WO2015021921A1

WO2015021921A1 - Environmentally friendly fluorosiloxane-containing heavy-duty epoxy resin coating and preparation method thereof

Info

Publication number: WO2015021921A1
Application number: PCT/CN2014/084286
Authority: WO
Inventors: 戴李宗; 毛杰; 陈凌南; 曾碧榕; 许一婷; 常迎; 程玲; 罗伟昂; 高辉; 林康斌
Original assignee: 厦门大学
Priority date: 2013-08-13
Filing date: 2014-08-13
Publication date: 2015-02-19
Also published as: CN103450725A; CN103450725B

Abstract

An environmentally friendly fluorosiloxane-containing heavy-duty epoxy resin coating, the formula (in parts by weight) of the coating being: 30-70 parts of epoxy resin containing fluorine, 10-40 parts of curing agent, 0.1-5 parts of POSS, 0.5-5 parts of silane coupling agent, 10-30 parts of reactive diluent, 0.5-3 parts of dispersant, and 0.1-3 parts of light stabilizer. The coating has excellent corrosion resistance and weatherability.

Description

Environment-friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating and preparation method thereof

The invention relates to a fluorine-containing silicon epoxy resin coating and a preparation method thereof, in particular to an environment-friendly fluorine-containing silicon heavy-duty anti-corrosion epoxy resin coating and a preparation method thereof. technical background

With the development of modern industry, the emergence of a number of new industrial fields and the construction of many modern projects, such as the rapid development of China's offshore oil industry, there are more and more fixed steel structures at sea. At present, there are nearly 100 oil platforms in China, which are distributed in the Bohai Sea, East China Sea and South China Sea. It is predicted that China's offshore oil resources will account for about 1/4 of the country's total oil reserves, and it is expected that more offshore oil platforms will be built in the next few years. Most of these platforms will be made of steel materials, so the corrosion control of offshore steel is directly related to the safety of the use of these facilities; it is known that the marine environment is a specific and extremely complex corrosive environment, along with China's ocean transportation industry and marine warships. The rapid development has put forward higher requirements on the ability and service life of anti-corrosion coatings to withstand the environment. The commonly used anti-corrosion coatings can no longer meet the needs. So the concept of "Heavy-duty coating" was put forward. The heavy-duty coating system refers to a high-performance anti-corrosion coating system used in harsh corrosive environments. Generally, the dry film thickness of the coating is less than 1000 μm. Generally, the heavy anti-corrosion coating system has the following properties: weather resistance, good water resistance, long life of the coating system, and can reach more than 15 years; impact resistance, wear resistance Good properties, the coating system is resistant to sea ice collisions and ship docking wear: The coatings are required to have a high solids content and the organic volatiles (VOC) meet national or international standards.

Conventional anti-corrosion treatments are usually treated with heavy metal chromium passivation, but chromium is highly toxic, carcinogenic, and environmentally polluting. The key to the future development of heavy-duty coatings is high-performance, environmentally-friendly synthetic resins. Epoxy resin is widely used because of its ease of processing and excellent properties of cured products. It can be made into an anticorrosive coating by modification with epoxy resin. Epoxy resin coating has excellent physical and mechanical properties, the most prominent is its strong adhesion to metal, low curing shrinkage; in addition, its chemical resistance and oil resistance are also very good, especially alkali resistance is very good .

However, the epoxy resin is easy to absorb water due to the presence of the epoxy group and the hydroxyl group on the molecular chain, and the waterproof property needs to be improved, and the heat resistance of the unmodified epoxy resin is not high, and the resin has poor viscosity and high leveling property and is difficult to coat. The fluoropolymer has many excellent properties such as heat resistance, corrosion resistance, hydrophobic oil, electrical insulation, low friction coefficient, biocompatibility and non-combustibility, making it the leader in many applications. More and more people are paying attention. Fluorine has the largest electronegativity, a small atomic radius, a short fluorocarbon bond, and a large bond energy. The fluorine element is introduced into the epoxy resin to impart excellent solvent resistance and oil resistance to the fluorine-containing epoxy resin. Resistance to friction, surface self-cleaning and other properties. And because the fluorine-containing epoxy resin CF bond energy is large, strong in action, sensitive to heat, low in melt viscosity, good in leveling, no need for primer coating film, strong coating film, good mechanical properties, excellent reactivity And storage stability, corrosion resistance, chemical resistance.

In the field of anti-corrosion coatings, Guo Zaichun et al. (a high chlorinated polyethylene-epoxy anticorrosive coating system, Chinese patent, publication number CN 101691464A) uses high chlorinated polyethylene anticorrosive topcoat, high chlorinated polyethylene/epoxy Resin semi-interpenetrating network anti-corrosion intermediate paint, epoxy resin cloud iron anti-rust primer coating system to effectively improve the corrosion resistance of metal, but the preparation process and coating process are complex and costly. Hao Jian et al. (Fluorinated Heavy-Duty Anticorrosive Coatings and Applications, Chinese Patent, Publication No. CN 102732124A) discloses a fluorine-containing heavy-duty anticorrosive coating and its application, which is used in the presence of an epoxy vinyl resin to hexamethacrylate Fluorine-modified epoxy resin anticorrosive coating prepared by free copolymerization of fluorobutyl ester and methacrylate to improve the anticorrosive performance of epoxy resin coating, but the resin has low fluorine content and difficult product performance. Controlled, and the epoxy vinyl resin used makes the heat resistance of the material not high. Liu Bin et al (a fluorine-containing anticorrosive coating, Chinese patent, publication number CN 101962504A) fluororubber-based film-forming material with additives, reinforcing agents and additives, used in organic solvents to obtain a corrosion protection after mixing coating. The coating has excellent weather resistance, abrasion resistance and corrosion resistance, but is mainly composed of fluorocarbon bonds, lacks necessary reactive groups, and has poor adhesion to the surface of the coated substrate, which easily causes the coating to fall off. . Qi Chuanwei et al. (An anti-corrosion fluorocarbon resin coating, Chinese patent, publication number CN 103045029A) An anti-corrosion fluorocarbon resin coating was prepared using PEVE fluorocarbon resin and modified silicone. This coating has good weatherability, but the coating also lacks adsorption and is easy to fall off.

Summary of the invention

The invention provides a green and convenient method for preparing a fluorine-containing silicon heavy anti-corrosion epoxy resin coating. Reactive diluents that can participate in the reaction are used as solvents to replace the traditional volatile organic solvents, which avoids the solvent evaporation of solvent-based coatings in the drying process, resulting in pores and better resistance to chloride ion permeation. It is an environmentally friendly anticorrosive coating, especially suitable for use. In harsh environments such as the ocean. At the same time, the fluorine-containing epoxy resin used is sensitive to heat due to the rigid benzene ring and the CF bond with strong interaction force. The high temperature viscosity is low, the leveling property is good, and the primer coating is not required. Membrane, the construction process is simple, and the coating film is firm and does not fall off. The POSS component added to the coating enhances the heat resistance of the coating to meet the needs of extreme environments.

The formulation of the environmentally friendly fluorine-containing silicon heavy-duty anti-corrosive epoxy resin coating is (parts by weight, the same below): 70 parts of fluorine-containing epoxy resin 30, 40 parts of curing agent, 0.10 parts of POSS, silicon germanium 5至份份。 The coupling agent 0. 5-5 parts, reactive diluent 10 30 parts, dispersing agent 0. 5~3 parts, light stabilizer 0.3~1 parts.

The fluorine-containing epoxy resin is synthesized from a fluorine-containing intermediate and epichlorohydrin under a base catalysis. The fluorine-containing intermediate is (3-trifluoromethylbenzene) hydroquinone, 1, 1-bis(4-hydroxyphenyl)-1-(3-trifluoromethylphenyl)-2, 2, 2-Trifluoroacetamidine, 1, 1-bis(4-hydroxyphenyl)-1-phenyl-2, 2, 2-trifluoroacetamidine, 1, 1-bis(4-hydroxyphenyl)-1 - (4-Fluorophenyl)-2,2,2-trifluoroacetamidine or 2,2-bis(hydroxyphenyl)-, 1, 1, 3. 3, 3-hexafluoropropionate, and the like. The preparation method is as follows:

(1) 30 40 parts of the fluorine-containing intermediate and 20 30 parts of the epichlorohydrin are added to the reaction vessel, and the solution is stirred and heated at 60-70 °C.

(2) Mix 5~10 parts NaOH and 15~20 parts deionized water into lye, and add to the reaction vessel for 1~1.5 hours. The temperature control is still controlled at 60-70 °C.

(3) The lye was added dropwise, and the reaction was refluxed at 70 ° C for 1.5 hours, and the system was milky yellow.

(4) Add deionized water and toluene, stir evenly, and then stand for liquid separation, remove the water layer, repeat the operation several times to remove the water layer, separate the organic phase, and distill the solvent to remove the solvent toluene and unreacted epoxy chloride under reduced pressure. Propionate, a pale yellow viscous resin.

The curing agent is an amine or an acid anhydride compound used in combination with a fluorine-containing epoxy resin, an amine such as ethylenediamine, diethylenetriamine, m-phenylenediamine or the like; an acid anhydride such as phthalic anhydride, Pyromellitic anhydride, methylcyclohexene tetracarboxylic anhydride, and the like.

The POSS structure is as follows:

Wherein R is a non-reactive group, including isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, phenyl, etc.; ^ is a reactive functional group, and the package mainly includes an amino group- or epoxy group-containing functional group. The silicon germanium coupling agent uses a silicon germanium coupling agent of the formula Y(CH ₂ ) nSi 3⁄4, wherein n=0~3; X is a chlorine group, a methoxy group, an ethoxy group, a methoxyethoxy group. A group, an acetoxy group or the like, and Y is an amino group or an epoxy group.

The reactive diluent is 1,6-hexanediol diacrylate, ?-hydroxyethyl methacrylate, tolyl glycidyl ether, castor oil polyglycidyl ether or ethylene glycol diglycidyl ether.

The dispersing agent is: an inorganic dispersing agent or an organic dispersing agent, and the inorganic dispersing agent is a silicate or an alkali metal phosphate such as water glass, sodium tripolyphosphate or sodium hexametaphosphate; and the organic dispersing agent is three Ethylhexylphosphoric acid, sodium dodecyl sulfate, methylpentanol, cellulose derivatives, guar gum, sodium carboxymethylcellulose or polyethylene glycol esters of fatty acids.

The light stabilizers are salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines or hindered amines.

The preparation method of the environmentally friendly fluorine-containing silicon heavy-duty anti-corrosion epoxy resin coating is as follows: according to the coating composition, firstly dissolving in the active diluent according to the silicon germanium coupling agent, the curing agent POSS and the dispersing agent, and stirring 0.5 The emulsion is obtained in ~1 hour; secondly, the fluorine-containing epoxy resin is added to the solution in batches under stirring, and stirred for 1 to 2 hours until homogeneous. When used, the anti-corrosion coating is applied to a metal substrate and then cured at about 80 to 120 ° C for 2 hours.

The environmentally friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating of the invention has the following characteristics;

(1) The fluorine-containing epoxy resin is directly synthesized by using a fluorine-containing monomer as an anticorrosive coating, thereby improving the fluorine content and improving the two hydrophobicity (hydrophobicity and oleophobicity) of the epoxy resin, thereby improving the anticorrosive property of the material. Compared with the common fluorine-containing coatings, it has a better bonding effect on the coated substrate, making the coating less likely to fall off.

(2) The rigid benzene ring of fluorine-containing epoxy resin and the C-F bond with strong interaction force are sensitive to heat, low viscosity at high temperature, good leveling property, no need for primer coating film, and strong coating film.

(3) The coating uses a reactive diluent that can participate in the reaction as a solvent, and does not contain a volatile organic solvent, thereby avoiding the solvent-vaporized solvent to cause pores in the drying, and the chloride ion penetration resistance is better, and is environmentally friendly. Anticorrosive coating;

(4) The POSS component added to the coating can improve the heat resistance of the coating. The POSS component can also be bonded to the epoxy group to participate in the curing reaction of the coating and have better compatibility with the substrate resin.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an infrared spectrum of a fluorine-containing epoxy resin of Example 1.

2 is a nuclear magnetic spectrum of a fluorine-containing epoxy resin of Example 1. detailed description

The present invention will be further described in detail below with reference to the embodiments.

Example 1

Preparation of fluorine-containing epoxy resin:

(1) Adding 35gl,l-bis(4-hydroxyphenyl)-1-(3-trifluoromethylphenyl)-2,2,2-trifluoroacetamidine and 26g of epichlorohydrin to the band In a three-necked flask equipped with a stir bar and a temperature control device, the solution was stirred and heated to 65 °C.

(2) Take 7g of NaOH and 15ml of deionized water to form an alkali solution, and add it to the reaction vessel within 1.5 hours. The temperature control is still controlled at 65 °C.

(4) Add 27 ml of deionized water and 54 ml of toluene, stir evenly, and then dispose to separate the liquid layer, remove the water layer, repeat the operation several times to remove the water layer, separate the organic phase, and distill the solvent to remove the solvent toluene and unreacted under reduced pressure. The epoxy chlorpromide gives a pale yellow viscous resin.

Preparation of fluorine-containing silicon heavy-duty epoxy resin coating:

4,4'-methylenebis(2,6-diethylaniline) 30 g, POSS 2 g, γ-glycidyloxypropyltrimethoxysilane oxime 0.5 g, ethylene glycol diglycidyl ether 25 g, 1.5 g of sodium hexametaphosphate, 0.3 g of N-(ethoxycarbonylphenyl)-Ν'-methyl-oxime-phenylphenylhydrazine were uniformly mixed under a high-speed disperser, and 60 g of the above was added under a low-speed disperser. A fluorine-containing epoxy resin prepared. The uniformly stirred slurry was applied to a metal substrate and cured at 150 ° C for 2 hours.

Example 2

(1) Adding 30 gl,l-bis(4-hydroxyphenyl)-1-phenyl-2,2,2-trifluoroacetamidine and 28 g of epichlorohydrin to a stirrer and a temperature control device In a three-necked flask, the solution was stirred and heated to 65 °C.

(2) Take 6g of NaOH and 17ml of deionized water to form an alkali solution, and add it to the reaction vessel within 1.5 hours. The temperature control is still controlled at 65 °C.

Preparation of fluorosilicone heavy-duty epoxy resin coating:

4,4'-methylenebis(2,6-diethylaniline) 35g, POSS 1.5g, γ-glycidyloxypropyltrimethoxy 0. 5g, ethylene glycol diglycidyl ether 30g, sodium hexametaphosphate 1.5g, N-(ethoxycarbonylphenyl) - _Ν '-methyl- _Ν '-phenyl formazan _0. 3g The mixture was uniformly mixed under a high speed disperser, and _{60 g} of the fluorine-containing epoxy resin prepared above was added under a low speed disperser. The uniformly stirred slurry was applied to a metal substrate and cured at 150 ° C for 2 hours.

Example 3

(1) 30 g (3-trifluoromethylbenzene) hydroquinone and 32 g of epichlorohydrin were added to a three-necked flask equipped with a stir bar and a temperature control device, and the solution was stirred and heated at 65 °C.

(2) Take 8g of NaOH and 17ml of deionized water to form an alkali solution, and add it to the reaction vessel within 1.5 hours. The temperature control is still controlled at 65 °C.

Preparation of fluorosilicone heavy-duty epoxy resin coating:

4,4'-methylenebis(2,6-diethylaniline) 35g, POSS 2g, γ-glycidyloxypropyltrimethoxysilane lg, ethylene glycol diglycidyl ether 30g, six partial 1.5 g of sodium phosphate, 0.3 g of N-(ethoxycarbonylphenyl)-Ν'-methyl-oxime-phenylphenylhydrazine were uniformly mixed under a high-speed disperser, and 70 g of the above-prepared content was added under a low-speed disperser. Fluorine epoxy resin. The uniformly stirred slurry was applied to a metal substrate and cured at 150 ° C for 2 hours.

Example 4

(1) Add 30g of 2,2-bis(hydroxyphenyl)-, 1, 1, 3. 3, 3-hexafluoropropene and 26g of epoxidized chlorohydrazine to a three-necked flask with a stir bar and temperature control device The solution was stirred and heated to 65 °C.

(2) Take 6g of NaOH and 15ml of deionized water to form an alkali solution, and add it to the reaction vessel within 1.5 hours. The temperature control is still controlled at 65 °C.

Preparation of fluorosilicone heavy-duty epoxy resin coating:

4,4'-methylenebis(2,6-diethylaniline) 40g, POSS lg, γ-glycidyloxypropyltrimethoxy Silicon germanium lg, ethylene glycol diglycidyl ether 20g, sodium hexametaphosphate 1.5g, N-(ethoxycarbonylphenyl)-Ν'-methyl-Ν'-phenylformamidine 0.3g in high-speed dispersing machine Under uniform mixing, 70 g of the fluorine-containing epoxy resin prepared above was added under a low speed disperser. The uniformly stirred slurry was applied to a metal substrate and cured at 150 ° C for 2 hours.

The fluorine-containing heavy anti-corrosion paint obtained by the embodiment provided by the invention has good leveling property, firm adhesion, excellent weather resistance and can be used in various environmental systems, and the main test performances thereof are shown in Table 1. Table 1

The above embodiments are only used to further illustrate a gas control device of the present invention, but the present invention is not limited to the embodiments, and any simple modifications, equivalent changes, and modifications made to the above embodiments in accordance with the technical spirit of the present invention are It falls within the scope of protection of the technical solution of the present invention.

Industrial applicability

The fluorine-containing silicon heavy-duty anti-corrosion epoxy resin coating prepared by the invention replaces the traditional volatile organic solvent by using the reactive diluent which can participate in the reaction, thereby avoiding the solvent volatilization caused by the solvent evaporation of the solvent-based coating, and the chloride ion permeation resistance is more Good, it is an environmentally friendly anti-corrosion coating, especially suitable for harsh environments such as the ocean. At the same time, the fluorine-containing epoxy resin used is sensitive to heat due to the rigid benzene ring and the CF bond with strong interaction force. The high temperature viscosity is low, the leveling property is good, the primer coating film is not needed, the construction process is simple, and the coating film is firm. Does not fall off. The POSS component added to the coating improves the heat resistance of the coating and meets the needs of extreme environments.

Claims

Rights request

1. An environmentally friendly fluorine-containing silicone heavy anti-corrosion epoxy resin coating, characterized in that the formula of the coating is (parts by weight): 30-70 parts of fluorine-containing epoxy resin, 10-40 parts of curing agent, POSS 0.1 ~5 parts, 0.5-5 parts of silicone coupling agent, 10-30 parts of reactive diluent, 0.5-3 parts of dispersant, and 0.3-1 part of light stabilizer.

2. An environmentally friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating according to claim 1, characterized in that the fluorine-containing epoxy resin is synthesized from a fluorine-containing intermediate and epoxy chloropropane under alkali catalysis , where the fluorine-containing intermediate is (3-trifluoromethylbenzene) hydroquinone, or 1,1-bis(4-hydroxyphenyl)-1-(3-trifluoromethylphenyl)-2, 2, 2-trifluoroethane, or 1, 1-bis(4-hydroxyphenyl)-1-phenyl-2, 2, 2-trifluoroethane, or 1, 1-bis(4-hydroxyphenyl) base) -1- (4-fluorophenyl) -2, 2, 2-trifluoroethane or 2, 2-bis (hydroxyphenyl) -, 1, 1, 3. 3, 3-hexafluoropropane kind of.

3. An environment-friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating according to claim 2, characterized in that the preparation method of the fluorine-containing epoxy resin is as follows:

(1) Add 30-40 parts of fluorine-containing intermediates and 20-30 parts of epoxychloropropane into the reaction vessel, stir the solution, and raise the temperature to 60-70°C;

(2) Use 5 to 10 parts of NaOH and 15 to 20 parts of deionized water to prepare an alkali solution, add it to the reaction vessel in 1 to 1.5 hours, and still control the temperature at 60-70°C;

(3) After adding the alkali solution dropwise, reflux the reactant at 70°C for 1.5 hours. The system will appear milky yellow;

(4) Add deionized water and toluene, stir evenly, let it stand for liquid separation, remove the water layer, repeat the operation several times to remove the water layer, separate the organic phase, and evaporate under reduced pressure to remove the solvent toluene and unreacted epoxy chlorine Propylene yields a light yellow viscous resin.

4. An environmentally friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating according to claim 3, characterized in that the curing agent is an amine or acid anhydride compound used in conjunction with the fluorine-containing epoxy resin, including ethanol. Diamine, diethylenetriamine, m-phenylenediamine; phthalic anhydride, pyromellitic anhydride, methylcyclohexenetetracarboxylic anhydride.

5. An environment-friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating according to claim 4, characterized in that the POSS structure is as follows:

Where R is a non-reactive group, including isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, phenyl, etc.; ! ^ is an active functional group, including mainly functional groups containing amino or epoxy groups.

6. An environmentally friendly fluorine-containing silicone heavy anti-corrosion epoxy resin coating according to claim 5, characterized in that the silane coupling agent adopts a silane coupling agent with the general formula Y( _CH2 )nSi¾ , where n=0~3; X is chlorine group, methoxy group, ethoxy group, methoxyethoxy group, acetoxy group, Y is amino group or epoxy group.

7. An environment-friendly fluorosilicone heavy anti-corrosion epoxy resin coating according to claim 6, characterized in that the reactive diluent is 1,6-hexanediol diacrylate, methacrylic acid-β- One or more of hydroxyethyl ester, toluene glycidyl ether, castor oil polyglycidyl ether or ethylene glycol diglycidyl ether.

8. An environment-friendly fluorosilicone heavy anti-corrosion epoxy resin coating according to claim 7, characterized in that the dispersant is: an inorganic dispersant or an organic dispersant, and the inorganic dispersant is a silicate Or alkali metal phosphates, including water glass, sodium tripolyphosphate or sodium hexametaphosphate; the organic dispersant includes triethylhexyl phosphate, sodium lauryl sulfate, methylpentanol, cellulose derivatives, Glue, sodium carboxymethylcellulose or fatty acid polyethylene glycol esters.

9. An environmentally friendly fluorine-containing silicon heavy anti-corrosion epoxy resin coating according to claim 8, characterized in that the light stabilizer is salicylate, benzophenone, benzotriazole, substituted One or more of acrylonitriles, triazines or hindered amines. .