CN105399903B - A kind of biodegradable macromolecular anti-fouling agent and the preparation method and application thereof - Google Patents
A kind of biodegradable macromolecular anti-fouling agent and the preparation method and application thereof Download PDFInfo
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- CN105399903B CN105399903B CN201510735861.9A CN201510735861A CN105399903B CN 105399903 B CN105399903 B CN 105399903B CN 201510735861 A CN201510735861 A CN 201510735861A CN 105399903 B CN105399903 B CN 105399903B
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- fouling agent
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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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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to marine antifouling coating technical field, a kind of biodegradable macromolecular anti-fouling agent and the preparation method and application thereof is disclosed.The macromolecular anti-fouling agent is prepared by cyclic ester shape monomer, the antifouling monomer of double bond class, initiator and organic solvent constituent.The macromolecular anti-fouling agent of the present invention has environmental-friendly, high anti-fouling agent load factor and controlled release；And the dissolubility in marine paint Conventional solvents is good, and synthesis technology is simple, and cost is relatively low, and industrialized production, the material is suitble to prepare marine anti-pollution coatings art with good application prospect.
Description
Technical field
The invention belongs to marine antifouling coating technical fields, are related to a kind of marine antifoulant, can be given birth to more particularly to one kind
The macromolecular anti-fouling agent and the preparation method and application thereof of object degradation.
Background technology
Marime fouling (Marine Biofouling) refers to marine microorganism and animals and plants on hull or marine facility surface
The biofouling that Absorption Growth is formed, it to ocean shipping and the exploration of marine resources, exploitation, using bringing many adverse effects.
Application antifouling paint is current most convenient, effective and economic method.In fact, from the point of view of the development of current anti-fouling material, adopt
It will not occur to sexually revise at all with the anti-pollution measure of anti-fouling agent, but since conventional antifouling agents have toxic action to aufwuch, make
It at expendable damage, and pollutes the environment, destroys marine ecology balance.Therefore, it is using nontoxic environmental-friendly anti-fouling agent
The important directions of future development.
Although current many environmental-friendly anti-fouling agents can reach validity, broad spectrum activity and hypotoxicity, mostly due to anti-
Dirty phase effect is too short and cannot be applied.Its main restricting factor is to need to solve realizing controlled-release of the anti-fouling agent in macromolecule resin
It puts.Existing anti-fouling agent in physical mixed to macromolecule resin, causes anti-fouling agent to painting mostly in the form of small molecule due to being separated
Layer surface is spread so that anti-fouling agent is caused with the amount quick release far more than effective concentration there are burst release phenomenons release initial stage
The excessive consumption of anti-fouling agent in a short time；And to the release later stage, because the antifouling agent concentration in coating reduces, lead to anti-fouling agent
Burst size cannot meet the concentration for inhibiting biodeterioration to need." the front is high and the back is low " phenomenon during this anti-fouling agent release, makes
Obtaining anti-fouling agent cannot be utilized effectively, and substantially reduce antifouling phase effect.In fact, the control release of anti-fouling agent is to improve environment
One important channel of friendly anti-fouling agent utilization rate and effect of antifouling phase.Under the premise of reaching anti-fouling effect, anti-fouling agent is with constant
Speed, minimum release are optimal states, all highly beneficial to ecology, economy.
Invention content
In order to overcome the shortcomings of current material and technology, the purpose of the present invention is to provide a kind of biodegradable to divide greatly
Sub- anti-fouling agent.The macromolecular anti-fouling agent of the present invention is by cyclic ester shape monomer and the antifouling monomer of double bond class by hydridization copolymerization or freely
Prepared by base ring-opening polymerisation, the random copolymer that structure is made of polyester segment and the antifouling unit of vinyl.In antifouling paint
In, anti-fouling agent of the invention can make it be not easy diffusion and be lost in the polymer by chemical bonds；It again can be with simultaneously
The slow release by fracture of ester bond in master (side) chain.Under marine environment, anti-fouling agent is by the company with the degradation of polymer
Continue stable release, to while improving anti-fouling agent with macromolecule resin compatibility, realize the slow/controlled release of anti-fouling agent.It is special
It is not that this degradation is influenced independent of the speed of a ship or plane, not by the layover time, the utilization rate of anti-fouling agent can be improved.In addition,
Antifouling agent molecule is introduced in the polyester, while assigning polymer soil resistance, can also improve its crystallinity, parent/hydrophobicity,
To be expected to carry out Effective Regulation to its degradation speed and mechanical property.The present invention macromolecular anti-fouling agent have it is environmental-friendly,
The characteristics of high anti-fouling agent load factor and controlled release, disclosure satisfy that marine anti-pollution applies needs.
Another object of the present invention is to provide the preparation method of above-mentioned biodegradable macromolecular anti-fouling agent.
It is still another object of the present invention to provide the applications of above-mentioned biodegradable macromolecular anti-fouling agent.It is described can biology
Application of the macromolecular anti-fouling agent of degradation in marine antifouling coating.
The purpose of the present invention is achieved through the following technical solutions：
A kind of biodegradable macromolecular anti-fouling agent by cyclic ester shape monomer, the antifouling monomer of double bond class, initiator and has
Solvent component is prepared.The cyclic ester shape monomer and the antifouling monomer mass proportioning of double bond class are：(1：99)~(80：20)；
The dosage of the initiator is the 0.01~10% of monomer gross mass.Monomer gross mass and the volume ratio of organic solvent are 100g:
(10-1000mL)。
The cyclic monomer be lactide, glycolide, 6-caprolactone, 2- methyl-epsilon-caprolactones, the chloro- 6-caprolactones of 2-,
Gamma-butyrolacton, δ-valerolactone, gamma-valerolactone, 2- methylene -1,3- Dioxepanes, ethylene carbonate, propene carbonate,
Trimethylene Carbonate, 2,2- dimethyltrimethylenes cyclic carbonate ester, dimethylamino Trimethylene Carbonate, 2- ethyls-
2- oxazolines, 2- methyl -2- oxazolines, ethylene oxide, propylene oxide, epoxychloropropane and γ-glycidyl ether oxygen propyl three
It is one or more in methoxy silane；
The antifouling monomer of double bond class is one or more of acrylic ester monomer or 1- vinyl imidazoles, the propylene
Esters of gallic acid monomer is preferably N- acryloyloxymethyls isothiazolinone, 3- (acryloyloxymethyl) substituted indoles or 3- (N-
One or more of methyl-N- acryloyl-oxies Ethylaminomethyl) substituted indole.The acrylic ester monomer be by it is antifouling because
Son and acryloyl chloride react 0.5-48h at 0-60 DEG C and are prepared, and the antifouling factor is methylol/ethylisothiazol quinoline
Ketone, 3- indole-alcohols or 3- (N- methyl-N- hydroxyethylaminos methyl) substituted indole.
The initiator is low mass molecule alcohol, low molecule amine, mercaptan, phosphonitrile, phosphonitrile salt (including inorganic phosphonitrile salt and organophosphor
Nitrile salt), phosphine oxide, one or more of azodiisobutyronitrile or benzoyl peroxide.
The low molecule amine is at least one of the aliphatic amine of carbon atoms 2~10.The low mass molecule alcohol is carbon containing
At least one of the aliphatic alcohol of atom 2~10.
The organic solvent is tetrahydrofuran, dimethylformamide, dimethylacetylamide, toluene, dimethylbenzene, acetone and just
One or more of butanol.
The preparation method of the biodegradable macromolecular anti-fouling agent is：
Under inert gas protection, cyclic ester shape monomer and the antifouling monomer of double bond class are added in organic solvent, are then added
Initiator is reacted in 25~150 DEG C, is precipitated, dry, obtains biodegradable macromolecular anti-fouling agent.
The reaction time is 0.5-48h；The precipitating reagent of the precipitation is methanol, water or n-hexane, the sedimentation time
For 4~for 24 hours.The temperature of the drying is 25~120 DEG C, and drying time is 6~48h.
Application of the biodegradable macromolecular anti-fouling agent in marine antifouling coating.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) it is antifouling to prepare biodegradable macromolecular by the way that antifouling functional group to be introduced into degradability polyester by the present invention
Agent.Since anti-fouling agent is to make it be not easy diffusion and be lost in the polymer by chemical bonds, while it again can be with poly-
The release for closing the degradation of object and continuous-stable, to make anti-fouling agent be efficiently utilized.
(2) antifouling agent molecule is introduced in the polyester, while assigning polymer soil resistance, can also improve its crystallization
Property, parent/hydrophobicity, to be expected to carry out Effective Regulation to its degradation speed and mechanical property.
(3) the macromolecular anti-fouling agent that the present invention obtains has environmental-friendly, high anti-fouling agent load factor and controlled release.
(4) dissolubility of macromolecular anti-fouling agent of the invention in marine paint Conventional solvents is good, and synthesis technology is simple, at
This is relatively low, and industrialized production, the material is suitble to prepare marine anti-pollution coatings art with good application prospect.
Specific implementation mode
Below by specific embodiment, the present invention will be described in detail, but the present invention is not limited only to following embodiment.
Embodiment 1
Under conditions of inert gas, 10g ε-are added into there-necked flasks of the 250mL with blender and thermometer in oneself
100 μ L phosphonitriles (t-BuP are added in ester, 90g N- acryloyloxymethyls isothiazolinone, 0.1g methanol and 100mL dimethylbenzene4)
Normal hexane solution (0.8mol/L), under the conditions of 25 DEG C react 6h after, precipitate 12h in methyl alcohol, in 60 DEG C vacuum drying
For 24 hours, biodegradable macromolecular anti-fouling agent is obtained, the number-average molecular weight of yield 95%, anti-fouling agent is 15000g/mol.
By 3g macromoleculars anti-fouling agent and 10g acrylic resins, 6g rosin, 30g cuprous oxide, 7g zinc oxide and 4ml bis-
Toluene is stirred, and marine antifouling coating is made.According to GB/T5370-2007《Anti-fouling paint model shallow sea soak test method》,
Shallow sea panel experiment (2014.4-2015.4) has been carried out in Xiamen sea area, without marine organism growth, has been illustrated anti-based on this within 12 months
Antifouling paint prepared by dirty agent has good anti-fouling effect.
Embodiment 2
Under conditions of inert gas, in 250mL there-necked flasks be added 5g 2- methylene -1,3- Dioxepanes,
95g 3- (acryloyloxymethyl) substituted indole, 0.5g azodiisobutyronitriles and 100mL toluene, 70 DEG C of reaction 12h, reaction knot
Shu Houyong n-hexanes precipitate 4h, and filtering is dried in vacuo 12h in 60 DEG C, and yield 90% detects it by gel permeation chromatograph
Number-average molecular weight is 1.3 × 104g/mol。
By 5g macromoleculars anti-fouling agent and 16g polyurethane resins, 20g cuprous oxide, 12g zinc oxide and 5g dimethylbenzene stir
Mixing, is made marine antifouling coating.It by way of brushing, forms a film on epoxy resin board, shallow sea has been carried out in Xiamen sea area
Panel experiment (2014.4-2015.4), 12 months without marine organism growth.
Embodiment 3
Under conditions of inert gas, 50g 2- methyl-epsilon-caprolactones, 50g3- (N- first are added into 100mL there-necked flasks
Base-N- acryloyl-oxies Ethylaminomethyl) substituted indole, 0.1g benzoyl peroxides and 100mL dimethylbenzene mixings, 70 DEG C of reactions
For 24 hours, water sedimentation 24 hours is used after reaction, and filtering, 60 DEG C are dried in vacuo 12h, and yield 80% passes through gel permeation chromatography
It is 2.3 × 10 that instrument, which detects its number-average molecular weight,4g/mol。
Embodiment 4
Under conditions of inert gas, the chloro- 6-caprolactones of 80g 2-, 20g 4- vinyl are added into 250mL there-necked flasks
The t-BuP of 7 μ L is added in pyridine, 0.1g ethyl alcohol and 100mL toluene, mixing4Hexane solution (0.8mol/L), 25 DEG C are anti-
12h is answered, then precipitates 12h in methyl alcohol, is filtered, 60 DEG C are dried in vacuo for 24 hours, yield 90%.
Embodiment 5
Under conditions of inert gas, 50g 2- methylene -1,3- Dioxepanes are added into 250mL there-necked flasks,
50g 1- vinyl imidazoles, 0.5g azodiisobutyronitriles and 100mL xylene solutions, 70 DEG C of reactions for 24 hours, are used just after reaction
Hexane precipitation 12h, filtering, 60 DEG C of vacuum drying 12h, yield 94% detect it by gel permeation chromatograph and count equal molecule
Amount is 1.0 × 104g/mol。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (7)
1. a kind of biodegradable macromolecular anti-fouling agent, it is characterised in that：By cyclic monomer, the antifouling monomer of double bond class, initiation
Agent and organic solvent constituent are prepared；
The cyclic monomer is lactide, glycolide, 6-caprolactone, 2- methyl-epsilon-caprolactones, the chloro- 6-caprolactones of 2-, γ-fourth
Lactone, δ-valerolactone, gamma-valerolactone, 2- methylene -1,3- Dioxepanes, ethylene carbonate, propene carbonate, Sanya
Methyl cyclic carbonate ester, 2,2- dimethyltrimethylenes cyclic carbonate ester, dimethylamino Trimethylene Carbonate, 2- ethyls -2- are disliked
Oxazoline, 2- methyl -2- oxazolines, ethylene oxide, propylene oxide, epoxychloropropane and γ-glycidyl ether oxygen propyl trimethoxy
It is one or more in base silane；
The antifouling monomer of double bond class is one or more of acrylic ester monomer or 1- vinyl imidazoles；
The initiator is low mass molecule alcohol, low molecule amine, mercaptan, phosphonitrile, phosphonitrile salt, phosphine oxide, azodiisobutyronitrile or mistake
One or more of Benzoyl Oxide；
The acrylic ester monomer is N- acryloyloxymethyls isothiazolinone, 3- (acryloyloxymethyl) substituted indole
Or one or more of 3- (N- methyl-N- acryloyl-oxies Ethylaminomethyl) substituted indole；
The low molecule amine is at least one of the aliphatic amine of carbon atoms 2~10；The low mass molecule alcohol is carbon atoms 2
At least one of~10 aliphatic alcohol.
2. biodegradable macromolecular anti-fouling agent according to claim 1, it is characterised in that：The acrylic ester monomer
It is to be prepared by the antifouling factor and acryloyl chloride reaction, the antifouling factor is hydroxymethyl isothiazolinone, 3- indoles first
Alcohol or 3- (N- methyl-N- hydroxyethylaminos methyl) substituted indole.
3. biodegradable macromolecular anti-fouling agent according to claim 1, it is characterised in that：The cyclic monomer and double bond
The antifouling monomer mass of class, which matches, is：(1：99)~(80：20)；The dosage of the initiator be monomer gross mass 0.01~
10%；
Monomer gross mass and the volume ratio of organic solvent are 100g:(10~1000mL).
4. biodegradable macromolecular anti-fouling agent according to claim 1, it is characterised in that：The organic solvent is tetrahydrochysene
One or more of furans, dimethylformamide, dimethylacetylamide, toluene, dimethylbenzene, acetone and n-butanol.
5. according to the preparation method of any one of Claims 1 to 4 biodegradable macromolecular anti-fouling agent, feature exists
In：The specific steps are：
Under inert gas protection, cyclic monomer and the antifouling monomer of double bond class are added in organic solvent, initiator are then added,
It is reacted, is precipitated in 25~150 DEG C, it is dry, obtain biodegradable macromolecular anti-fouling agent.
6. the preparation method of biodegradable macromolecular anti-fouling agent according to claim 5, it is characterised in that：The reaction
Time is 0.5~48h；The precipitating reagent of the precipitation be methanol, water or n-hexane, the sedimentation time be 4~for 24 hours；
The temperature of the drying is 25~120 DEG C, and drying time is 6~48h.
7. according to any one of Claims 1 to 4 biodegradable macromolecular anti-fouling agent answering in marine antifouling coating
With.
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| CN110711496B (en) * | 2019-10-09 | 2022-01-14 | 东莞东阳光科研发有限公司 | Anti-biological-pollution porous membrane and preparation method and application thereof |
| CN114702627B (en) * | 2022-04-27 | 2023-07-21 | 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 |
| 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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| CN102977332A (en) * | 2012-11-30 | 2013-03-20 | 华南理工大学 | Autocrine biomimetic anti-fouling material and application thereof |
| CN103012243A (en) * | 2012-12-06 | 2013-04-03 | 青岛大学 | Acrylic ester functional monomer containing donaxine structure and preparation method thereof |
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| CN103044632A (en) * | 2012-12-14 | 2013-04-17 | 华南理工大学 | Hybrid hydrolysis resin, and preparation method and application thereof |
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| WO2011129015A1 (en) * | 2010-04-16 | 2011-10-20 | 株式会社ネオス | Imparting agent for antifouling properties |
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| CN102977332A (en) * | 2012-11-30 | 2013-03-20 | 华南理工大学 | Autocrine biomimetic anti-fouling material and application thereof |
| CN103012243A (en) * | 2012-12-06 | 2013-04-03 | 青岛大学 | Acrylic ester functional monomer containing donaxine structure and preparation method thereof |
| CN103044351A (en) * | 2012-12-06 | 2013-04-17 | 青岛大学 | N-substituted propylene acyloxy methyl benzisothiazolinone functional monomer and preparation method thereof |
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