CN104927618B - A kind of low-surface-energy is from polishing type polyurethane marine antifouling coating and preparation method - Google Patents
A kind of low-surface-energy is from polishing type polyurethane marine antifouling coating and preparation method Download PDFInfo
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- CN104927618B CN104927618B CN201510311325.6A CN201510311325A CN104927618B CN 104927618 B CN104927618 B CN 104927618B CN 201510311325 A CN201510311325 A CN 201510311325A CN 104927618 B CN104927618 B CN 104927618B
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Abstract
The present invention provides a kind of low-surface-energy from polishing type polyurethane marine antifouling coating and preparation method thereof, use ring-opening polymerisation, the method that polycondensation reaction and hydrophobization combine, with stannous octoate as catalyst, with nano silicon as initiator, L lactic acid monomer open loop pre-polymerization is caused with groups such as a certain amount of hydroxyls contained by nano-silica surface, again by prepolymer and 4, 4 methyl diphenylene diisocyanates react, use 1, 4 butanediols are that its chain extension synthesizes crude product, crude product i.e. obtains low-surface-energy from polishing type polyurethane marine antifouling coating after hydrophobization processes.Experimentation shows, this coating Static water contact angles is 108。, there is relatively low surface energy, have well from polishing ability, degradation cycle is 6 months, and this coating also has certain antibiotic property, has a extensive future, and provides a kind of new way for solving boats and ships marine biofouling, promotes ocean development construction and national defense construction.
Description
Technical field
The invention belongs to chemistry painting industry field, be specifically related to a kind of low-surface-energy and be coated with from polishing type polyurethane marine anti-pollution
Material and preparation method thereof.
Background technology
The mankind continually develop, utilize in the process of ocean, and a difficult problem all the time is how to solve marine biofouling
This problem.Marine biofouling, refer to submergence equipment surface in the seawater by the various microorganisms living in ocean, plant
Thing, animal etc. adhere to, constantly growth and breeding, thus the biofouling formed.Human use ocean is sought by marine biofouling
Development aspect causes certain negative effect, whether sea transport, or the exploration of marine resources, exploitation all receive resistance
Hindering, such as marine biofouling can increase roughness and the ship resistance on oceanographic equipment surface, and the consumption of the fuel such as boats and ships can be big
Amount increases, and carbon dioxide discharges in a large number, thus aggravates Global Greenhouse Effect, and tellurian environment constantly deteriorates；Ocean is raw
Thing is stained and can reduce ship navigating speed, weakens the operational efficiency of naval；Marine biofouling also can block fish culture apparatus
Mesh so that fish and shrimp mortality rate aggravate；Marine biofouling can change the apparent condition of other marine facilities, ultimately results in it
Corrosion rate quickening etc..Up to now, the method preventing marine biofouling is varied, and commonly used has brush anti-fouling
Coating Method, electrolysis heavy metal method, electrolytic seawater method, conductive coat method, manually or mechanically removing method etc..And current most convenient,
Effective and most economical method is to use antifouling paint.Along with the theory of protection environment is rooted in the hearts of the people, nontoxic, efficient, environment-friendly type
Antifouling paint becomes the up-to-date guiding of marine antifouling coating undoubtedly.
Polyurethane is extensive due to character such as its solvent resistance, thermostability, compliance, resistance to water, wearability and intensity are high
It is applied in coating.The primary raw material of polyurethane is isocyanates, and its character is the most active.Isocyanates can be with hydroxy resin
In conjunction with, it is also possible to and the hydroxy combining in ground, promote the formation of hydrogen bond and other chemical bonds, thus enhance between ground
Adhesion, exactly because these performances, just make isocyanates become the primary raw material of synthesis of polyurethane, it has other thing
Advantage not available for matter, the method utilizing ring-opening polymerisation and polycondensation reaction to combine such as horse spring breeze etc. is prepared for a class main chain fall
Solving type polyurethane material, this material has the adhesion that degradation property is high and excellent, and this research has greatly facilitated marine anti-pollution
The research and development of coating, but this polyurethane material due to surface can higher and make hull navigation during be prone to defaced life
Thing adheres to, and adds ship resistance, it is impossible in real navigation, (marine anti-pollution is high for horse spring breeze, Wu Bo, Xu Wentao, Zhang Guangzhao
The development of molecular material, macromolecule circular, 2013,9,87 95.).Nano-meter SiO_22Certain activated silica hydroxyl is there is on surface
Base, this feature allows Nano-meter SiO_22Surface, show certain hydrophilic thin oil properties, condensation of easily reuniting, research find
By modified Nano-meter SiO_22There is good hydrophobicity, there is relatively low surface energy, synthesized nanometer such as Majumdar P etc.
Silicon dioxide polyurethane copolymer, owing to both are incompatible, forms well-bedded coating, and upper strata is low-surface-energy poly dimethyl
Silicone elastomer, bottom is to have high surface energy to obtain polyurethane, so solves tradition while improving mechanical property low
The problem that surface-energy material adhesion is weak, but the degradability of this copolymer is poor, i.e. more weak from polishing ability, it is stained life
Thing is longer and corrode hull surface (Majumdar P, Webster D C. Preparation in the hull surface attachment time
of siloxane-urethane coatings having spontaneously formed stable biphasic
Microtopograpical surfaces [J]. Macromolecules, 2005,38 (14): 5857-5859), Keefe
Quaternary ammonium salt, triclosan grafting silicones, amphoteric ion polymer are grafted in polydimethylsiloxaneelastomer elastomer by A J etc., system
It is stained for having suppression and reduces the anti-fouling material being stained adsorption effect, although this anti-fouling material has certain antibiotic property,
But do not possess low-surface-energy and the big critical nature of degradable two, bacteriostasis can only be played in the early section time in actual applications,
Can not be the most antibacterial, which also limits range of application (Keefe A J, Brault the N D, Jiang S of such anti-fouling material
Y. Suppressing surface reconstruction of superhydrophobic PDMS using a
superhydrophilic zwitterionic polymer[J]. Biomacromolecules, 2012, 13(5):
1683-1687.).Lactic acid (Lactioac) has another name called lactic acid, formal name used at school α-hydracrylate, is in the middle of organic acid important one
Kind.The more environmental protection of the source of polylactic acid, obtains the accreditation of people.The base stock of PLA is fermented by Semen Maydis or potato starch and prepares,
Polymer is produced again by ring-opening polymerisation or polycondensation.After the most important thing is that polylactic acid article is discarded, the biology in nature can
So that its degraded, generate carbon dioxide and water, nontoxic.So scholars all think, PLA is a kind of environmental friendliness section bar
Expecting, it returns again in the Nature after coming from the Nature, use, and this makes polylactic acid be widely applied to degradable environmental protection material
In material.
Summary of the invention
It is an object of the invention to provide a kind of low-surface-energy preparation method from polishing type polyurethane marine antifouling coating, for
Solve boats and ships marine biofouling and provide a kind of new way, promote ocean development construction and national defense construction.By ring-opening polymerisation,
Polycondensation reaction and hydrophobization operate the method combined, and successfully prepare low-surface-energy and are coated with from polishing type polyurethane marine anti-pollution
Material, the method is simple to operate, the response time is short, percent grafting is high, productivity is high.Prepared low-surface-energy is from polishing type polyurethane sea
Ocean antifouling paint can be widely applied to Ship body and spray paint the fields such as anti-marine biofouling, can be as a kind of novel environment friendly coating
Put into production.
For achieving the above object, the technical solution used in the present invention is: a kind of low-surface-energy is from polishing type polyurethane ocean
The preparation method of antifouling paint, is made up of the method comprising the following steps:
(1) take oxolane in flask, be sequentially added into nano silicon, Pfansteihl, catalyst-stannous octoate, super
Sonication 20-30 min is allowed to mix homogeneously, is stirred at reflux and is allowed to react 20-24 h i.e. under nitrogen protection at 100-120 DEG C
Obtain prepolymer (SiO2/ PLA).Described reaction equation is as follows:
(2) prepolymer is obtained intermediate pre-polymer by being dried 10-12 h at after washing 20-30 DEG C；
(3) take intermediate pre-polymer join with condensing tube and be connected with nitrogen there-necked flask reaction unit in, add four
Hydrogen furan, after making prepolymer be completely dissolved under stirring, add 4,4-methyl diphenylene diisocyanate, 60 DEG C-
React 2-4 h at 80 DEG C and obtain oligomer, be subsequently adding BDO, after mix homogeneously, temperature be increased to 90 DEG C,
Reaction 8-10 h obtains macromole line polymer；After terminating reaction, treat that temperature drops to room temperature, solution is added drop-wise to 5 ~ 8 times of bodies
Long-pending normal hexane precipitates, centrifugal filtration, duration 5-10 min, product is put into vacuum drying 10-12 in 40-50 DEG C of environment
H, obtains from polishing polyurethane coating crude product.
(4) take crude product to be dissolved in dehydrated alcohol, add deionized water/perfluor silane mixture at constant temperature 60-70 DEG C molten
Liquid, reacts 5-8 h, centrifugal 5 times, product is put into vacuum drying 10-12 h in 40-50 DEG C of environment and obtains low-surface-energy from throwing
Light polyurethane coating (SiO2/ PLA/PU).
Described nano silicon, oxolane and normal hexane need to remove water purification.
The dry water-eliminating method of described nano silicon is: takes nano silicon in beaker, is placed on baking oven
In, control temperature about 70 DEG C-80 DEG C, be dried 12 h.
The water-eliminating method of described oxolane/normal hexane is: measure the oxolane/normal hexane of 300 mL in 500 mL circles
In end flask, take 2-3 g metallic sodium and be chopped into sodium grain, add in oxolane/normal hexane, use heat collecting type heated at constant temperature magnetic force
Agitator, about 100 DEG C condensing refluxes 3-7 days, adds indicator benzophenone in good time, until solution turned blue color or purple,
The fraction of 65-68 DEG C is collected in distillation, except water completes.
In step (1), described oxolane and nano silicon, Pfansteihl, the proportioning of catalyst-stannous octoate be:
20-25 mL:1.0-1.2 g:1.0-1.2 g:1-2 mL.Optimize, described oxolane and nano silicon, L-breast
Acid, the proportioning of catalyst-stannous octoate are 25ml:1g:1g:1ml.
In step (2), the washing methods of described prepolymer is: prepolymer naturally cools to room temperature, uses centrifugal filtration,
Crude product after filtering is dissolved in the methanol of 30-35 mL, then adds the 40-50 mL containing 1-2 mL concentrated hydrochloric acid in the solution
In methanol, centrifugal filtration；Wash with 20-30 mL dichloromethane, centrifugal filtration, finally wash with 50-60 mL methanol, be centrifuged
Filter, is vacuum dried 24 h, obtains intermediate pre-polymer at product is placed in 30-40 DEG C.In said method, the time of centrifugal filtration is equal
For 5-10min.
In step (3), first with double hydroxyls and 4 of intermediate pre-polymer, the isocyanide of 4-methyl diphenylene diisocyanate
Acid end group reaction obtains oligomer, and the Carbimide. end group of recycling oligomer carries out chain extending reaction with the terminal hydroxy group of BDO
Obtain macromole line polymer.Described intermediate pre-polymer, oxolane, 4,4-methyl diphenylene diisocyanate, 1,4-fourth
The proportioning of glycol is: 1.0-1.2 g:40-50 mL:2.0-2.2 g:3.0-3.2 g.Optimize, described intermediate pre-polymer,
Oxolane, 4,4-methyl diphenylene diisocyanate, the proportioning of 1,4-butanediol be: 1.0g:50ml:2.0g:3.0g.
In step (4), the proportioning of described crude product, dehydrated alcohol, deionized water/perfluor silane mixture solution is 1.0-
1.2 g:100-120 mL:10-12 mL.In described deionized water/perfluor silane mixture solution, perfluor silane accounts for volume ratio
20%.Optimizing, the proportioning of described crude product, dehydrated alcohol, deionized water/perfluor silane mixture solution is 1.0g:100ml:
10ml。
The present invention also provides for low-surface-energy polishing type polyurethane marine antifouling coating certainly prepared by a kind of said method.
The present invention also provides for low-surface-energy making from polishing type polyurethane marine antifouling coating prepared by a kind of said method
By method, including: low-surface-energy is dissolved in oxolane from polishing polyurethane coating, supersound process 5 min, will above-mentioned mix
Liquid is applied on epoxy link plate uniformly, natural air drying, by dry ocean link plate submergence in the seawater.Described low-surface-energy is certainly
The proportioning of polishing polyurethane coating and oxolane is 2 g:20 mL.
The present invention uses the method that ring-opening polymerisation, polycondensation reaction and hydrophobization combine, and prepares low-surface-energy efficiently
From polishing polyurethane coating, have that step is simple, the response time is short, percent grafting is high, productivity high；Raw materials used price is low
Honest and clean and environment friendly and pollution-free, modified nano silicon has certain hydrophobicity, and the maximum contact angle that experiment records is
108。, there is relatively low surface energy；The low-surface-energy of preparation is easier to fall from polishing type polyurethane marine antifouling coating owing to containing
The polylactic acid solved and polyurethane so that this coating has good degradability, i.e. have preferably from polishing ability, and experiment records
Coating degradation cycle be 6 months；With nano silicon for coating base material, the suspension stability improving coating is poor, thixotroping
Property poor, weatherability is poor and abrasion resistance difference etc., make film and hull bond strength increase substantially, hardness of film increase, surface
Self-cleaning ability also obtains improvement.Prepared low-surface-energy can be widely applied to boats and ships from polishing type polyurethane marine antifouling coating
Hull sprays paint the fields such as anti-marine biofouling, understand from the panel experiment of ocean this coating have preferably from polishing ability and
Antibiotic property, safety non-toxic, provide a kind of new way for solving boats and ships marine biofouling.
Accompanying drawing explanation
Fig. 1 is specific embodiments of the present invention, Technology Roadmap；
Fig. 2 is the product pictorial diagram of the product 1-6 of embodiment 1 to embodiment 6；
Fig. 3 is SiO2/ PLA (a) and SiO2The infrared spectrogram of/PLA/PU (b)；
Fig. 4 is SiO2/ PLA/PU hydrogen nuclear magnetic resonance spectrogram；
Fig. 5 is SiO2 (a) and SiO2The thermogravimetric curve of/PLA (b)；
Fig. 6 is SiO2/ PLA (b) and SiO2The thermogravimetric curve of/PLA/PU (c)；
Fig. 7 is pure polyurethane (PU) and SiO2The ocean link plate comparison diagram of/PLA/PU.
Detailed description of the invention
Embodiments of the invention are given below.It is pointed out that following embodiment is that the several of the present invention are embodied as
Method, protection scope of the present invention is not limited to this.
Embodiment 1:
A kind of low-surface-energy from polishing type polyurethane marine antifouling coating, concrete steps and method is:
(1) reagent purification:
1) being dried of nano silicon: take 4 g nano silicons in beaker, be placed in baking oven, control temperature
Spend about 70 DEG C-80 DEG C (may not exceed 110 DEG C, the groups such as nano-silica surface hydroxyl can be made to come off), be dried 12
h。
2) oxolane/normal hexane except water: measure the oxolane/normal hexane of certain volume in 500 mL round-bottomed flasks
In, take appropriate metallic sodium and be chopped into sodium grain, add in oxolane/normal hexane, use heat collecting type constant-temperature heating magnetic stirring apparatus
About 100 DEG C condensing refluxes 3-7 days, add indicator (benzophenone) in good time, until solution turned blue color (or purple), steam
Evaporate the fraction collecting about 67 DEG C, except water completes.(note: can not be evaporated completely by solution, if being evaporated remaining metallic sodium completely
Meet water meeting vigorous reaction, cause bigger danger).
(2) nano silicon grafted polylactic acid: take 25 mL oxolanes in flask, be sequentially added into nanometer titanium dioxide
Silicon 1.0 g, Pfansteihl 1.0 g, catalyst-stannous octoate 1 mL, supersound process 30 min is allowed to mix homogeneously, under nitrogen protection
It is stirred at reflux at 120 DEG C and is allowed to react 24 h and obtains prepolymer (SiO2/ PLA).
(3) washing of prepolymer: by prepolymer (SiO2/ PLA) naturally cool to room temperature, use centrifugal filtration, duration 5
min；Crude product after filtering is dissolved in the methanol of 30 mL, then adds the 50 mL methanol containing 1 mL concentrated hydrochloric acid in the solution
Middle removing Sn residue, centrifugal filtration, duration 5 min；With 20 mL dichloromethane washings, centrifugal filtration, duration 5 min；Finally
With 50 mL methanol washings, centrifugal filtration, duration 5 min.Product is placed in 30 DEG C of environment and is vacuum dried 24 h, obtain middle in advance
Polymers.
(4) from the preparation polishing polyurethane coating crude product: take SiO2/ PLA 0.2 g joins with condensing tube and leads to
Have in the there-necked flask reaction unit of nitrogen, add oxolane 50 mL, make prepolymer dissolve under stirring, the most molten
Xie Hou, adds 4,4-methyl diphenylene diisocyanate 2.0 g, reacts 2 h and obtain oligomer, be subsequently adding at 80 DEG C
BDO 3.0 g, after mix homogeneously, is increased to 90 DEG C by temperature, reacts 10 h and obtains macromole line polymer.
After terminating reaction, treat that temperature drops to room temperature, solution is added drop-wise in the normal hexane of 8 times of volumes precipitation, centrifugal filtration, duration 5
Min, puts into product vacuum drying oven 12 h in 50 DEG C of environment and obtains from polishing polyurethane coating crude product (SiO2/PLA/
PU).
(5) crude product hydrophobization: take crude product (SiO2/ PLA/PU) (0.20 g) be dissolved in 20 mL dehydrated alcohol, permanent
Add deionized water/perfluor silane (wherein perfluor silane the accounts for volume ratio 20%) mixed solution of 2 mL at temperature 70 DEG C, react 5
H, centrifugal 5 times, puts into product and is vacuum dried 12 h in 50 DEG C of environment and obtains product 1.Experiment finds that product 1 is reunited the most strict
Evil, granule is relatively big, and poor dispersion, color is dark brown.
Embodiment 2: add SiO2The amount of/PLA is 0.3 g, and other step and method, with embodiment 1, obtain product 2, real
Issuing after examination and approval existing product 2 relatively embodiment 1 to reunite and slightly reduce, granule diminishes, and color is taupe.
Embodiment 3: add SiO2The amount of/PLA is 0.5 g, and other step and method, with embodiment 1, obtain product 3, real
Issuing after examination and approval existing product 3 relatively embodiment 2 to reunite and slightly reduce, granule diminishes, and color is Lycoperdon polymorphum Vitt.
Embodiment 4: add SiO2The amount of/PLA is 0.8 g, and other step and method, with embodiment 1, obtain product 4, real
Issuing after examination and approval existing product 4 relatively embodiment 3 to reunite and slightly reduce, granule diminishes, and in fine-powdered, color is canescence.
Embodiment 5: add SiO2The amount of/PLA is 1.0 g, and other step and method, with embodiment 1, obtain product 5, real
Issuing after examination and approval the reunion of existing product 5 relatively embodiment 4 has reduction, granule to diminish, and in fine-powdered, color is rice white.
Embodiment 6: add SiO2The amount of/PLA is 1.0 g, and the amount of 4,4-methyl diphenylene diisocyanates is 4.0 g,
Other conditions, with embodiment 1, obtain product 6, and experiment finds product 6 relatively embodiment 5 soilless sticking phenomenon, without granule, in powder,
Color is pure white, and quality is bigger than embodiment 5.
Embodiment 7: take 4,4-methyl diphenylene diisocyanate (2.0 g), add BDO (3.0 g), mixing
After Jun Yun, at 90 DEG C, react 10 h.After terminating reaction, treat that temperature drops to room temperature, solution is added drop-wise to 8 times of volumes
Normal hexane precipitates, centrifugal filtration, duration 5 min, product is put into vacuum drying oven 12 h in 50 DEG C of environment and obtains pure poly-
Urethane (PU).
Embodiment 8: be dissolved in 20 mL oxolanes by the pure polyurethane of 2 g (PU), supersound process 5 min, by above-mentioned mixed
Liquid is applied on epoxy link plate uniformly, natural air drying, by dry ocean link plate submergence in the seawater, within 5 days, changes a sea water
(ocean panel experiment is carried out in the lab, need to regularly replace sea water), observed and recorded.
Embodiment 9: 2 g low-surface-energies are dissolved in 20 mL oxolanes from polishing polyurethane coating, supersound process 5
Min, is applied on epoxy link plate uniformly by above-mentioned mixed liquid, natural air drying, by dry ocean link plate submergence in the seawater, and 5
It changes a sea water (ocean panel experiment is carried out in the lab, need to regularly replace sea water), observed and recorded.
Claims (9)
1. a low-surface-energy is from the preparation method polishing type polyurethane marine antifouling coating, it is characterised in that include walking as follows
Rapid:
(1) take oxolane in flask, be sequentially added into nano silicon, Pfansteihl, catalyst-stannous octoate, ultrasonic place
Reason 20-30 min is allowed to mix homogeneously, is stirred at reflux and is allowed to react 20-24 h and i.e. obtains under nitrogen protection at 100-120 DEG C
Prepolymer；
(2) prepolymer is obtained intermediate pre-polymer by being dried 10-12 h at after washing 20-30 DEG C；
(3) take intermediate pre-polymer join with condensing tube and be connected with nitrogen there-necked flask reaction unit in, add tetrahydrochysene furan
Muttering, after making prepolymer be completely dissolved, add 4 under stirring, 4-methyl diphenylene diisocyanate, at 60-80 DEG C
Reaction 2-4 h obtains oligomer, is subsequently adding BDO, after mix homogeneously, temperature is increased to 90 DEG C, reacts 8-10
H obtains macromole line polymer；After terminating reaction, treat that temperature drops to room temperature, solution is added drop-wise to the normal hexane of 5 ~ 8 times of volumes
Middle precipitation, centrifugal filtration, duration 5-10 min, puts into product vacuum drying 10-12 h in 40-50 DEG C of environment and obtains from throwing
Light polyurethane coating crude product；
(4) taking crude product to be dissolved in dehydrated alcohol, the deionized water/perfluor silane adding 10 mL at constant temperature 60-70 DEG C mixes
Close solution, react 5-8 h, centrifugal 5 times, product is put into vacuum drying 10-12 h in 40-50 DEG C of environment and obtains low-surface-energy
From polishing polyurethane coating.
A kind of low-surface-energy the most according to claim 1 polishes the preparation method of type polyurethane marine antifouling coating certainly, its
Being characterised by, described nano silicon, oxolane and normal hexane need to remove water purification.
A kind of low-surface-energy the most according to claim 1 polishes the preparation method of type polyurethane marine antifouling coating certainly, its
Being characterised by, in step (1), described oxolane and nano silicon, Pfansteihl, the proportioning of catalyst-stannous octoate be:
20-25 mL:1.0-1.2 g:1.0-1.2 g:1-2 mL.
A kind of low-surface-energy the most according to claim 1 polishes the preparation method of type polyurethane marine antifouling coating certainly, its
Being characterised by, in step (2), the washing methods of described prepolymer is: prepolymer naturally cools to room temperature, uses and was centrifuged
Filter, the crude product after filtering is dissolved in the methanol of 30-35 mL, then adds the 40-50 containing 1-2 mL concentrated hydrochloric acid in the solution
ML methanol, centrifugal filtration；Wash with 20-30 mL dichloromethane, centrifugal filtration, finally wash with 50-60 mL methanol, be centrifuged
Filter, is vacuum dried 24 h, obtains intermediate pre-polymer at product is placed in 30-40 DEG C.
A kind of low-surface-energy the most according to claim 1 polishes the preparation method of type polyurethane marine antifouling coating certainly, its
Be characterised by, in step (3), described intermediate pre-polymer, oxolane, 4,4-methyl diphenylene diisocyanate, Isosorbide-5-Nitrae-fourth two
The proportioning of alcohol is: 1.0-1.2 g:40-50 mL:2.0-2.2 g:3.0-3.2 g.
A kind of low-surface-energy the most according to claim 1 polishes the preparation method of type polyurethane marine antifouling coating certainly, its
Being characterised by, in step (4), the proportioning of described crude product, dehydrated alcohol, deionized water/perfluor silane mixture solution is 1.0-
1.2 g:100-120 mL:10-12 mL.
7. according to a kind of low-surface-energy described in claim 1 or 6 from the preparation method of polishing type polyurethane marine antifouling coating,
It is characterized in that, in described deionized water/perfluor silane mixture solution, perfluor silane accounts for volume ratio 20%.
8. the low-surface-energy polishing type polyurethane marine anti-pollution certainly that prepared by the method as described in claim 1-7 any one
Coating.
9. low-surface-energy as claimed in claim 8 is from a using method for polishing type polyurethane marine antifouling coating, and it is special
Levying and be, be dissolved in oxolane from polishing polyurethane coating by low-surface-energy, supersound process 5-10 min, by above-mentioned mixed liquid
Being applied to uniformly on epoxy link plate, natural air drying, by dry epoxy link plate submergence in the seawater, described low-surface-energy is from throwing
The proportioning of light polyurethane coating and oxolane is 2 g:20 mL.
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| CN105860813A (en) * | 2016-06-25 | 2016-08-17 | 董植深 | Convertible self-polishing marine antifouling coating |
| CN107189669B (en) * | 2017-07-01 | 2019-01-29 | 湖南科技大学 | A kind of low-surface-energy aqueous polyurethane/nano SiO2Marine anti-pollution coating material and preparation method |
| CN107474715A (en) * | 2017-07-25 | 2017-12-15 | 宁波盾科新材料有限公司 | A kind of antifouling paint peculiar to vessel and preparation method thereof |
| CN108659190B (en) * | 2018-05-18 | 2020-10-09 | 海南大学 | Self-polishing type low-surface-energy polyurethane and preparation method and application thereof |
| CN109651907A (en) * | 2018-11-07 | 2019-04-19 | 成都普瑞斯特新材料有限公司 | Novel tin-free self-polishing type antifouling paint |
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| CN115710339A (en) * | 2022-11-10 | 2023-02-24 | 江苏休伦新材料有限公司 | Bio-based waterborne polyurethane for clothing leather surface layer and preparation method thereof |
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