CN114196279B - Low-surface-energy ship primer and preparation method thereof - Google Patents
Low-surface-energy ship primer and preparation method thereof Download PDFInfo
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- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
Abstract
The invention discloses a low surface energy ship primer and a preparation method thereof. The silane groups on the branched chains in the fluorine-silicon copolymer can form a stable net structure through complex hydrolysis condensation reaction, barrier effect is generated on the absorption of corrosive media, and the fluorine-containing side chains can reduce the attachment of dirt on the coating due to lower surface free energy; the polymer with the six-membered oxazine ring structure and the fluorine-silicon copolymer are combined together by taking zinc ions as a chelating center, so that the temperature required by curing is reduced, the diffusion path of a corrosive medium can be prolonged, and the barrier capability of the coating is further improved.
Description
Technical Field
The invention relates to the technical field of preparation of organic coatings, in particular to a low-surface-energy ship primer and a preparation method thereof.
Background
During the course of a ship's voyage, corrosion and pollution caused by seawater and aquatic organisms are a common problem. The surface of the ship body is rough, corrosive substances or organisms are easy to attach, metal corrosion is aggravated, the frictional resistance of navigation is enhanced, and the normal operation of human marine activities is seriously influenced. The application of the coating can effectively inhibit the adhesion of marine organisms, however, the continuous erosion of corrosive media can weaken the barrier effect of the coating, so that the long-term effective reduction of the erosion of the coating by the organisms or the corrosive media is the key for prolonging the service life of the ship.
Patent CN 110041769A discloses a urushiol/fluorocarbon resin/zinc powder composite marine salt spray resistant paint and a preparation method thereof, urushiol, fluorocarbon resin and zinc powder are mixed according to the mass ratio of 3:4:3, then preservative sodium benzoate accounting for 1% of the total mass of the mixture is added, and the mixture is mechanically stirred and mixed for 10min at room temperature, so that the urushiol/fluorocarbon resin/zinc powder composite marine anticorrosive paint is obtained, and the fluorocarbon resin is utilized to improve the comprehensive use performance of the urushiol. Patent CN 109913096A provides a nano modified epoxy ship primer coating, which is modified by adopting nano silicon dioxide through optimizing a formula, so that the bonding strength of the epoxy paint is increased, and the nano modified epoxy ship primer coating has good corrosion resistance. The above patent has a problem of high surface energy of the coating, and a technical problem of poor adhesion of the anti-fouling substances may occur in practical use.
Disclosure of Invention
In view of the above defects of the prior art, the technical problems solved by the invention are: (1) the ship primer has the characteristics of low surface energy and good resistance to marine organisms and corrosive media; (2) the technical problem of high curing temperature of benzoxazine compounds in the primer is solved, the curing temperature of the primer is reduced, and the operability of the product is improved.
The constant erosion of marine organisms and corrosive media causes the inevitable destruction of the metallic material of the ship's hull. Painting organic paint on ships in the prior art is a common method for protecting metal materials. However, this method is difficult to have long-term effectiveness because the coating is soaked in the electrolyte for a long time, and the corrosion components continuously permeate, so that the protection of the coating is ineffective, and the surface of the metal material is seriously polluted by marine organisms and corroded. Since the conventional coating has a high risk of corrosion failure, it is urgently required to design and develop an antifouling coating having excellent anticorrosive property.
The inventors have observed that the corrosion resistance of the coating is closely related to the barrier properties against corrosive agents, and that coating defects formed during curing or use of conventional coatings accelerate the penetration of electrolyte through the coating. In order to solve the technical problem, the inventor prepares a fluorine-silicon copolymer by carrying out free radical polymerization reaction on n-propyl acrylate, pentafluorobenzyl methacrylate, methacryloxymethyltriethoxysilane, glycidyl methacrylate and hydroxypropyl acrylate; the silane groups on the branched chains in the fluorine-silicon copolymer can form a stable net structure through complex hydrolysis condensation reaction, and barrier effect is generated on the absorption of corrosive media, so that the corrosion resistance of the coating is greatly improved; the fluorine-containing side chain in the fluorine-silicon copolymer can reduce the attachment of dirt on the coating due to lower surface free energy, and after the ship primer with low surface energy is cured, the crosslinking degree of the silicon-containing branched chain is increased to form a net-shaped Si-O-Si structure, so that a fluorinated group can be fixed, and the damage of the fluorinated group on the surface of the coating caused by water flow and other impacts is reduced.
A preparation method of a low-surface-energy ship primer comprises the following steps: introducing zinc ions into a fluorosilicone copolymer with a terminal hydroxyl group on a branched chain and a polymer with a six-membered oxazine ring structure to form a chelate so as to combine, wherein the zinc ions are positioned in the center of the chelate; the fluorine-silicon copolymer is obtained by carrying out free radical polymerization reaction on n-propyl acrylate, pentafluorobenzyl methacrylate, methacryloxy methyl triethoxysilane, glycidyl methacrylate and hydroxypropyl acrylate.
Preferably, the preparation method of the low surface energy ship primer comprises the following steps:
s1, under the oxygen-free condition, taking azo compounds as initiators, and carrying out free radical polymerization reaction on n-propyl acrylate, pentafluorobenzyl methacrylate, methacryloxy methyl triethoxysilane, glycidyl methacrylate and hydroxypropyl acrylate to obtain a fluorine-silicon copolymer;
s2 dissolving n-octylamine in ether, and mixing with paraformaldehyde to obtain a mixed reactant; dissolving urushiol in diethyl ether, adding the mixed reactant, reacting, removing the diethyl ether after the reaction is finished, re-dissolving the reaction product in dichloromethane, washing with water for 3-5 times, and drying to remove water to obtain a hexabasic oxazine ring polymer solution;
And S3, mixing the hexatomic oxazine ring polymer solution with the fluorosilicone copolymer under an anaerobic condition, and continuously adding an ether solution of zinc chloride for reaction after mixing to obtain the low-surface-energy ship primer.
In practice the inventors have observed that the introduction of silane groups results in a primer having poor compatibility with the coating system, which adversely affects the coating properties. The reason for this phenomenon may be structural defects such as micropores generated by shrinkage during the curing process of the fluorosilicone copolymer, the micropores and defects of the coating may serve as channels through which corrosive media permeate into the coating, the permeation of the electrolyte may cause the coating to swell and form blisters, and the osmotic pressure caused by the swelling of the coating may break the blisters, thereby forming a direct path through which corrosive substances reach the interface of the metal substrate, which is subject to corrosive attack, and finally, the coating may fail.
The inventors tried to introduce benzoxazine into the original fluorosilicone copolymer; the benzoxazine has no release of small molecules in the curing process, the curing shrinkage rate is almost zero, the modulus is high, the strength is high, and the defects generated in the curing process can be effectively relieved. However, the benzoxazine has low polymer crosslinking density and higher brittleness than a fluorosilicone copolymer, and the temperature required for curing the polymer is higher than 200 ℃, so that the practical application of the benzoxazine is limited.
In order to solve the technical problems, the inventor firstly reacts with n-octylamine, paraformaldehyde and urushiol to form a polymer with a six-membered oxazine ring structure, then the polymer with the six-membered oxazine ring structure is subjected to ring opening to form amino and hydroxyl, the amino and the hydroxyl are combined with a fluorine-silicon copolymer containing terminal hydroxyl on a branched chain through a zinc ion formed chelate, and the polymer with the six-membered oxazine ring structure and the fluorine-silicon copolymer are combined together by taking the zinc ion as a chelate center, so that the temperature required by curing is reduced, meanwhile, the diffusion path of a corrosive medium can be prolonged, and the barrier capability of a coating is further improved.
Further preferably, the preparation method of the low surface energy marine primer comprises the following steps of:
a1, under the anaerobic condition, taking 0.04-0.08 part of azo compound as an initiator, and carrying out free radical polymerization reaction on 18-24 parts of n-propyl acrylate, 2.5-4.5 parts of pentafluorobenzyl methacrylate, 1.5-2.5 parts of methacryloyloxymethyl triethoxysilane, 4.2-6 parts of glycidyl methacrylate and 3.6-8 parts of hydroxypropyl acrylate to obtain a fluorine-silicon copolymer;
a2, dissolving 5-7.5 parts of n-octylamine in 20-30 parts of diethyl ether, and mixing with 2.4-6 parts of paraformaldehyde to obtain a mixed reactant; dissolving 12-16 parts of urushiol in 20-30 parts of diethyl ether, adding the obtained mixture into the obtained solution, reacting, removing the diethyl ether after the reaction is finished, re-dissolving the reaction product in 40-60 parts of dichloromethane, washing with water for 3-5 times, and drying to remove water to obtain a hexabasic oxazine ring polymer solution;
And A3, mixing the hexa-oxazine ring polymer solution with the fluorosilicone copolymer under an oxygen-free condition, continuously adding 3.3-6.8 parts of zinc chloride ethanol solution after mixing, and carrying out reaction after ultrasonic treatment to obtain the low-surface-energy ship primer.
Further preferably, in step a1, the initiator is any one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
Further preferably, the reaction temperature of the free radical polymerization reaction in the step A1 is 80-95 ℃, and the reaction time is 1.5-3 h.
Further preferably, the reaction temperature in the step A2 is 85-110 ℃, and the reaction time is 3-8 h.
Further preferably, the preparation method of the ethanol solution of zinc chloride in the step a3 comprises the following steps: dissolving 0.3-0.8 part of zinc chloride in 3-6 parts of ethanol.
Preferably, the ultrasonic power of the ultrasonic treatment in the step A3 is 550-800W, the ultrasonic frequency is 28-40 kHz, and the ultrasonic time is 15-30 min.
Further preferably, the reaction temperature in the step A3 is 65-80 ℃, and the reaction time is 2-5 h.
The invention discloses a curing method of a low-surface-energy ship primer, which comprises the following steps:
spraying the low-surface-energy ship primer on the surface of a substrate, firstly curing at room temperature for 1-2 h, and then sequentially curing at 120-140 ℃ for 1-2 h and 155-180 ℃ for 0.5-1 h after the room-temperature curing is completed.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The introduction and the function of part of raw materials in the formula of the invention are as follows:
n-propyl acrylate: organic matter, colorless liquid, is used as raw material for synthesizing fluorosilicone copolymer in the invention.
Pentafluorobenzyl methacrylate: the organic matter is used as a raw material for synthesizing the fluorosilicone copolymer in the invention.
Glycidyl methacrylate: the ester compound is colorless transparent liquid and is used as a raw material for synthesizing the fluorine-silicon copolymer.
Hydroxypropyl acrylate: the organic compound, a colorless transparent liquid, is used as a raw material for synthesizing the fluorosilicone copolymer in the present invention.
Azo initiator: the free radical initiator containing nitrogen-nitrogen double bonds in a molecular structure is easy to break to form free radicals.
The invention has the beneficial effects that:
compared with the prior art, the fluorine-silicon copolymer is prepared by free radical polymerization, and the silane groups on the branched chains in the fluorine-silicon copolymer can form a stable net structure through complex hydrolysis condensation reaction, so that barrier effect is generated on the absorption of corrosive media, and the corrosion resistance of the coating is greatly improved.
Compared with the prior art, the fluorine-silicon copolymer has lower surface free energy, can reduce the attachment of dirt on a coating, increases the crosslinking degree of the silicon-containing branched chain after the low-surface-energy ship primer is cured to form a net structure, can fix the fluorinated group, and reduces the damage of the fluorinated group on the surface of the coating caused by water flow and other impacts.
Compared with the prior art, the hexabasic oxazine ring structure polymer synthesized by the method forms amino and hydroxyl through ring opening, and forms chelate through zinc ions with the fluorine-silicon copolymer containing terminal hydroxyl on the branched chain so as to be combined, so that the temperature required by curing is reduced, the diffusion path of a corrosive medium can be prolonged, and the barrier capability of the coating is further improved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Some of the raw material parameters in the comparative examples and examples of the present invention are as follows:
pentafluorobenzyl methacrylate, CAS number: 114859-23-3;
Methacryloxymethyltriethoxysilane, CAS No.: 5577-72-0;
glycidyl methacrylate, CAS No.: 106-91-2;
hydroxypropyl acrylate, CAS No.: 25584-83-2;
urushiol, the urushiol used in the examples of the present invention is urushiol (15:1), CAS No.: 35237-02-6.
Example 1
A preparation method of a low-surface-energy ship primer comprises the following steps:
under the protection of A1 nitrogen, 3.5kg of pentafluorobenzyl methacrylate, 2kg of methacryloyloxymethyltriethoxysilane, 4.2kg of glycidyl methacrylate and 3.6kg of hydroxypropyl acrylate were subjected to radical polymerization using 0.04kg of azobisisobutyronitrile as an initiator to obtain the low surface energy marine primer.
The reaction temperature of the free radical polymerization reaction in the step A1 is 85 ℃, and the reaction time is 2 h.
Example 2
A preparation method of a low-surface-energy ship primer comprises the following steps:
under the protection of A1 nitrogen, 21kg of n-propyl acrylate, 2kg of methacryloxymethyltriethoxysilane, 4.2kg of glycidyl methacrylate and 3.6kg of hydroxypropyl acrylate were subjected to radical polymerization using 0.04kg of azobisisobutyronitrile as an initiator to obtain the low surface energy marine primer.
The reaction temperature of the free radical polymerization reaction in the step A1 is 85 ℃, and the reaction time is 2 h.
Example 3
A preparation method of a low-surface-energy ship primer comprises the following steps:
under the protection of A1 nitrogen, using 0.04kg of azobisisobutyronitrile as an initiator, and carrying out free radical polymerization on 21kg of n-propyl acrylate, 3.5kg of pentafluorobenzyl methacrylate, 2kg of methacryloxymethyltriethoxysilane and 3.6kg of hydroxypropyl acrylate to obtain the low surface energy marine primer.
The reaction temperature of the free radical polymerization reaction in the step A1 is 85 ℃, and the reaction time is 2 h.
Example 4
A preparation method of a low-surface-energy ship primer comprises the following steps:
under the protection of A1 nitrogen, using 0.04kg of azobisisobutyronitrile as an initiator, and carrying out free radical polymerization on 21kg of n-propyl acrylate, 3.5kg of pentafluorobenzyl methacrylate, 2kg of methacryloyloxymethyl triethoxysilane, 4.2kg of glycidyl methacrylate and 3.6kg of hydroxypropyl acrylate to obtain the low surface energy marine primer.
The reaction temperature of the free radical polymerization reaction in the step A1 is 85 ℃, and the reaction time is 2 h.
Example 5
A preparation method of a low-surface-energy ship primer comprises the following steps:
a1 dissolving 6.25kg of n-octylamine in 25kg of diethyl ether, and mixing with 2.4kg of paraformaldehyde to obtain a mixed reactant; dissolving 14kg of urushiol in 30kg of diethyl ether, adding the mixed reactant, reacting, distilling under reduced pressure to remove the diethyl ether after the reaction is finished, re-dissolving the reaction product in 40kg of dichloromethane, washing with water for 3 times, drying with anhydrous sodium sulfate to remove water, and filtering to obtain filtrate, thereby obtaining a hexa-oxazine ring polymer solution;
and adding 3.3kg of zinc chloride ethanol solution into the hexa-oxazine ring polymer solution under the protection of A2 nitrogen, and carrying out ultrasonic treatment and reaction to obtain the low-surface-energy ship primer.
The reaction temperature in step A1 was 95 ℃ and the reaction time was 3.5 h.
The preparation method of the ethanol solution of zinc chloride in the step A2 comprises the following steps: 0.3kg of zinc chloride was dissolved in 3kg of ethanol.
The ultrasonic power of the ultrasonic treatment in the step A2 is 550W, the ultrasonic frequency is 28kHz, and the ultrasonic time is 15 min.
The reaction temperature in step A2 was 75 ℃ and the reaction time was 3 h.
Example 6
A preparation method of a low-surface-energy ship primer comprises the following steps:
a1 under the protection of nitrogen, taking 0.04kg of azobisisobutyronitrile as an initiator, and carrying out free radical polymerization on 21kg of n-propyl acrylate, 3.5kg of pentafluorobenzyl methacrylate, 2kg of methacryloyloxymethyl triethoxysilane, 4.2kg of glycidyl methacrylate and 3.6kg of hydroxypropyl acrylate to obtain a fluorine-silicon copolymer;
A2 dissolving 6.25kg of n-octylamine in 25kg of diethyl ether, and mixing with 2.4kg of paraformaldehyde to obtain a mixed reactant; dissolving 14kg of urushiol in 30kg of diethyl ether, adding the mixed reactant, reacting, distilling under reduced pressure to remove the diethyl ether after the reaction is finished, re-dissolving the reaction product in 40kg of dichloromethane, washing with water for 3 times, drying with anhydrous sodium sulfate to remove water, and filtering to obtain filtrate, thereby obtaining a hexa-oxazine ring polymer solution;
and A3, mixing the hexatomic oxazine ring polymer solution with the fluorosilicone copolymer under the protection of nitrogen, and performing ultrasonic treatment to obtain the low-surface-energy ship primer.
The reaction temperature of the free radical polymerization reaction in the step A1 is 85 ℃, and the reaction time is 2 h.
The reaction temperature in step A2 was 95 ℃ and the reaction time was 3.5 h.
The ultrasonic power of the ultrasonic treatment in the step A3 is 550W, the ultrasonic frequency is 28kHz, and the ultrasonic time is 15 min.
The reaction temperature in step A3 was 75 ℃ and the reaction time was 3 h.
Example 7
A preparation method of a low-surface-energy ship primer comprises the following steps:
a1 under the protection of nitrogen, taking 0.04kg of azobisisobutyronitrile as an initiator, and carrying out free radical polymerization on 21kg of n-propyl acrylate, 3.5kg of pentafluorobenzyl methacrylate, 2kg of methacryloyloxymethyl triethoxysilane, 4.2kg of glycidyl methacrylate and 3.6kg of hydroxypropyl acrylate to obtain a fluorine-silicon copolymer;
A2 dissolving 6.25kg of n-octylamine in 25kg of diethyl ether, and mixing with 2.4kg of paraformaldehyde to obtain a mixed reactant; dissolving 14kg of urushiol in 30kg of diethyl ether, adding the mixed reactant, reacting, distilling under reduced pressure to remove the diethyl ether after the reaction is finished, re-dissolving the reaction product in 40kg of dichloromethane, washing with water for 3 times, drying with anhydrous sodium sulfate to remove water, and filtering to obtain filtrate, thereby obtaining a hexa-oxazine ring polymer solution;
and A3, mixing the hexa-oxazine ring polymer solution with the fluorosilicone copolymer under the protection of nitrogen, continuously adding 3.3kg of ethanol solution of zinc chloride after mixing, and carrying out reaction after ultrasonic treatment to obtain the low-surface-energy ship primer.
The reaction temperature of the free radical polymerization reaction in the step A1 is 85 ℃, and the reaction time is 2 h.
The reaction temperature in step A2 was 95 ℃ and the reaction time was 3.5 h.
The preparation method of the ethanol solution of zinc chloride in the step A3 comprises the following steps: 0.3kg of zinc chloride was dissolved in 3kg of ethanol.
The ultrasonic power of the ultrasonic treatment in the step A3 is 550W, the ultrasonic frequency is 28kHz, and the ultrasonic time is 15 min.
The reaction temperature in step A3 was 75 ℃ and the reaction time was 3 h.
Test example 1
Preparation of paint film samples: the low surface energy ship primer in the embodiments 1-7 is respectively sprayed on the surface of a substrate, the thickness of the primer is 80 μm, the primer is firstly cured for 1.5h at room temperature, and after the room temperature curing is completed, the primer is sequentially cured for 1h at 120 ℃ and cured for 0.5h at 155 ℃.
The algae resistance test of the low surface energy ship primer is carried out according to the specific requirements in GB/T21353 and 2008 'paint film algae resistance determination method'. The culture medium is an Allen culture medium; the specification of the paint film sample is 2.8cm multiplied by 2.8cm, and 3 test samples are prepared for each group; the test strain is Chlorella (Chlorella vulgaris) ATCC 11468. Placing the inoculated sample into a constant-temperature constant-humidity illumination incubator, wherein the temperature is 25 ℃, the relative humidity is 90%, the illumination intensity is 2000lx, and the illumination is carried out for 14h every day; keeping the surface of the sample wet, and recording the growth conditions of the sample and the algae in the culture dish; the culture was continued for 21 days, and the test results were checked and recorded. After the test is finished, the growth condition of algae on the surface of the paint film is observed by naked eyes, the degree of the algae growing on the surface of the sample is evaluated according to the grade in the table 1, and the culture method, the test algae species, the illumination time and the test period adopted by the test are reported. The results of the algae resistance test of the low surface energy marine primer are shown in table 2.
TABLE 1
TABLE 2
The lower the level of anti-algae, the better the anti-algae of the paint film, according to the definition in the above national standard. As can be seen by comparing the above examples with the best reference, example 7 has the best anti-algae properties. The result of this phenomenon may be that the silane groups on the side chains in the fluorosilicone copolymer can form a stable network structure through a complex hydrolysis condensation reaction, which has a barrier effect on the absorption of corrosive media, thereby greatly improving the corrosion resistance of the coating; the fluorine-containing side chain in the fluorine-silicon copolymer can reduce the attachment of dirt on the coating due to lower surface free energy.
Test example 2
Preparation of paint film samples: the low surface energy ship primers in the embodiments 4, 6 and 7 are respectively sprayed on the surface of the substrate, the thickness of the primer is 80 μm, the primer is firstly cured for 1.5h at room temperature, and after the room temperature curing is completed, the primer is sequentially cured for 1h at 120 ℃ and cured for 0.5h at 155 ℃.
The surface free energy of the low surface energy marine primer was measured by a full-automatic contact angle measuring instrument water drop angle measuring instrument (provided by minty precision measuring instrument, inc., suzhou). The surface free energy of some examples was calculated from the contact angle by the analysis software associated with the measuring instrument. Each group was tested 3 times and the results were arithmetically averaged. The surface free energy test results for the low surface energy marine primer are shown in table 3.
TABLE 3
Sample combination | Surface free energy (mJ. m) -2 ) |
Example 4 | 37.2 |
Example 6 | 28.1 |
Example 7 | 24.8 |
The adhesion of dirt on the surface of the marine primer tends to decrease and then increase as the free energy of the surface decreases. When the surface free energy is 23-25 mJ.m -2 The adhesion of dirt within the range is minimal. As can be seen from the comparison between the above examples, example 7 has the best effect of preventing the adhesion of dirt, and the reason for this phenomenon may be that the fluorine-containing side chain in the fluorosilicone copolymer can reduce the adhesion of dirt on the coating layer due to the lower surface free energy.
Test example 3
Preparation of paint film samples: the low surface energy ship primer in the embodiments 4-7 is respectively sprayed on the surface of a substrate, the thickness of the primer is 80 μm, the primer is firstly cured for 1.5h at room temperature, and after the room temperature curing is completed, the primer is sequentially cured for 1h at 120 ℃ and cured for 0.5h at 155 ℃.
The salt water resistance of the low-surface-energy ship primer is determined according to the specific requirements in GB/T10834-2008 'method for determining salt water and hot brine soaking of ship paint'. The size of the test groove is 700mm multiplied by 400 mm; the test pieces were 300 mm. times.100 mm. times.2 mm in size, and four test pieces were prepared for each set. Hot saline water soaking is selected for testing, the temperature of the saline water is 35 ℃, soaking is carried out for 7d for one period, and a hot saline water soaking test with the temperature of 80 ℃ is carried out in the last 2h of each period; the test was performed for 12 cycles. The phenomena of light loss, color change, rusting, bubbling, falling, cracking and the like of a coating system are detected by referring to GB/T1766 and 2008 'rating method for color paint and varnish coating aging'. The results of the salt water resistance tests of the low surface energy marine primer are shown in table 4.
TABLE 4
Sample combination | Grade of degree of change | Grade of number of damage | Destruction size rating |
Example 4 | 3 | 3 | S3 |
Example 5 | 3 | 3 | S4 |
Example 6 | 2 | 1 | S2 |
Example 7 | 0 | 0 | S1 |
According to the definition in GB/T1766-. As can be seen from the comparison of the above examples, example 7 has the best salt water resistance, which may be caused by the fact that the crosslinking degree of the silicon-containing branched chain is increased to form a net-shaped Si-O-Si structure, so that the fluorinated groups can be fixed, and the damage of the fluorinated groups on the surface of the coating layer due to the impact of water flow and the like is reduced; the polymer of the hexatomic oxazine ring structure forms amino and hydroxyl through ring opening, the amino and hydroxyl are combined with the fluorine-silicon copolymer containing terminal hydroxyl on the branched chain through forming a chelate through zinc ions, and the polymer of the hexatomic oxazine ring structure and the fluorine-silicon copolymer are combined together by taking the zinc ions as a chelating center, so that a diffusion path of a corrosive medium is prolonged, and the barrier capability of the coating is further improved.
Claims (8)
1. The preparation method of the low-surface-energy ship primer is characterized by comprising the following steps of:
a1, under the anaerobic condition, taking 0.04-0.08 part of azo compound as an initiator, and carrying out free radical polymerization reaction on 18-24 parts of n-propyl acrylate, 2.5-4.5 parts of pentafluorobenzyl methacrylate, 1.5-2.5 parts of methacryloyloxymethyl triethoxysilane, 4.2-6 parts of glycidyl methacrylate and 3.6-8 parts of hydroxypropyl acrylate to obtain a fluorine-silicon copolymer;
a2, dissolving 5-7.5 parts of n-octylamine in 20-30 parts of diethyl ether, and mixing with 2.4-6 parts of paraformaldehyde to obtain a mixed reactant; dissolving 12-16 parts of urushiol in 20-30 parts of diethyl ether, adding the obtained mixture into the obtained solution, reacting, removing the diethyl ether after the reaction is finished, re-dissolving the reaction product in 40-60 parts of dichloromethane, washing with water for 3-5 times, and drying to remove water to obtain a hexabasic oxazine ring polymer solution;
and A3, mixing the hexa-oxazine ring polymer solution with the fluorosilicone copolymer under an oxygen-free condition, continuously adding 3.3-6.8 parts of zinc chloride ethanol solution after mixing, and carrying out reaction after ultrasonic treatment to obtain the low-surface-energy ship primer.
2. The method of preparing a low surface energy marine primer according to claim 1, wherein: the initiator in the step A1 is any one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
3. The method of preparing a low surface energy marine primer according to claim 1, wherein: the reaction temperature of the free radical polymerization reaction in the step A1 is 80-95 ℃, and the reaction time is 1.5-3 h.
4. The method for preparing the low surface energy marine primer according to claim 1, wherein: the reaction temperature in the step A2 is 85-110 ℃, and the reaction time is 3-8 h.
5. The method of preparing a low surface energy marine primer according to claim 1, wherein: the preparation method of the ethanol solution of zinc chloride in the step A3 comprises the following steps: dissolving 0.3-0.8 part of zinc chloride in 3-6 parts of ethanol.
6. The method of preparing a low surface energy marine primer according to claim 1, wherein: the ultrasonic power of the ultrasonic treatment in the step A3 is 550-800W, the ultrasonic frequency is 28-40 kHz, and the ultrasonic time is 15-30 min.
7. The method of preparing a low surface energy marine primer according to claim 1, wherein: the reaction temperature in the step A3 is 65-80 ℃, and the reaction time is 2-5 h.
8. A low surface energy marine primer characterized by: prepared by the method of any one of claims 1 to 7.
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