CN106280969A - Preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas - Google Patents
Preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas Download PDFInfo
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- CN106280969A CN106280969A CN201610807709.1A CN201610807709A CN106280969A CN 106280969 A CN106280969 A CN 106280969A CN 201610807709 A CN201610807709 A CN 201610807709A CN 106280969 A CN106280969 A CN 106280969A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The present invention relates to polymeric material field, a kind of preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas.Its step is as follows: polyether Glycols and diisocyanate are reacted and obtain Polyether-Polyol Polyurethane Prepolymer by (1) in a nitrogen atmosphere；(2) silane coupler modified terminal hydroxy group fluorosilicon oil is utilized to prepare end aminopropyl fluorosilicon oil in a nitrogen atmosphere；(3) reaction of (1) and (2) product obtaining modified polyether fluorosilicon oil, addition catalyst, solvent, defoamer, filler, dispersant, levelling agent obtain low surface energy antifouling coating for seas.This preparation method is simple, and gained coating highlights with substrate/base material, primary coat, the cohesive force of floating coat, adhesive force, and surface can be low, and self-cleaning performance is excellent, has long-acting marine anti-pollution function.
Description
Technical field
The present invention relates to the production field of a kind of macromolecular material, specifically a kind of low based on modified polyether fluorosilicon oil
The preparation method of surface energy antifouling coating for seas.
Background technology
It is known that the mankind manufacture relate to marine facies close various microorganisms that equipment surface is easy to be lived in ocean,
Plant, animal etc. adhere to, constantly growth and breeding, form biofouling.Marine biofouling increases oceanographic equipment surface
Roughness and ship resistance, reduce ship navigating speed, weakens the operational efficiency of naval, and marine fuel consumption simultaneously can show
Writing and increase, carbon dioxide discharges in a large number, and then aggravation Global Greenhouse Effect；Marine biofouling also can block mariculture
The mesh of apparatus so that fish and shrimp mortality rate strengthens；Marine biofouling can change the apparent condition of other marine facility, causes it
Corrosion rate is accelerated, and increases maintenance cost etc..Preventing and treating marine biofouling through frequently with have brushing antifouling paint method, electrolysis weight
Metal method, electrolytic seawater method, conductive coat method, manually or mechanically removing method etc..Wherein brushing antifouling paint be current most convenient,
Most effective and most economical method.Along with the enhancing of people's environmental consciousness, nontoxic, efficient, environmental protection type anti-pollution paint becomes undoubtedly
The mainstream development direction that marine antifouling coating is most potential.
Fluorosilicon oil is being commonly called as containing fluoroalkylpolysiloxane, refers in polymer containing C-F key, C-Si key and Si-O-Si
Key, but without Si-F key, and the carbon-based group of fluorination is not directly coupled on silicon atom, there is a base polymer of spacer groups centre.
Owing to fluorosilicon oil has the Common advantages of siloxanes and fluorocarbons concurrently, thus show excellent weatherability, resistant of high or low temperature,
Chemical stability and water and oil-resistant, be widely used in cosmetics, leather, paper, medicine, aerospace, automobile, petrochemical equipment dress be coated with,
The fields such as boats and ships anticorrosion, bridge, building, and become the recent studies on focus of Material Field.
Simple fluorosilicon oil cannot have preferably adhesion with substrate/base material, primary coat, floating coat owing to surface energy is low
Power.Therefore, fluorosilicon oil introduces polar block formation block copolymer will assist in and base material formation adhesive force.Have been reported that
Aqueous polyether group is claimed to have anti-protein adsorption and cell attachment characteristic.Polyurethane is due to its solvent resistance, thermostability, submissive
Property, the character such as resistance to water, wearability and intensity is high and be widely used in coating.The primary raw material of polyurethane is isocyanates,
Its character is the most active.Isocyanates can be combined with hydroxy resin, it is also possible to and hydroxy combining in ground, promote hydrogen bond with
The formation of other chemical bond, can strengthen the adhesion between ground.Reacted with fluorosilicon oil by Polyether-Polyol Polyurethane Prepolymer
Form copolymer, not only there is the low-surface-energy antifouling property of fluorosilicon oil, with ground, there is good adhesive force simultaneously.
Marine antifouling coating is a kind of sapecial coating, is mainly made up of macromolecule resin, anti-fouling agent, color stuffing, solvent etc.,
Wherein anti-fouling agent is biotoxin, and its function is suppression or the attachment preventing marine fouling organism.Macromolecule resin is whole painting
The substrate of layer and the carrier of anti-fouling agent, directly affect the performance of coating and control the release of anti-fouling agent.Preferably macromolecule resin
Substrate should have good mechanical property, the most steadily in the long term.Additionally, also should have the preferable compatibility with anti-fouling agent.
As the macromolecule resin of carrier, performance and its feature of environmental protection to antifouling paint play pivotal role.Marine antifouling coating has very
Multiple types, the antifouling painting of low-surface-energy that wherein organic fluorinated silicone marine antifouling coating is is film forming matter substrate with organic fluorinated silicone resin
Material, has inorganic and inorganic material advantage concurrently, and surface can be extremely low, and marine organisms cannot adhere to, and this makes it have excellent preventing
Dirt, thus avoid the anti-fouling agent pollution to ocean water body environment, comply fully with the requirement of environmental conservation.
Chinese patent CN105017910A relates to a kind of modified super-hydrophobic marine antifouling coating, with POSS modification resin, receives
Rice corpuscles additive and solvent, n-butanol are constituted, and have ultra-hydrophobicity, have " the self-cleaning effect of Folium Nelumbinis after the solidification of this coating film forming
Should ".Containing Red copper oxide in its nano particle additive, easily cause environmental pollution.Chinese patent CN103122188A is open
A kind of " from polishing organic silicon-fluorine modified propylene vinegar low surface energy anti-fouling paint ", by organic silicon-fluorine modification acrylate, antifouling
Agent, filler and organic solvent are constituted, and after coating film forming, brightness is lasting, from polishability and satisfactory mechanical property, does not produce and splits
Stricture of vagina and other defect, can realize low-surface-energy and the collaborative antifouling effect from polishing, show the long-acting and anti-fouling performance of excellence.But
The anti-fouling agent that this coating uses is Red copper oxide and copper pyrithione, has toxicity, pollutes marine environment equally.China
Patent CN104927618A provides a kind of low-surface-energy from polishing type polyurethane marine antifouling coating and preparation method thereof.This coating
Polylactic acid to be grafted to nano-silica surface, then react generation polyurethane prepolymer with isocyanates, be mixed into perfluor silicon
The low-surface-energy obtaining totally nontoxic after alkane is degraded from polishing type polyurethane marine antifouling coating, slow by wherein polylactic acid
It is done step-by-step from polishing performance.In view of the complex characteristics of marine environment, the degradation cycle of polylactic acid needs to be investigated further；
Perfluor silane cost is the highest simultaneously, how to balance low-surface-energy characteristic and coating cost becomes the key issue of this coating.
Summary of the invention
The purpose of the present invention is contemplated to overcome above-mentioned existing technical deficiency, it is provided that a kind of based on modified polyether fluorosilicon oil
The preparation method of low surface energy antifouling coating for seas, the marine antifouling coating according to said method prepared is antifouling without any heavy metal
Agent, safety and environmental protection, can be used for the coating protection of the building field such as marine ship, dock.
The present invention solves above-mentioned technical problem and the technical scheme is that a kind of based on modified polyether fluorosilicon oil low-surface-energy
The preparation method of marine antifouling coating, it is characterised in that first 80～90 DEG C, use polyether Glycols and two under nitrogen atmosphere
Isocyanates reacts 4～5h with mol ratio 1:2, generates Polyether-Polyol Polyurethane Prepolymer standby；Then 50 DEG C, under nitrogen atmosphere
By Silane coupling agent KH550 and terminal hydroxy group fluorosilicon oil with mol ratio > 2:1 reaction 4～5h, unnecessary KH550 is evaporated off and obtains holding ammonia third
Base fluorosilicon oil；Finally by polyether-polyurethane performed polymer and end aminopropyl fluorosilicon oil with mol ratio 2.5～3.5:1 70～80 DEG C,
React 1h under nitrogen atmosphere and obtain modified polyether fluorosilicon oil, add catalyst, solvent, defoamer, filler, dispersant, levelling agent,
Mix homogeneously obtains low surface energy antifouling coating for seas.
Described polyether Glycols be Polyethylene Glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran diol (PTMG) or
The combined polyether Glycols of person；Described diisocyanate is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate
(MDI), the own diisocyanate resin of 1,6-(HDI), isophorone diisocyanate (IPDI) or the mixture of diisocyanate；Institute
The terminal hydroxy group fluorosilicon oil stated be by trifluoro propyl methyl cyclotrisiloxane (D3F) ring-opening polymerisation after homopolymer (degree of polymerization be 3～
4) copolymer or by octamethylcy-clotetrasiloxane (D4) obtained with trifluoro propyl methyl cyclotrisiloxane (D3F) ring opening copolymer
(degree of polymerization of D4 and D3F is 3～4)；With by weight, described modified polyether fluorosilicon oil 100 parts, catalyst 0.01～
0.1 part, solvent 40～60 parts, defoamer 1～2 parts, filler 45～55 parts, dispersant 0.2～0.6 part, levelling agent 0.02～0.8
Part；Described catalyst is dibutyl tin laurate or stannous octoate, and solvent is by the dimethylbenzene that weight ratio is 1:1 and butanone
Mix；Described defoamer is polyacrylamide；Described filler is mica powder, Pulvis Talci or wollastonite；Described divides
Powder is polyacrylic sodium, potassium or ammonium salt；Described levelling agent is glycerol or propylene glycol.
The invention has the beneficial effects as follows, polyurethane-modified polyether polyol component is introduced film-forming resin strand, wherein
Polyethers component has anti-protein absorption and cell attachment characteristic, improves the static antifouling capacity of coating, and polyethers and poly-ammonia
Ester composition also can increase the adhesive force with primary coat or base material；Fluorine silicon composition therein greatly reduces the surface energy of coating, enters one
Step improves antimicrobial adhesive ability, and therefore the present invention has long-acting antifouling capacity as Marine Paints.Meanwhile, the present invention
Film-forming resin does not contains any extra anti-fouling agent, will not pollute marine environment, belong to nontoxic type marine antifouling coating.
Accompanying drawing explanation
With embodiment, this utility model is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the syntheti c route of fluorosilicon oil in the present invention-modified polyether block copolymer.
Detailed description of the invention
Below by embodiment, the present invention is described in further details.
Embodiment 1:
At room temperature being added in reactor by toluene di-isocyanate(TDI) (TDI), logical nitrogen also starts stirring, will be through vacuum high-temperature
Except the PEG200 of water is gradually added drop-wise in toluene di-isocyanate(TDI) (TDI) in 1h, controln TDI: n PEG200=2:1, is warming up to 80
DEG C stirring reaction 4h, obtain isocyanate-terminated PU performed polymer；By through vacuum high-temperature except water terminal hydroxy group fluorosilicon oil (=
642 g/mol) add reactor, logical nitrogen also starts stirring, is added drop-wise in terminal hydroxy group fluorosilicon oil by KH550, controls end in 1h
The mol ratio ＞ 2:1 of hydroxy terminated fluorosilicone oil and KH550, is warming up to 50 DEG C of stirring reaction 4h, then is warming up to 120 DEG C of evacuation 2h removings
The KH550 of excess, obtains holding aminopropyl fluorosilicon oil；PU performed polymer is at room temperature added reactor, and logical nitrogen also starts stirring,
End aminopropyl fluorosilicon oil is gradually added drop-wise in PU performed polymer in 0.5h, controls PU performed polymer and hold rubbing of aminopropyl fluorosilicon oil
Your ratio is 2:1, is warming up to 70 DEG C of stirring reaction 1h and obtains modified polyether fluorosilicon oil, according to modified polyether fluorosilicon oil 100 weight portion,
Add dimethylbenzene and butanone mixed solvent 50 parts that weight ratio is 1:1, stannous octoate 0.05 part, polyacrylamide 1 part, mica powder
50 parts, ammonium polyacrylate 0.4 part, propylene glycol 0.02 part, obtain low surface energy antifouling coating for seas.
Embodiment 2:
By toluene di-isocyanate(TDI) (TDI)/1,6-own diisocyanate resin (HDI) mixture at room temperature adds in reactor, logical
Nitrogen also starts stirring, will gradually be added drop-wise to toluene di-isocyanate(TDI) (TDI) through vacuum high-temperature except the PTMG650 of water in 1h
In, the mol ratio controlling isocyanates and PTMG650 is 2:1, is warming up to 80 DEG C of stirring reaction 4h, obtains isocyanate-terminated
PU performed polymer；To add reactor through vacuum high-temperature except the terminal hydroxy group fluorosilicon oil (=642 g/mol) of water, logical nitrogen also starts
Stirring, is added drop-wise to KH550 in terminal hydroxy group fluorosilicon oil in 1h, controls terminal hydroxy group fluorosilicon oil and the mol ratio ＞ 2:1 of KH550, rises
Temperature is to 50 DEG C of stirring reaction 4h, then is warming up to 120 DEG C of excessive KH550 of evacuation 2h removing, obtains holding aminopropyl fluorosilicon oil；Will
PU performed polymer and toluene di-isocyanate(TDI) (TDI) (the two mol ratio is 2:1) at room temperature add reactor, and logical nitrogen also starts
Stirring, is gradually added drop-wise to end aminopropyl fluorosilicon oil in PU performed polymer in 0.5h, controls PU performed polymer and toluene diisocynate
The isocyanates molal quantity of ester (TDI) is 3:1 with the ratio of the amino molal quantity of end aminopropyl fluorosilicon oil, is warming up to 70 DEG C of stirrings anti-
Answer 1h to obtain modified polyether fluorosilicon oil, according to modified polyether fluorosilicon oil 100 weight portion, add dimethylbenzene that weight ratio is 1:1 and
Butanone mixed solvent 50 parts, stannous octoate 0.03 part, polyacrylamide 1 part, wollastonite 50 parts, ammonium polyacrylate 0.2 part, the third two
Alcohol 0.05 part, obtains low surface energy antifouling coating for seas.
Embodiment 3:
At room temperature being added in reactor by HDI, logical nitrogen also starts stirring, will remove the PPG500 of water through vacuum high-temperature at 1h
The most gradually it is added drop-wise to 1, in the own diisocyanate resin of 6-(HDI), controlsn HDI: n PPG500=2:1, is warming up to 90 DEG C of stirring reaction 4h,
Obtain isocyanate-terminated PU performed polymer；Terminal hydroxy group copolymerization fluorosilicon oil (the wherein prestox ring of water will be removed through vacuum high-temperature
The tetrasiloxane degree of polymerization is 4, and the trifluoro propyl methyl cyclotrisiloxane degree of polymerization is 3) add reactor, logical nitrogen starting stirs
Mix, in 1h, KH550 is added drop-wise in terminal hydroxy group copolymerization fluorosilicon oil, control terminal hydroxy group copolymerization fluorosilicon oil and mol ratio ＞ of KH550
2:1, is warming up to 50 DEG C of stirring reaction 4h, then is warming up to 120 DEG C of excessive KH550 of evacuation 2h removing, obtain holding aminopropyl altogether
Poly-fluorosilicon oil；PU performed polymer and toluene di-isocyanate(TDI) (TDI) (the two mol ratio is 2:1) are at room temperature added reactor,
Logical nitrogen also starts stirring, is gradually added drop-wise in PU performed polymer by end aminopropyl copolymerization fluorosilicon oil, controls PU pre-polymerization in 0.5h
The isocyanates molal quantity of body and toluene di-isocyanate(TDI) (TDI) with the ratio of the amino molal quantity of end aminopropyl copolymerization fluorosilicon oil is
3:1, is warming up to 70 DEG C of stirring reaction 1h and obtains modified polyether fluorosilicon oil, according to modified polyether fluorosilicon oil 100 weight portion, add weight
Amount than being the dimethylbenzene of 1:1 and butanone mixed solvent 55 parts, stannous octoate 0.02 part, polyacrylamide 1 part, Pulvis Talci 50 parts,
Ammonium polyacrylate 0.2 part, propylene glycol 0.1 part, obtain low surface energy antifouling coating for seas.
Claims (10)
1. a preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is characterised in that first exist
80～90 DEG C, use under nitrogen atmosphere polyether Glycols and diisocyanate to react 4～5h with mol ratio 1:2, generate polyether-type
Base polyurethane prepolymer for use as is standby；Then 50 DEG C, under nitrogen atmosphere by Silane coupling agent KH550 and terminal hydroxy group fluorosilicon oil with mol ratio
> 2:1 reaction 4～5h, obtain holding aminopropyl fluorosilicon oil；Finally by polyether-polyurethane performed polymer and end aminopropyl fluorosilicon oil 70～
80 DEG C, obtain modified polyether fluorosilicon oil with mol ratio 2.5～3.5:1 reaction 1h under nitrogen atmosphere, add catalyst, solvent, disappear
Infusion, filler, dispersant, levelling agent, mix homogeneously obtains low surface energy antifouling coating for seas.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be that described polyether Glycols is Polyethylene Glycol, polypropylene glycol, polytetrahydrofuran diol or combined polyether Glycols.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy be described diisocyanate be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the own diisocyanate resin of 1,6-,
Isophorone diisocyanate or the mixture of diisocyanate.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy be described terminal hydroxy group fluorosilicon oil be by trifluoro propyl methyl cyclotrisiloxane ring-opening polymerisation after homopolymer, its degree of polymerization
It is 3～4, or the copolymer obtained with trifluoro propyl methyl cyclotrisiloxane ring opening copolymer by octamethylcy-clotetrasiloxane, eight
The degree of polymerization of methyl cyclotetrasiloxane and trifluoro propyl methyl cyclotrisiloxane is 3～4.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be in parts by weight, described modified polyether fluorosilicon oil 100 parts, catalyst 0.01～0.1 part, solvent 40～60 parts, disappear
Infusion 1～2 parts, filler 45～55 parts, dispersant 0.2～0.6 part, levelling agent 0.02～0.8 part.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be that described catalyst is dibutyl tin laurate or stannous octoate, solvent by the dimethylbenzene that weight ratio is 1:1 and
Butanone mixes.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be that described defoamer is polyacrylamide.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be that described filler is mica powder, Pulvis Talci or wollastonite.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be that described dispersant is polyacrylic sodium, potassium or ammonium salt.
The most according to claim 1, preparation method based on modified polyether fluorosilicon oil low surface energy antifouling coating for seas, it is special
Levy and be that described levelling agent is glycerol or propylene glycol.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329822A (en) * | 2017-12-28 | 2018-07-27 | 姜菊芳 | A kind of stain resistant polyurethane coatings and preparation method thereof |
| CN109535408A (en) * | 2018-11-21 | 2019-03-29 | 广东中瀚新材料有限公司 | A kind of thermoplastic polyester elastomeric material of fluorine silicon and its preparation method and application |
| CN109836583A (en) * | 2019-01-28 | 2019-06-04 | 浙江大学 | A kind of preparation method and applications of degradable organosilicon self-polishing marine anti-fouling material |
| CN110387186A (en) * | 2019-07-18 | 2019-10-29 | 武汉长弢新材料有限公司 | A kind of antifouling anti-flaming dope and its construction method |
| CN111662428A (en) * | 2020-05-22 | 2020-09-15 | 中国船舶重工集团公司第七二五研究所 | Self-curing modified organic fluorine-silicon antifouling resin and preparation method thereof |
| CN111808515A (en) * | 2020-06-24 | 2020-10-23 | 中国船舶重工集团公司第七二五研究所 | Preparation method of degradable amphiphilic fouling-resistant antifouling resin |
| CN112608703A (en) * | 2020-11-25 | 2021-04-06 | 广州市白云化工实业有限公司 | Antifouling silane modified polyether adhesive and preparation method thereof |
| CN113845830A (en) * | 2021-10-13 | 2021-12-28 | 常州正邦数码科技有限公司 | Fingerprint-resistant coating of functional film for decorative film surface layer and preparation method thereof |
| CN114276486A (en) * | 2022-01-18 | 2022-04-05 | 陕西科技大学 | Preparation method and application of super-hydrophobic cross-linked structure fluorine-containing acrylate resin |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329822A (en) * | 2017-12-28 | 2018-07-27 | 姜菊芳 | A kind of stain resistant polyurethane coatings and preparation method thereof |
| CN109535408A (en) * | 2018-11-21 | 2019-03-29 | 广东中瀚新材料有限公司 | A kind of thermoplastic polyester elastomeric material of fluorine silicon and its preparation method and application |
| CN109836583A (en) * | 2019-01-28 | 2019-06-04 | 浙江大学 | A kind of preparation method and applications of degradable organosilicon self-polishing marine anti-fouling material |
| CN110387186A (en) * | 2019-07-18 | 2019-10-29 | 武汉长弢新材料有限公司 | A kind of antifouling anti-flaming dope and its construction method |
| CN111662428A (en) * | 2020-05-22 | 2020-09-15 | 中国船舶重工集团公司第七二五研究所 | Self-curing modified organic fluorine-silicon antifouling resin and preparation method thereof |
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Application publication date: 20170104 |