A kind of modified polyurethane resin coating and preparation method thereof
Technical field
The present invention relates to a kind of modified polyurethane resin coating and preparation method thereof.
Background technology
The Water-borne modification of urethane resin progressively replaces solvent-borne type, becomes the important directions of polyurethane industrial development.Urethane can be widely used in coating, tackiness agent, fabric coating and finishing composition, hide finishes, sheet surface treating agent and Fiber strength agent.Aqueous polyurethane emulsion is not only the coating comparing environmental protection, and has oil-proofness, sea water resistance, the premium properties such as wear-resistant and shock-resistant.Existingly formulating of recipe carried out to urethane and adjusts the requirement that uses with satisfied reality, and high performance aqueous polyurethane can be prepared by combining nano hybridization technique.Be main film forming matter with urethane or modified polyurethane, add appropriate auxiliary film forming matter component, the coating of auxiliary agent solvent is generally polyurethane coating.Polyurethane resin coating has and is obviously better than the specific of other coating, and the advantage of polyurethane coating is that paint film wear resistance is strong, and decorate properties is good, film adhesive is strong, and be coated with film elasticity high, film corrosion resistance nature is strong, bake out temperature wide ranges, high temperature resistant low-temperature performance is given prominence to, excellent insulation performance, assortment are many, but it also has obvious shortcoming, such as guarantor's light tint retention is poor, resin emulsion poor stability, easy damage coating, construction requirement is high.
When being applied to metallurgical metal process, the coating formed easily is corroded and produces destruction, if when such as metallic copper is in the etchant solution containing ion (such as chlorion, sulfate ion etc.), easily there is spot corrosion and (namely occur the corrosion aperture of developing in depth and breadth in local, metallic surface.Facts have proved in a large number; the anticorrosion ability of hybrid corrosion inhibitor benzotriazole and its derivative to copper is more satisfactory; Application comparison is extensive; its mechanism of action is the complex compound protective membrane that can form one deck benzotriazole and cupric ion on copper surface; and can in anode film forming; also at cathode filming, water and oxygen in water can be stoped to the diffusion of metallic surface, reduce the corrosion speed of copper.
As previously mentioned, along with the change of extraneous corrosive medium, need inhibiter to be discharged into longer by corrosion failure region, comparing effective means is directly joined by inhibiter in metal treatment coating, the effect of physical barrier that what coating mainly played is.But; this method of directly mixing sometimes can not play enough provide protections; inhibiter directly contacts with coating; in most of the cases; this system does not possess the ability of stimulating responsive release inhibiter; if when inhibiter solubleness is in the coating higher, the inhibiter of release fast can make coating generation foaming phenomena, and can destroy the integrity of coating.
Summary of the invention
The object of the present invention is to provide a kind of modified polyurethane resin coating, previously prepared good load is coated with the nanoparticle dispersion of inhibiter in urethane resin by it, thus coated for support materials inhibiter is mixed in coating, the loss that these carriers not only can avoid inhibiter unnecessary, and inhibiter directly destroys coating, and there is certain environment stimulating responsive, such as physical disturbance, PH change and illumination etc.
Technical scheme of the present invention is: a kind of modified polyurethane resin coating, described coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, hexanodioic acid 4-8 part, Synolac 1-5 part, epoxy resin 2-4 part, propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part, vinyl acetic monomer 5-10 part, phosphoric acid 0.5-1 part, deionized water 10-30 part; And polymer nano-particle 8-16 part.
The preparation method of this coating is as follows:
1) tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, vinyl acetic monomer 5-10 part are added reactor, stirrer is used fully to stir, be warming up to 90-100 DEG C, slowly add hexanodioic acid 4-8 part;
2) continue to add Synolac 1-5 part, epoxy resin 2-4 part, fully stir more than 1h,
3) chainextender, activator and catalyzer is added: add propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part according to dividing equally four minor tick 30min, phosphoric acid 0.5-1 part, then be incubated 80 degrees Celsius of more than 4h, add ionized water and carry out more than emulsification 30min;
4) polymer nano-particle being coated with benzotriazole is mixed in above-mentioned emulsion by ultrasonic disperse, at insulation 50 DEG C of abundant more than stirring reaction 1h, obtains modified polyurethane resin-Nanocomposites coating.
Compared with prior art, the coated inhibiter of polymer nano granules of the present invention, this polymer nano granules can in corrosive medium, there is pH value responsiveness, in external stimulus coating or when damaging coating, due to the soda acid change of corrosion local, inhibiter is discharged according to situation difference, in metallic surface absorption film-forming, play the effect of initiatively reparation, the polymer nano-particle that the multi-step emulsion polymerization that the present invention simultaneously adopts obtains coated inhibiter has superior coated function and stability, yield rate is higher, polymer nano-particle is combined with coating, be scattered in modified polyurethane resin, form effective corrosion-resistant composite coating, there is oil-proofness, sea water resistance, the premium properties such as wear-resistant and shock-resistant.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
A kind of modified polyurethane resin-Nanocomposites coating, described coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, hexanodioic acid 4-8 part, Synolac 1-5 part, epoxy resin 2-4 part, propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part, vinyl acetic monomer 5-10 part, phosphoric acid 0.5-1 part, deionized water 10-30 part; And polymer nano-particle 8-16 part.
The preparation method of this coating is as follows:
1) tolylene diisocyanate 60-80 part, dicyclohexyl methane diisocyanate 5-10 part, hexamethylene diisocyanate 5-10 part, vinyl acetic monomer 5-10 part are added reactor, stirrer is used fully to stir, be warming up to 90-100 DEG C, slowly add hexanodioic acid 4-8 part;
2) continue to add Synolac 1-5 part, epoxy resin 2-4 part, fully stir more than 1h,
3) chainextender, activator and catalyzer is added: add propylene glycol 1-3 part, methyldiethanolamine 1-3 part, dibutyl tin diacetate 1-4 part according to dividing equally four minor tick 30min, phosphoric acid 0.5-1 part, then be incubated 80 degrees Celsius of more than 4h, add ionized water and carry out more than emulsification 30min;
4) polymer nano-particle being coated with benzotriazole is mixed in above-mentioned emulsion by ultrasonic disperse, at insulation 50 DEG C of abundant more than stirring reaction 1h, obtains modified polyurethane resin-Nanocomposites coating.
This preparation method being coated with the polymer nano-particle of benzotriazole is as follows:
Step 1): by n-butyl acrylate 2.5 weight part (or gram), methyl methacrylate 1.1 weight part, methacrylic acid 0.4 weight part, the mix monomer of myo-Inositol hexaphosphate 0.25 weight part joins in the reaction vessel of 1L capacity, then Potassium Persulphate 0.23 weight part will be contained according in every premium on currency, the aqueous solution 200ml that sodium lauryl sulphate 0.22 weight ratio obtains adds in reactor, pass into nitrogen in the reactor, temperature is increased to 85-90 DEG C, permanent magnet direct current motor is used to carry out mechanic whirl-nett reaction 24-36 hour, obtain primary emulsion,
Step 2): the aqueous solution 150mL containing Potassium Persulphate 0.2 weight part, sodium lauryl sulphate 0.45 weight part is joined in above-mentioned primary emulsion, then slowly butyl acrylate 2 weight part, methyl methacrylate 30 weight part is instilled, the mix monomer of methacrylic acid 14 weight part, time for adding is 40min, temperature of reaction remains on 85-90 DEG C, use permanent magnet direct current motor to carry out mechanic whirl-nett reaction 8 hours, obtain one-level core emulsion; Configuration quality concentration be 4% benzotriazole aqueous solution 400ml be placed in another reactor (capacity can be 1L), the one-level core emulsion 50ml getting above-mentioned synthesis joins in the benzotriazole aqueous solution, temperature is increased to 85-90 DEG C, keep more than 3h, obtain the one-level core emulsion being adsorbed with a certain amount of benzotriazole.
Step 3): 0.5 weight part Potassium Persulphate is joined the above-mentioned one-level core emulsion containing being adsorbed with a certain amount of benzotriazole, slowly instill butyl acrylate 3.8 weight part, methyl methacrylate 40 weight part subsequently, the mix monomer of methacrylic acid 2 weight part, drip process lasts 40min, temperature of reaction remains on 85-90 DEG C, sustained reaction is more than 8h at least, obtains the secondary core emulsion being coated with benzotriazole;
Step 4): the secondary core emulsion 100ml getting above-mentioned synthesis, add the aqueous solution 200ml containing 0.2 weight part Potassium Persulphate, temperature of reaction remains on 85-90 DEG C, the speed being 0.04g/min according to rate of addition slowly instills vinylbenzene 0.5 weight part, then about using aqueous sodium hydroxide solution (10wt%) to regulate the pH value to 10 of reaction soln, finally again slowly instill vinylbenzene 15 weight part, time for adding is no less than 40min, constant temperature keeps 85-90 DEG C and continues at least 8 hours, be separated by whizzer after completing above-mentioned steps, first use absolute ethanol washing twice, after use deionized water wash more than three times, be placed in dry 24 hours of the air dry oven of 50 DEG C, obtain the polymer nano-particle being coated with benzotriazole.
Embodiment 1
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60 parts, dicyclohexyl methane diisocyanate 5 parts, hexamethylene diisocyanate 5 parts, hexanodioic acid 4 parts, Synolac 1 part, epoxy resin 2 parts, propylene glycol 1 part, methyldiethanolamine 1 part, dibutyl tin diacetate 1 part, vinyl acetic monomer 6 parts, phosphoric acid 0.5 part, deionized water 15 parts; And polymer nano-particle 8 parts.Preparation method as previously mentioned.
Embodiment 2
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 70 parts, dicyclohexyl methane diisocyanate 10 parts, hexamethylene diisocyanate 10 parts, hexanodioic acid 8 parts, Synolac 3 parts, epoxy resin 4 parts, propylene glycol 3 parts, methyldiethanolamine 2 parts, dibutyl tin diacetate 4 parts, vinyl acetic monomer 10 parts, phosphoric acid 0.5 part, deionized water 30 parts; And polymer nano-particle 10 parts.Preparation method as previously mentioned.
Embodiment 3
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60 parts, dicyclohexyl methane diisocyanate 8 parts, hexamethylene diisocyanate 7 parts, hexanodioic acid 5 parts, Synolac 4 parts, epoxy resin 4 parts, propylene glycol 3 parts, methyldiethanolamine 1 part, dibutyl tin diacetate 3 parts, vinyl acetic monomer 5 parts, phosphatase 11 part, deionized water 25 parts; And polymer nano-particle 12 parts.Preparation method as previously mentioned.
Embodiment 4
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 80 parts, dicyclohexyl methane diisocyanate 10 parts, hexamethylene diisocyanate 8 parts, hexanodioic acid 8 parts, Synolac 5 parts, epoxy resin 4 parts, propylene glycol 2 parts, methyldiethanolamine 3 parts, dibutyl tin diacetate 1 part, vinyl acetic monomer 6 parts, phosphatase 11 part, deionized water 30 parts; And polymer nano-particle 14 parts.Preparation method as previously mentioned.
Embodiment 5
Urethane resin-Nanocomposites coating is made up according to weight proportion of following raw material: tolylene diisocyanate 60 parts, dicyclohexyl methane diisocyanate 8 parts, hexamethylene diisocyanate 5 parts, hexanodioic acid 6 parts, Synolac 2 parts, epoxy resin 2 parts, propylene glycol 2 parts, methyldiethanolamine 3 parts, dibutyl tin diacetate 4 parts, vinyl acetic monomer 10 parts, phosphoric acid 0.5 part, deionized water 25 parts; And polymer nano-particle 16 parts.Preparation method as previously mentioned.
The coating obtained by above-described embodiment 1-5 carries out surface treatment to same metal works, and efficacy parameter is compared as follows:
Embodiment 1-5 the performance test results comparative analysis table
Although give detailed description and explanation to the specific embodiment of the present invention above; but what should indicate is; we can carry out various equivalence according to conception of the present invention to above-mentioned embodiment and change and amendment; its function produced do not exceed that specification sheets contains yet spiritual time, all should within protection scope of the present invention.Such as, weight part can be chosen as gram or other weight unit.The above; be only preferred embodiment of the present invention; not in order to limit the present invention, every above embodiment is done according to technical spirit of the present invention any trickle amendment, equivalently replace and improve, within the protection domain that all should be included in technical solution of the present invention.