, and time of drying is 6 ~ 48h.
10. the application of biodegradable macromole stain control agent in marine antifouling coating according to any one of claim 1 ~ 7.
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| CN201510735861.9A CN105399903B (en) | 2015-10-30 | 2015-10-30 | A kind of biodegradable macromolecular anti-fouling agent and the preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110711496A (en) * | 2019-10-09 | 2020-01-21 | 东莞东阳光科研发有限公司 | Anti-biological-pollution porous membrane and preparation method and application thereof |
| CN114702627A (en) * | 2022-04-27 | 2022-07-05 | 南方海洋科学与工程广东省实验室(湛江) | Degradable polymer and preparation method and application thereof |
| CN115594851A (en) * | 2022-10-31 | 2023-01-13 | 华南理工大学（Cn） | Reactive amphiphilic additive and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110711496A (en) * | 2019-10-09 | 2020-01-21 | 东莞东阳光科研发有限公司 | Anti-biological-pollution porous membrane and preparation method and application thereof |
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| CN114702627A (en) * | 2022-04-27 | 2022-07-05 | 南方海洋科学与工程广东省实验室(湛江) | Degradable polymer and preparation method and application thereof |
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| CN115594851A (en) * | 2022-10-31 | 2023-01-13 | 华南理工大学（Cn） | Reactive amphiphilic additive and preparation method and application thereof |
| CN115594851B (en) * | 2022-10-31 | 2024-02-13 | 华南理工大学 | Reactive amphiphilic additive and preparation method and application thereof |
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