CN101289591B - Environment protection type corrosion resistant coating and method for preparing same - Google Patents
Environment protection type corrosion resistant coating and method for preparing same Download PDFInfo
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- CN101289591B CN101289591B CN2008101148138A CN200810114813A CN101289591B CN 101289591 B CN101289591 B CN 101289591B CN 2008101148138 A CN2008101148138 A CN 2008101148138A CN 200810114813 A CN200810114813 A CN 200810114813A CN 101289591 B CN101289591 B CN 101289591B
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Abstract
The invention provides an environment-protection corrosion resistant material and a method for making the same, and is used in the surface corrosion protection and protection of a metal material. The environment-protection corrosion resistant material is obtained through the following method that: low-molecular liquid polybutadiene which is grafted with maleic anhydride is used as basic resin and non-benzene series material solvent is used as a diluent agent; and a curing agent is added to carry out thermal cross-linking. The compositions in percentage by weight of the coating material are: 20 to 70 percent of maleated low molecular liquid polybutadiene, 10 to 50 percent of diluent agent, 0.5 to 5 percent of crosslinking agent, 0.5 to 5 percent of curing agent and 5 to 25 percent of pigment. The coating shows excellent corrosion resistance, fingerprint resistance, water resistance, chemical resistance and ideal physical and mechanical properties when used; moreover, the coating material has simple preparation process and easy generalization, and is suitable to be used in a metal surface; meanwhile, the coating material is particularly suitable to be used as a corrosion-resistant coating material on metal surfaces such as a color-coated plate coating material on a galvanized plate and a corrosion-resistant decorative material on a magnesium alloy surface, thereby having an ideal application prospect.
Description
Technical field
The present invention relates to the Chemicals field, more particularly relate to environment protection type corrosion resistant coating.
Background technology
Corrosion resistant coating is that base resin adds various auxiliary agents, filler forms through certain Process configuration with epoxy, polyester, urethane and fluorine resin etc. mainly.The Resins, epoxy corrosion resisting property is good, shows as hard and crisp but solidify the back performance; The antiseptic property of urethane resin is good, but the cost height; Vibrin needs high solidification value and kindliness poor; Fluorine resin antiseptic property excellence but execution conditions harshness and cost are very high.In addition, because the restriction of execution conditions or coating property, these resins mainly are that the benzene series thing is a thinner with organic solvent mostly, cause environmental pollution easily.Along with the growing interest of people to environment and health, various countries use " volatile organic solvent " restriction (TVOC), various novel environment friendly corrosion resistant coatings are developed, and mainly comprise with non-benzene series thing solvent being that thinner and water are two kinds of coating systems of dispersion agent.Only however belong to the organic solvent of TVOC limited field such as alcohols, ester class equal solvent is very limited to the influence of environment, is considered to environmental protection coating material with the coating of this kind solvent preparation; In addition, be the coating that dispersion agent is prepared into water, do not contain the coating that poisonous additive obtains and belong to environmental protection coating material yet.
Divinol claims that again liquid polybutadiene is the oligomer of divinyl, and relative molecular mass is generally 500-5000, mainly is used as a rubber crosslinker etc.; Its modified product can also be as the base resin that is used for coating except that being used as linking agent.Publication number CN1184112A has described the technological method of preparation divinol first in China; The technology of low molecule divinyl as pipeline of oil production equipment wax removing agent described in the patent application of publication number CN1218068, has the advantage that consumption is few, efficient is high.But China does not also have the utilisation technology of divinol modified product.It is the method that solidifying agent prepares the fast setting insulation compound with the superoxide that U.S. Pat P4250276 has described divinol.U.S. Pat P3959198 has described the technology that toxilic acid anhydridization divinyl and other unsaturated polyester prepare cathode electrophoresis dope, U.S. Pat P4202746 has introduced the technological approaches that the epoxidation divinol prepares cathode electrodip painting, has obtained toughness coated material preferably at coating metal surfaces.These technology are mostly a kind of as film-forming components of divinol, and seldom as main film forming substance, material proportioning and technology are not and the similar bibliographical information of the present invention.
Summary of the invention
It is base resin that the present invention proposes with toxilic acid anhydridization low molecular weight liquid polyhutadiene, is that thinner makes environment protection type corrosion resistant coating with non-benzene series thing solvent.This coating lacquer film hardness height and good toughness, wear resisting property are good, anti-finger printing can be good, highly corrosion resistant and to ground adhesion property height, simultaneously preparation technology is simple, aspect the protection against corrosion of color coated metal coating that is used for galvanized sheet and magnesium alloy and the decoration good future is being arranged.
The present invention is a main raw material with toxilic acid anhydridization low molecular weight liquid polyhutadiene, prepares environment protection type corrosion resistant coating by adding other component, and the weight fraction proportioning of its raw material is as follows:
Toxilic acid anhydridization low molecular weight liquid polyhutadiene 20～70%
Thinner 10～50%
Linking agent 0.5～5%
Solidifying agent 0.5～5%
Pigment 5～25%
Toxilic acid anhydridization low molecular weight liquid polyhutadiene of the present invention is meant that maleic anhydride and divinol are the product of 500-5000 by the molecule relative mass that grafting obtains.
Described thinner comprises ester class such as ethyl acetate, diethyl oxalate, butyl methacrylate, alcohol ethers such as butyl glycol ether, ethylene glycol ethyl ether, ketone such as butanone, pimelinketone, one or more in the solvent such as non-benzene series thing such as alcohols such as butanols, Virahol etc. mix.
Described linking agent is to contain more than two amino organic amine, comprises that a kind of in propylene diamine, hexanediamine, diethyl toluene diamine, triethylene tetramine, diethanolamine, the di-alcohol diamines or some kinds mix.
Described solidifying agent is a superoxide, comprise benzoyl peroxide, hydrogen peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, dicumyl peroxide, dibenzoyl peroxide, 2, in 5-dimethyl-2, the 5 di-t-butyl peroxy hexane one or several mixes.
Described pigment comprises a kind of of mineral compound such as red iron oxide, chrome yellow, iron oxide black, gives the coating shades of colour.
The preparation technology of environment protection type corrosion resistant coating of the present invention is as follows:
A, stirring are diluted toxilic acid anhydridization low molecular weight liquid polyhutadiene down with thinner, obtain the solution that resin content is 20～70 weight %;
B, the linking agent that will be equivalent to toxilic acid anhydridization low molecular weight liquid polyhutadiene 0.5～5 weight % add a solution, stir 0.5-1 hour;
C, the peroxide firming agent that is equivalent to toxilic acid anhydridization low molecular weight liquid polyhutadiene 0.5～5 weight % is added in the b solution, stir the coating that was not contained pigment in 0.5-1.0 hour;
D or the pigment that is equivalent to toxilic acid anhydridization low molecular weight liquid polyhutadiene 5～25 weight % added in the described coating of c obtained the coating of different colours in high-speed stirring 0.5-1 hour.
Compared with prior art, the present invention is base resin with the low-molecular-weight oligomer, can obtain the coating of high solids content organic constituent, is thinner with the environment-friendly type solvent, and preparation technology is simple, is applicable to the anticorrosion protection of multiple metallic surface.Coating of the present invention is owing to wherein contain two keys, and can obtain the hydro carbons main chain after the curing has good water tolerance and chemical resistant properties; The present invention adopts amido and anhydride reaction and makes the acid anhydrides open loop, promotes to be cross-linked to form three-dimensional net structure; Amination reaction is introduced a large amount of hydroxyls and be can further improve the sticking power of coating on metallic matrix in addition.After testing, coating hardness can reach 3-5H, and sticking power can reach the 0-1 level, and impact strength is more than 60Kg.cm, and the salt spray resistance experiment reaches more than the 750h.
Embodiment
Adding 62ml butanols and 5ml butyl methacrylate stir in the embodiment 1:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene.Add 0.1 gram propylene diamine stirring 25 minutes, add 5 gram ferric oxide red colorant 1200r/min and stirred 30 minutes, the benzoyl peroxide and the 0.06 gram cyclohexanone peroxide that continue adding 0.04 gram stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the magnesium alloy of oil removing and processing of rust removing, and 180 ℃ were toasted 30 minutes, obtained the coating of 10～13 microns of thickness.Coating hardness 3H, sticking power are the 0-1 level, and impact strength is 30Kg.cm, and the salt spray resistance experiment reaches 350h.
Adding 60ml butanone, 5ml butyl methacrylate, 5ml butanols stir in the embodiment 2:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene.Add 1 gram di-alcohol diamines and 0.5 and restrain diethanolamine stirring 25 minutes, 1200r/min stirring 30 minutes continues to add 0.2 dibenzoyl peroxide that restrains and 0.2 and restrains dicumyl peroxide stirring 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the magnesium alloy of degreasing and rust removal processing, and 180 ℃ were toasted 30 minutes, obtained the coating of 10～12 microns of thickness.Coating hardness 2H, sticking power are the 0-1 level, and impact strength is 35Kg.cm, and the salt spray resistance experiment reaches 300h.
Adding 60ml butyl glycol ether and 8ml Jia Jibingxisuanyizhi stir in the embodiment 3:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene.Add 0.5 gram diethanolamine and stirred 25 minutes, adding 1 gram adds chrome yellow 1200r/min and stirred 30 minutes, continues 2 of adding 0.3 gram, and 5-dimethyl-2,5 di-t-butyl peroxy hexane stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the galvanized sheet of degreasing and rust removal processing, and 280 ℃ were toasted 1 minute, obtained the coating of 8～10 microns of thickness.Coating hardness 3-4H, sticking power are the 0-1 level, and impact strength is 30Kg.cm, and the salt spray resistance experiment reaches 600h.
Adding 25ml butyl glycol ether and 5ml butanols stir in the embodiment 4:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene.Add 1 diamines of restraining oneself and stirred 25 minutes, add 5 gram chrome yellow 1200r/min and stirred 30 minutes, the benzoyl peroxide and the 0.8 gram dicumyl peroxide that continue to add 0.2 gram stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the galvanized sheet of degreasing and rust removal processing, and 280 ℃ were toasted 1 minute, obtained the coating of 22～25 microns of thickness.Coating hardness 4-5H, sticking power are the 0-1 level, and impact strength is 50Kg.cm, and the salt spray resistance experiment reaches 740h.
Adding 22ml diethyl oxalate and 5ml butanols stir in the embodiment 5:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene.Add 1 diamines of restraining oneself and stirred 25 minutes, add 3 gram ferric oxide red colorant 1200r/min and stirred 30 minutes, continue to add the benzoyl peroxide and 0.8 gram 2 of 0.02 gram, 5-dimethyl-2,5 di-t-butyl peroxy hexane stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the magnesium alloy of degreasing and rust removal processing, and 180 ℃ were toasted 30 minutes, obtained the coating of 22～25 microns of thickness.Coating hardness 3H, sticking power are 0 grade, and impact strength is 60Kg.cm, and the salt spray resistance experiment reaches 350h.
Adding 25ml butyl glycol ether and 6ml butanone stir in the embodiment 6:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene.Add 0.1 gram diethanolamine stirring 25 minutes, add 5 gram ferric oxide red colorant 1200r/min and stirred 30 minutes, the benzoyl peroxide and the 0.2 gram dicumyl peroxide that continue adding 0.8 gram stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the galvanized sheet of degreasing and rust removal processing, and 280 ℃ were toasted 1 minute, obtained the coating of 18～21 microns of thickness.Coating hardness 4-5H, sticking power are 0 grade, and impact strength is 50Kg.cm, and the salt spray resistance experiment reaches 690h.
Adding the 8ml butyl glycol ether in the embodiment 7:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene stirs.Add 3.0 diamines of restraining oneself and stirred 25 minutes, add 4 gram ferric oxide red colorant 1200r/min and stirred 30 minutes, the benzoyl peroxide and the 0.2 gram cyclohexanone peroxide that continue to add 0.2 gram stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the galvanized sheet of degreasing and rust removal processing, and 280 ℃ were toasted 1 minute, obtained the coating of 33～35 microns of thickness.Coating hardness 4-5H, sticking power are 0 grade, and impact strength is 55Kg.cm, and the salt spray resistance experiment reaches 720h.
Adding 5ml butyl glycol ether, 5ml Jia Jibingxisuanyizhi and 1ml butanols in the embodiment 8:20 gram toxilic acid anhydridization low molecular weight liquid polyhutadiene stirs.Add 3 diethanolamine and stirred 25 minutes, 1200r/min stirred 30 minutes, continued to add the benzoyl peroxide and 0.6 gram 2 of 0.2 gram, and 5-dimethyl-2,5 di-t-butyl peroxy hexane stirred 20 minutes.The coating brushing or the dip-coating that obtain are passed through in the surface on the magnesium alloy of degreasing and rust removal processing, and 180 ℃ were toasted 25 minutes, obtained the coating of 38～41 microns of thickness.Coating hardness 4H, sticking power are 0 grade, and impact strength is 65Kg.cm, and the salt spray resistance experiment reaches 420h.
Claims (6)
1. the preparation method of an environment protection type corrosion resistant coating is characterized in that, preparation technology is:
A, stirring are diluted toxilic acid anhydridization low molecular weight liquid polyhutadiene down with thinner, obtain the solution that resin content is 20～70 weight %;
B, the linking agent that will be equivalent to toxilic acid anhydridization low molecular weight liquid polyhutadiene 0.5～5 weight % add a solution, stir 0.5-1 hour;
C, the peroxide firming agent that is equivalent to toxilic acid anhydridization low molecular weight liquid polyhutadiene 0.5～5 weight % is added in the b solution, stir the coating that was not contained pigment in 0.5-1.0 hour;
D or the pigment that is equivalent to toxilic acid anhydridization low molecular weight liquid polyhutadiene 5～25 weight % added in the described coating of c obtained the coating of different colours in high-speed stirring 0.5-1 hour;
Wherein said toxilic acid anhydridization low molecular weight liquid polyhutadiene is meant that maleic anhydride and divinol are the product of 500-5000 by the molecule relative mass that grafting obtains;
Described thinner is non-benzene series thing solvent;
Described linking agent is to contain organic amine amino more than two.
2. the preparation method of coating according to claim 1, it is characterized in that described thinner comprises one or more mixing in ethyl acetate, diethyl oxalate, butyl methacrylate, butyl glycol ether, ethylene glycol ethyl ether, butanone, pimelinketone, butanols, the Virahol.
3. the preparation method of coating according to claim 1 is characterized in that described linking agent comprises one or more mixing in propylene diamine, hexanediamine, diethyl toluene diamine, triethylene tetramine, diethanolamine, the di-alcohol diamines.
4. the preparation method of coating according to claim 1, it is characterized in that, described peroxide firming agent comprises benzoyl peroxide, hydrogen peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, dicumyl peroxide, dibenzoyl peroxide, 2, one or more mixing in 5-dimethyl-2, the 5 di-t-butyl peroxy hexane.
5. the preparation method of coating according to claim 1 is characterized in that, described pigment comprises a kind of of red iron oxide, chrome yellow, iron oxide black.
6. an environment protection type corrosion resistant coating is characterized in that being prepared by each method among the claim 1-5.
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| CN2008101148138A CN101289591B (en) | 2008-06-12 | 2008-06-12 | Environment protection type corrosion resistant coating and method for preparing same |
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| CN101289591B true CN101289591B (en) | 2011-12-14 |
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| KR101664765B1 (en) | 2013-12-04 | 2016-10-12 | 주식회사 쿠라레 | Modified liquid diene rubber and production method for same |
| CN104693367B (en) * | 2013-12-09 | 2019-04-23 | 沈阳经济区彰武神华橡塑助剂有限公司 | A kind of application of rubber adhesion promoter |
| CN105505065A (en) * | 2016-01-21 | 2016-04-20 | 苏州法斯特信息科技有限公司 | Fingerprint-resistant anticorrosive material and preparation method thereof |
| CN105925126A (en) * | 2016-05-06 | 2016-09-07 | 铜陵瑞莱科技有限公司 | Anti-microbial and mould-proof iron oxide red anti-corrosion paint and making method thereof |
| CN108912940A (en) * | 2018-08-14 | 2018-11-30 | 合肥岑遥新材料科技有限公司 | A kind of hot galvanizing color coating cladding plate production coating and preparation method thereof |
| CN110079203B (en) * | 2019-04-09 | 2020-10-30 | 北京科技大学 | Preparation and application method of water-resistant polyurethane coating material |
| CN115895379B (en) * | 2022-11-10 | 2023-08-29 | 浩力森涂料（上海）有限公司 | Castor oil modified emulsion resistant to alkali corrosion and preparation method thereof |
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