CN105131812A - Nano-particle modified coating for metal and preparation method therefor - Google Patents
Nano-particle modified coating for metal and preparation method therefor Download PDFInfo
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- CN105131812A CN105131812A CN201510533035.6A CN201510533035A CN105131812A CN 105131812 A CN105131812 A CN 105131812A CN 201510533035 A CN201510533035 A CN 201510533035A CN 105131812 A CN105131812 A CN 105131812A
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Abstract
The present invention discloses a nano-particle modified coating for metal. The nano-particle modified coating for metal comprises the following raw materials in parts by weight: 0.01-0.02 part of chloroplatinic acid, 600-700 parts of diphenylmethane diisocyanate, 340-370 parts of 2-(perfluoroalkyl)ethanol, 450-490 parts of polyoxytertramethylene glycol, 1-2 parts of 1,4-butylene glycol, 1.3-2 parts of 4-vinylcyclohexane, 90-100 parts of nano silicon dioxide, 16-20 parts of hydrogen-containing silicone oil, 0.6-1 part of silane coupling agent KH560, 2-3 parts of methanol, 14-20 parts of calcium acetylacetonate, 1-2 parts of alkanolamide, and 40-50 parts of dimethyl fumarate. According to the nano-particle modified coating for metal, silicone oil modified nano-particles are well embedded in the surface of a coating film formed by polyurethane, so that a micro-nano double-scale structure is constructed and the roughness of a material surface is greatly improved, so that the excellent ultra hydrophobicity is displayed and the service life of the material is prolonged.
Description
Technical field
The present invention relates to metal anti-corrosive paint technical field, particularly relate to a kind of metal nanometer particle-modified coating and preparation method thereof.
Background technology
Urethane is widely used in Mine haul with the antifatigue toughness of its excellence and erosion resistance, the dry state anti scuffing in the fields such as concrete mixer lining and silt hygrometric state anti scuffing coating, along with updating of urethane physicals and construction technology, elastic polyurethane coating is used as underwater concrete in hydro project, steel construction resistant abrasion protective coating is also more and more frequent, and show good high-low temperature resistant toughness, fatigue resistance and cavitation polishing machine, achieve good effect, but also there is some limitation, such as, wetting ability in polyurethane chain-CH2OH group easily absorbs water, urethane water resistance is caused to decline, polyurethane coating anti-cavitation polishing machine and work-ing life is had a strong impact under water surrounding,
Main method at present about raising Water-resistance of Waterborne Polyurethane is in polyurethane chain, introduce hydrophobic structure and crosslinking structure, wherein introduced hydrophobic structure is fluorine-containing groups and siliceous segment mainly, but siliceous segment can reduce the adhesive property of polyurethane coating to base material usually, comparatively speaking, fluorine element is expensive, but because fluorine-containing groups urethane (FPU) has the advantage of urethane and fluorochemicals concurrently, show high strength, antifatigue and high shock-absorbing capacity, water-fast, solvent resistant and chemicals, lower surface tension and low-friction coefficient etc., the research of current FPU is made still to become upsurge, and by fluorine, silicon segment applies in polyurethane coating simultaneously, its water repelling property will be improved greatly, good protected effect can be played to underwater engineering metallic substance.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of metal nanometer particle-modified coating and preparation method thereof.
The present invention is achieved by the following technical solutions:
The nanometer particle-modified coating of a kind of metal, it is made up of the raw material of following weight parts:
Platinic chloride 0.01-0.02, diphenylmethanediisocyanate 600-700, perfluoroalkyl ethyl alcohol 340-370, PTMG 450-490, BDO 1-2,4 vinyl epoxy cyclohexane 1.3-2, nano silicon 90-100, containing hydrogen silicone oil 16-20, silane coupling agent KH5600.6-1, methyl alcohol 2-3, calcium acetylacetonate 14-20, alkylolamide 1-2, dimethyl fumarate 40-50.
A described metal preparation method for nanometer particle-modified coating, comprises the following steps:
(1) joined by 4 vinyl epoxy cyclohexane in 2-3 times of toluene, add Platinic chloride, be heated to 40-45 DEG C, drip containing hydrogen silicone oil, after dropwising, under nitrogen protection, continue heating 10-12 hour, underpressure distillation removing toluene, obtains epoxy modified polysiloxane;
(2) joined in 10-12 times of dehydrated alcohol by above-mentioned silane coupling agent KH560, add nano silicon, be uniformly mixed 10-12 hour under nitrogen protection, distillation removing ethanol, vacuum-drying, obtains amino modified nanoparticle;
(3) above-mentioned amino modified nanoparticle is joined in 16-20 times of dehydrated alcohol, ultrasonic disperse 3-5 minute, raised temperature is 50-60 DEG C, drip epoxy modified polysiloxane, stirring reaction 10-12 hour under nitrogen protection after dropwising, suction filtration, by filter cake vacuum-drying, obtains silicon oil modified nanoparticle;
(4) by above-mentioned PTMG vacuum hydro-extraction 2-3 hour at 80-90 DEG C;
(5) being joined by perfluoroalkyl ethyl alcohol in 2-3 times of DMF, stir, is liquid a;
(6) joined in 16-20 times of DMF by above-mentioned alkylolamide, stir, add calcium acetylacetonate, raised temperature is 60-70 DEG C, adds dimethyl fumarate, insulated and stirred 30-40 minute, obtains esterification calcium;
(7) get the 75-80% of above-mentioned diphenylmethanediisocyanate weight, mix with esterification calcium, 300-400 rev/min is stirred 10-20 minute, obtains modified monomer;
(8) above-mentioned modified monomer is joined in 2.8-3 DMF doubly, stir, raised temperature is 60-65 DEG C, passes into nitrogen, drips above-mentioned liquid a, insulation reaction 2-3 hour at the temperature disclosed above after dropwising, add the PTMG after dehydration, stirring reaction 50-60 minute, add remaining diphenylmethanediisocyanate, 1,4-butyleneglycol, raised temperature is 75-80 DEG C, insulation reaction 1.8-2 hour, obtains base polyurethane prepolymer for use as;
(9) in above-mentioned base polyurethane prepolymer for use as, add silicon oil modified nanoparticle, raised temperature is 80-85 DEG C, adds methyl alcohol, ultrasonic disperse 3-5 minute, and cooling discharging obtains described coating.
Advantage of the present invention is:
(1) film that the present invention is formed has good water resisting property:
Because the fluorocarbon chain of low surface energy forms micro/nano level raised structures to material surface migration on surface, the structural arrangement of these projections forms the organic fluorine film with " lotus leaf hydrophobic effect ", thus the water tolerance of film is strengthened;
(2) the present invention formed film and metal base there is good cohesiveness;
The fluorine carbon structure of low surface energy hinders moisture to the dipping of bonding interface and diffusion, thus ensure that the stability of cohesive force between urethane and metal base;
(3) film that invention is formed has high resistance erosion property;
There is a large amount of hydrogen bond structure in urethane therein, covalent linkage in these hydrogen bond structure relative polymer has undemanding selectivity and directivity, and be mainly present in soft, hard section is alternate and play physical crosslinking effect, because the fluorin radical polarity introduced is high, the intermolecular internal cohesive energy of fluorine-containing F-MDI in hard section component is increased, improve Young's modulus and the tensile strength of hard segment domains, in addition the bond energy on nearly surface is higher, C-F chain has good intensity and water tolerance, prevent wearing and tearing further expanding to coating depths, a part is passed to soft section of phase of elastic state by hard segment domains from the ballistic work that wear particle and bubble are crumbled and fall simultaneously, a part of ballistic work is cushioned by the motion of soft segment molecule chain, thus improve the anti-erosion property of fluorochemical urethane,
Silicon oil modified nanoparticle is well embedded in the film coated surface that urethane is formed by the present invention, construct micro-nano double scales structure, substantially increase the roughness of material surface, it is made to present remarkable super-hydrophobicity, simultaneously the combination of the SiO2 nanoparticle modified of this epoxy modified polysiloxane and urethane is comparatively firm, be difficult to be immersed in water and rinse out, extend the work-ing life of material.
Embodiment
The nanometer particle-modified coating of a kind of metal, it is made up of the raw material of following weight parts:
Platinic chloride 0.01, diphenylmethanediisocyanate 600, perfluoroalkyl ethyl alcohol 340, PTMG 450, Isosorbide-5-Nitrae butyleneglycol 1,4 vinyl epoxy cyclohexane 1.3, nano silicon 90, containing hydrogen silicone oil 16, silane coupling agent KH5600.6, methyl alcohol 2, calcium acetylacetonate 14, alkylolamide 1, dimethyl fumarate 40.
A described metal preparation method for nanometer particle-modified coating, comprises the following steps:
(1) joined in 2 times of toluene by 4 vinyl epoxy cyclohexanes, add Platinic chloride, be heated to 40 DEG C, drip containing hydrogen silicone oil, after dropwising, under nitrogen protection, continue heating 10 hours, underpressure distillation removing toluene, obtains epoxy modified polysiloxane;
(2) joined in 10 times of dehydrated alcohols by above-mentioned silane coupling agent KH560, add nano silicon, be uniformly mixed 10 hours under nitrogen protection, distillation removing ethanol, vacuum-drying, obtains amino modified nanoparticle;
(3) join in 16 times of dehydrated alcohols by above-mentioned amino modified nanoparticle, ultrasonic disperse 3 minutes, raised temperature is 50 DEG C, drip epoxy modified polysiloxane, stirring reaction 10 hours under nitrogen protection after dropwising, suction filtration, by filter cake vacuum-drying, obtain silicon oil modified nanoparticle;
(4) by the vacuum hydro-extraction 2 hours at 80 DEG C of above-mentioned PTMG;
(5) being joined by perfluoroalkyl ethyl alcohol in 2 times of DMFs, stir, is liquid a;
(6) joined in 16 times of DMFs by above-mentioned alkylolamide, stir, add calcium acetylacetonate, raised temperature is 60 DEG C, adds dimethyl fumarate, and insulated and stirred 30 minutes, obtains esterification calcium;
(7) get 75% of above-mentioned diphenylmethanediisocyanate weight, mix with esterification calcium, 300 revs/min are stirred 10 minutes, obtain modified monomer;
(8) above-mentioned modified monomer is joined in the DMF of 2.8 times, stir, raised temperature is 60 DEG C, passes into nitrogen, drips above-mentioned liquid a, insulation reaction 2 hours at the temperature disclosed above after dropwising, add the PTMG after dehydration, stirring reaction 50 minutes, adds remaining diphenylmethanediisocyanate, 1,4 butyleneglycols, raised temperature is 75 DEG C, and insulation reaction 1.8 hours, obtains base polyurethane prepolymer for use as;
(9) in above-mentioned base polyurethane prepolymer for use as, add silicon oil modified nanoparticle, raised temperature is 80 DEG C, adds methyl alcohol, ultrasonic disperse 3 minutes, and cooling discharging, obtains described coating.
Performance test:
Water-intake rate 0.0149%, before water suction, cohesive force is 12.72MPa, keeps the high cohesive force of 10.40MPa, cavitation corrosion amount 0.9347 × 10 after water suction immersion test soaks 3200h
-3kg.
Claims (2)
1. the nanometer particle-modified coating of metal, is characterized in that what it was made up of the raw material of following weight parts:
Platinic chloride 0.01-0.02, diphenylmethanediisocyanate 600-700, perfluoroalkyl ethyl alcohol 340-370, PTMG 450-490, BDO 1-2,4 vinyl epoxy cyclohexane 1.3-2, nano silicon 90-100, containing hydrogen silicone oil 16-20, silane coupling agent KH5600.6-1, methyl alcohol 2-3, calcium acetylacetonate 14-20, alkylolamide 1-2, dimethyl fumarate 40-50.
2. a metal as claimed in claim 1 preparation method for nanometer particle-modified coating, is characterized in that comprising the following steps:
(1) joined by 4 vinyl epoxy cyclohexane in 2-3 times of toluene, add Platinic chloride, be heated to 40-45 DEG C, drip containing hydrogen silicone oil, after dropwising, under nitrogen protection, continue heating 10-12 hour, underpressure distillation removing toluene, obtains epoxy modified polysiloxane;
(2) joined in 10-12 times of dehydrated alcohol by above-mentioned silane coupling agent KH560, add nano silicon, be uniformly mixed 10-12 hour under nitrogen protection, distillation removing ethanol, vacuum-drying, obtains amino modified nanoparticle;
(3) above-mentioned amino modified nanoparticle is joined in 16-20 times of dehydrated alcohol, ultrasonic disperse 3-5 minute, raised temperature is 50-60 DEG C, drip epoxy modified polysiloxane, stirring reaction 10-12 hour under nitrogen protection after dropwising, suction filtration, by filter cake vacuum-drying, obtains silicon oil modified nanoparticle;
(4) by above-mentioned PTMG vacuum hydro-extraction 2-3 hour at 80-90 DEG C;
(5) being joined by perfluoroalkyl ethyl alcohol in 2-3 times of DMF, stir, is liquid a;
(6) joined in 16-20 times of DMF by above-mentioned alkylolamide, stir, add calcium acetylacetonate, raised temperature is 60-70 DEG C, adds dimethyl fumarate, insulated and stirred 30-40 minute, obtains esterification calcium;
(7) get the 75-80% of above-mentioned diphenylmethanediisocyanate weight, mix with esterification calcium, 300-400 rev/min is stirred 10-20 minute, obtains modified monomer;
(8) above-mentioned modified monomer is joined in 2.8-3 DMF doubly, stir, raised temperature is 60-65 DEG C, passes into nitrogen, drips above-mentioned liquid a, insulation reaction 2-3 hour at the temperature disclosed above after dropwising, add the PTMG after dehydration, stirring reaction 50-60 minute, add remaining diphenylmethanediisocyanate, 1,4-butyleneglycol, raised temperature is 75-80 DEG C, insulation reaction 1.8-2 hour, obtains base polyurethane prepolymer for use as;
(9) in above-mentioned base polyurethane prepolymer for use as, add silicon oil modified nanoparticle, raised temperature is 80-85 DEG C, adds methyl alcohol, ultrasonic disperse 3-5 minute, and cooling discharging obtains described coating.
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| CN201510533035.6A CN105131812A (en) | 2015-08-27 | 2015-08-27 | Nano-particle modified coating for metal and preparation method therefor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019215324A1 (en) * | 2018-05-11 | 2019-11-14 | Ucl Business Ltd | (super)hydrophobic material and coating |
| CN111234167A (en) * | 2020-04-03 | 2020-06-05 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585902A (en) * | 2009-06-26 | 2009-11-25 | 湖南大学 | Fluorinated polyurethane nanometer composite material and preparation method thereof |
-
2015
- 2015-08-27 CN CN201510533035.6A patent/CN105131812A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585902A (en) * | 2009-06-26 | 2009-11-25 | 湖南大学 | Fluorinated polyurethane nanometer composite material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019215324A1 (en) * | 2018-05-11 | 2019-11-14 | Ucl Business Ltd | (super)hydrophobic material and coating |
| CN112262167A (en) * | 2018-05-11 | 2021-01-22 | Ucl商业有限公司 | (super) hydrophobic materials and coatings |
| CN111234167A (en) * | 2020-04-03 | 2020-06-05 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN111234167B (en) * | 2020-04-03 | 2021-02-19 | 赵牧青 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
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