CN102358770B - Preparation method of copolymer coating with moisture self-repair function - Google Patents
Preparation method of copolymer coating with moisture self-repair function Download PDFInfo
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Abstract
The invention relates to a copolymer coating with a moisture self-repair function, and the coating is formed by copolymerization of isocyanate group-containing monomers and fluorinated acrylate monomers. The preparation method comprises the steps of: preparing isocyanate end group-containing functional monomers with diisocyanate, dihydric alcohol and hydroxyl-containing monomers as the raw materials, then subjecting the functional monomers to copolymerization with fluorine containing acrylic acid ester, a cross-linking agent and a photosensitizer under ultraviolet light initiation, thus obtaining a copolymer coating containing isocyanate monomers and fluorinated acrylate. The copolymer of the invention can be used as a protection coating of metallic and decoration materials, and the coating in the invention is not affected by ambient moisture. When the coating is damaged, a crack on the coating can be repaired on its own with the aid of ambient moisture. When the coating is damaged, a crack on the coating can be repaired on its own with the aid of ambient moisture, so that the original protection role of the coating is regained, the service life of the coating is extended, and the loss is reduced. The preparation method of the copolymer has the advantages of simple process, low cost, and easy implementation, and is suitable for large scale popularization and application.
Description
Technical field
The invention belongs to coated material polymkeric substance and preparation method thereof, particularly a kind of copolymer coated preparation method with moisture self-repair function.
Technical background
In the Present Global scope, annual because the financial loss that the corrosive attack of metal (iron, aluminium etc.) causes is very huge, therefore, solve the erosion-resisting problem of metal is an important field of research always.The protection of metal method commonly used is exactly to realize at the protective layer that its surface forms one deck inertia by methods such as coating, plating.Coating generally mostly is polymer materials, and polymer materials easily sustains damage under external force, destroys with the form of crackle, and can expand gradually increase, causes further infringement, thereby badly influences the performance of polymer materials.And crackle is very difficult to detect and control, so that the application of polymer materials is subjected to impact to a certain extent, because, in case coating is subject to external influence and destroys, the metal of substrate also can come out so, is subject to the erosion of external environment, thereby brings larger financial loss.
Summary of the invention
The objective of the invention is for above-mentioned existing problems, provide a kind of and have the multipolymer of moisture self-repair function as coated material, this coating is not subjected to the impact of ambient moisture under normal environment for use, and when coating sustained damage, coating crack can be by the moisture self-healing in the environment.
Technical scheme of the present invention:
A kind of have the copolymer coated of moisture self-repair function, formed by the monomer that contains isocyanate groups and fluorinated acrylate monomer copolymerization, the described monomer that contains isocyanate groups is the monomer based on tolylene diisocyanate, Triethylene glycol and hydroxyethyl methylacrylate; Monomer based on dimethylmethane vulcabond, Macrogol 200 and hydroxyethyl methylacrylate; Monomer based on isophorone diisocyanate, Liquid Macrogol and n-methylolacrylamide; Monomer based on hexamethylene diisocyanate, Polyethylene Glycol-600 and hydroxyethyl methylacrylate; Monomer based on isophorone diisocyanate, Triethylene glycol and hydroxyethyl methylacrylate; Described fluorinated acrylate monomer is vinylformic acid trifluoro methyl esters, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate or dodecafluoroheptyl methacrylate.
A kind of copolymer coated preparation method with moisture self-repair function, step is as follows:
1) contains the preparation of the monomer of isocyanate groups: under nitrogen protection, vulcabond is mixed with Benzoyl chloride, carry out the oil bath heating under stirring, when temperature reaches 65 ℃, add dibasic alcohol, and at 65 ℃ of lower reaction 2h that continue, make ending isocyanate prepolymer, prepared ending isocyanate prepolymer is dissolved with tetrahydrofuran (THF), then add the function monomer contain two keys, stir under the nitrogen protection and at 40 ℃ of reaction 4h, make and contain isocyanate-monomer;
2) copolymer coated preparation; After will containing the monomer of isocyanic ester, fluorine-containing (methyl) acrylate monomer, linking agent and photosensitizers mixing, film at sheet metal, then utilize UV-light to cause by the copolyreaction film forming;
3) anneal; Dry film is taken out, put into baking oven, at 120 ℃ of lower anneal 10min, then cooling gets final product at normal temperatures.
Described vulcabond is tolylene diisocyanate (TDI), dimethylmethane vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or dicyclohexyl methane diisocyanate (HMDI); Described dibasic alcohol comprises that molecular weight is any one ethers and the ester class dibasic alcohol of 100-1000.
The mol ratio of described vulcabond, Benzoyl chloride and dibasic alcohol is 4:0.01:1.
The described function monomer that contains two keys is hydroxyethyl methylacrylate or N hydroxymethyl acrylamide.
The volume ratio of described ending isocyanate prepolymer and tetrahydrofuran (THF) is 1:2; The amount ratio of ending isocyanate prepolymer and the function monomer that contains two keys is that the mol ratio of isocyano and hydroxyl is 2:1.
Described linking agent is ethylene glycol dimethacrylate (EDGMA) or trimethylol propane trimethyl methyl acrylate (TRIM).
Described photosensitizers is 2-hydroxy-2-methyl-1-phenyl-acetone (1173), 1-hydroxy-cyclohexyl phenyl ketone (184) and 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-mixture of one or both arbitrary proportions in the 1-acetone (907).
Describedly contain the monomer of isocyanic ester and the mass ratio of acrylate containing fluorine monomer is 7:3 to 5:5; The consumption of linking agent is the 5-10% of copolyreaction monomer total mass; The consumption of photosensitizers is the 2-4% of copolyreaction monomer total mass.
Principle of work of the present invention:
This multipolymer is formed with (methyl) acrylic ester monomer copolymerization that another includes the hydrophobicity fluorin radical by a kind of monomer that includes active terminal isocyanate groups.Isocyanic ester is very responsive to water, is exposed to be easy in the air and airborne reaction of moisture, and two molecule isocyanate can be reacted with a part water, generate urea.This reaction process is shown in chemical equation 1 and 2.Wherein isocyano elder generation generates the carboxylamine intermediate with water, and then carboxylamine decomposes rapidly, generates amido and carbonic acid gas, and the amido energy is rapid and another isocyano reaction generates urea.This series reaction becomes possibility so that contain the reparation of matrix under wet gas environments of isocyanate reactive group.
On the other hand, by in polymkeric substance, introducing fluorine-containing groups, the hydrophobicity of polymkeric substance institute film forming can be improved preferably, so that the water-intake rate of polymeric film reduces greatly, the effect of isocyanate groups in the good protection polymeric coating can be played.Simultaneously, in the process of multipolymer coating, fluorine-containing groups forms good aqueous vapor sealing coat because its low surface free energy is easier of the solid-air interface enrichment, so that isocyanate groups can get up in conductively-closed, avoids the effect of aqueous vapor; And isocyanate groups has strong polarity, and is easier in the enrichment of polar group surface, forms repair layer.So, when this coating was damaged, surperficial fluorine sealing coat was opened, so that inner isocyanate groups comes out.At this moment, coupled reaction can occur in the isocyanate groups on slight crack both sides under the effect of water in air gas, and two molecule isocyanate groups and a part water form urea, thereby reaches the effect of reparation.
Advantage of the present invention is: this multipolymer can be used as metal and finishing material protective coating; this coating is not subjected to the impact of ambient moisture under normal environment for use; and when coating sustains damage; coating crack can be by the moisture self-healing in the environment; recover original provide protection; thereby can prolong coating work-ing life, reduce the loss.Preparation method's technique of this multipolymer is simple, cost is low, easy to implement, be suitable for large-scale promotion application.
Description of drawings
Contrast photo before and after accompanying drawing 1 embodiment 1 sample is repaired.
Contrast photo before and after accompanying drawing 2 embodiment 2 samples are repaired.
Contrast photo before and after accompanying drawing 3 embodiment 3 samples are repaired.
Embodiment
Embodiment 1:
A kind of copolymer coated preparation method with moisture self-repair function, step is as follows:
1) get 80mmol TDI and the 0.44ml Benzoyl chloride mixes, temperature setting is set to 65 ℃, gets 20mmol Triethylene glycol (TEG) again, is added drop-wise in the reactor, regulates and drips speed, and TEG was dripped off in 30 minutes, reacts 2h again.Then, reaction product in the normal hexane solvent, is left standstill a few hours, pour out supernatant liquor, revolve steaming afterwards with being added to again in the mixed solvent (v/v=3/1) of normal hexane and ethyl acetate after the dissolving of 20mL tetrahydrofuran (THF), pour out supernatant liquor after leaving standstill, revolve steaming, vacuum-drying obtains ending isocyanate prepolymer.
2) ending isocyanate prepolymer and the hydroxyethyl methylacrylate with above-mentioned preparation reacts with mol ratio-NCO:-OH=2:1, and preparing end group is the methyl acrylic ester monomer of isocyanic ester.Get the 10mlTHF dissolving, under nitrogen protection, join in the there-necked flask.Then stir with magnetic stirrer, Heating temperature is set to 40 ℃, gets 10 gram hydroxyethyl methylacrylates and joins in the there-necked flask and react.The rate of addition of regulating hydroxyethyl methylacrylate dripped off about 30 minutes.Again at 40 ℃ of lower reaction 4h.Afterwards, reaction gained mixture is added in the mixed solvent (v/v=3/1) of 300mL normal hexane and ethyl acetate, leave standstill a few hours, pour out supernatant liquor, revolve steaming afterwards with being added drop-wise to again in the mixed solvent (vol:vol=1:1) of normal hexane and ethyl acetate after the tetrahydrofuran (THF) dissolving, repeat to precipitate twice, revolve steaming, product is collected in vacuum-drying, and cryopreservation is for subsequent use.
3) copolymer coated preparation; The Hexafluorobutyl mathacrylate that takes by weighing 3 grams mixes with mol ratio 3:7 with the function monomer that contains isocyanic ester of above-mentioned preparation, 5.0% the linking agent trimethylol propane trimethyl methyl acrylate (TRIM) that will account for again the monomer total mass joins in the there-necked flask, to account for simultaneously the photosensitizers 2-methyl-2-(4-morpholinyl) of total monomer quality 2.0%-1-[4-(methylthio group) phenyl]-1-acetone (907) joins in the reaction flask, mix with electromagnetism, after spin-coating film on the aluminium flake of treated mistake, put into the UV reactive device, under 1000 watts of power, react 2 minutes film forming.
The treatment process of described aluminium flake is: aluminium flake is cut to 2cm * 4cm size, removes the top layer zone of oxidation with sand papering first, then clean 10min with Virahol and acetone mixed solvent and deoil, use again twice of washed with de-ionized water, ultrasonic lower deionized water immersion treatment 10min pulls N out
2Under dry for subsequent use.
4) anneal; Dry film is taken out, put into baking oven, at 120 ℃ of lower anneal 10min, then cooling gets final product at normal temperatures.
This copolymer coated Performance Detection:
1) slight crack is processed: at the aluminium flake of the coating vestige of crossing, make slight crack with blade;
2) repairing test: the sample that will prepare slight crack is put into the container of the sealing of a fixed temperature and humidity.Design temperature T=30 ℃, humidity RH=95% processes sample 12h with this understanding.Be coated with before and after the film healing comparative test result picture as shown in Figure 1, visible coating crack can be by the moisture self-healing in the environment, thereby recovers original provide protection.
Embodiment 2:
A kind of copolymer coated preparation method with moisture self-repair function, step is as follows:
1) get 80mmol MDI and the 0.44ml Benzoyl chloride mixes, temperature setting is set to 65 ℃, gets the 20mmol Macrogol 200 again, is added drop-wise in the reactor, regulates and drips speed, and Macrogol 200 was dripped off in 30 minutes, reacts 2h again.Then, with reaction product in the normal hexane solvent, leave standstill a few hours, pour out supernatant liquor, revolve steaming afterwards with being added to again in the mixed solvent (v/v=3/1) of normal hexane and ethyl acetate after the dissolving of 20mL tetrahydrofuran (THF), pour out supernatant liquor after leaving standstill, revolve steaming, vacuum-drying obtains product, ending isocyanate prepolymer.
2) above-mentioned ending isocyanate prepolymer and hydroxyethyl methylacrylate are reacted with mol ratio-NCO:-OH=2:1, preparing end group is the methyl acrylic ester monomer of isocyanic ester.Get 10ml THF dissolving ending isocyanate prepolymer, under nitrogen protection, join in the there-necked flask.Then stir with certain speed with magnetic stirrer, Heating temperature is set to 40 ℃, gets 10 gram HEMA and joins in the there-necked flask and react.Regulate the rate of addition of hydroxyethyl methylacrylate, make it about 30 minutes, to drip off.Again at 40 ℃ of lower reaction 4h.Afterwards, reaction gained mixture is added in the mixed solvent (v/v=3/1) of 300mL normal hexane and ethyl acetate, leave standstill a few hours, pour out supernatant liquor, revolve steaming afterwards with being added drop-wise to again in the mixed solvent (vol:vol=1:1) of normal hexane and ethyl acetate after the tetrahydrofuran (THF) dissolving, repeat to precipitate twice, revolve steaming, product is collected in vacuum-drying, and cryopreservation is for subsequent use.
3) copolymer coated preparation; Claim 2 gram dodecafluoroheptyl methacrylates to mix with mol ratio 3:7 with the monomer that contains isocyanic ester of above-mentioned preparation, the linking agent ethylene glycol dimethacrylate (EDGMA) that will account for again total monomer quality 10.0% joins in the there-necked flask, to account for simultaneously the photosensitizers 2-hydroxy-2-methyl of monomer total mass 3.0%-1-phenyl-acetone (1173) joins in the reaction flask, mix with electromagnetism, after spin-coating film on the aluminium flake of treated mistake, put into the UV reactive device, under 1000 watts of power, reacted film forming 2 minutes.
The treatment process of described aluminium flake is identical with embodiment 1.
4) annealing conditions: the aluminium flake of above-mentioned UV-light reaction is filmed, put into baking oven, at 120 ℃ of lower anneal 10min, then cooling gets final product at normal temperatures.
This copolymer coated Performance Detection:
1) slight crack is processed: at the aluminium flake of the coating vestige of crossing, make slight crack with blade.
2) repairing test: the sample that will prepare slight crack is put into the container of the sealing of a fixed temperature and humidity.Design temperature T=30 ℃, humidity RH=95% processes sample 12h with this understanding.Be coated with before and after the film healing comparative test result picture as shown in Figure 2, visible coating crack can be by the moisture self-healing in the environment, thereby recovers original provide protection.
Embodiment 3:
A kind of copolymer coated preparation method with moisture self-repair function, step is as follows:
1) get 80mmol IPDI and the 0.44ml Benzoyl chloride mixes, temperature setting is set to 65 ℃, gets the 20mmol Liquid Macrogol again, is added drop-wise in the reactor, regulates and drips speed, and Liquid Macrogol was dripped off in 30 minutes, reacts 2h again.Then, with reaction product in the normal hexane solvent, leave standstill a few hours, pour out supernatant liquor, revolve steaming afterwards with being added to again in the mixed solvent (v/v=3/1) of normal hexane and ethyl acetate after the dissolving of 20mL tetrahydrofuran (THF), pour out supernatant liquor after leaving standstill, revolve steaming, vacuum-drying obtains product, ending isocyanate prepolymer.
2) ending isocyanate prepolymer and the N hydroxymethyl acrylamide with above-mentioned preparation reacts with mol ratio-NCO:-OH=2:1, prepares the methyl acrylamide monomer that end group is isocyanic ester.Get the 10mlTHF dissolving, under nitrogen protection, join in the there-necked flask.Then stir with certain speed with magnetic stirrer, Heating temperature is set to 40 ℃, gets 10 gram N hydroxymethyl acrylamides and joins 40 ℃ of lower reaction 4h in the there-necked flask.Afterwards, be added in the mixed solvent (v/v=3/1) of 300mL normal hexane and ethyl acetate filling reaction gained mixture, leave standstill a few hours, pour out supernatant liquor, revolve steaming afterwards with being added drop-wise to again in the mixed solvent (vol:vol=1:1) of normal hexane and ethyl acetate after the tetrahydrofuran (THF) dissolving, repeat to precipitate twice, revolve steaming, product is collected in vacuum-drying, and cryopreservation is for subsequent use.
3) copolymer coated preparation; Taking by weighing 4 gram vinylformic acid trifluoro methyl esters mixes with mol ratio 5:5 with the monomer that contains isocyanic ester of as above preparation, the linking agent ethylene glycol dimethacrylate (EDGMA) that will account for again total monomer quality 10.0% joins in the there-necked flask, the photosensitizers 1-hydroxy-cyclohexyl phenyl ketone (184) that will account for simultaneously monomer total mass 2.5% simultaneously joins in the reaction flask, mix with electromagnetism, after spin-coating film on the aluminium flake of treated mistake, put into the UV reactive device, under 1000 watts of power, reacted film forming 2 minutes.
The treatment process of described aluminium flake is identical with embodiment 1.
4) annealing conditions: the aluminium flake of above-mentioned UV-light reaction is filmed, put into baking oven, at 120 ℃ of lower anneal 10min, then cooling gets final product at normal temperatures.
This copolymer coated Performance Detection:
1) slight crack is processed: at the aluminium flake of the coating vestige of crossing, make slight crack with blade.
2) repairing test: the sample that will prepare slight crack is put into the container of the sealing of a fixed temperature and humidity.Design temperature T=30 ℃, humidity RH=95% processes sample 12h with this understanding.Be coated with before and after the film healing comparative test result picture as shown in Figure 3, visible coating crack can be by the moisture self-healing in the environment, thereby recovers original provide protection.
Claims (1)
1. copolymer coated preparation method with moisture self-repair function, described copolymer coated monomer and fluorinated acrylate monomer copolymerization by containing isocyanate groups forms, the described monomer that contains isocyanate groups is based on tolylene diisocyanate, the monomer of Triethylene glycol and hydroxyethyl methylacrylate, based on diphenylmethanediisocyanate, the monomer of Macrogol 200 and hydroxyethyl methylacrylate, based on isophorone diisocyanate, the monomer of Liquid Macrogol and N hydroxymethyl acrylamide, based on hexamethylene diisocyanate, the monomer of Polyethylene Glycol-600 and hydroxyethyl methylacrylate is based on isophorone diisocyanate, the monomer of Triethylene glycol and hydroxyethyl methylacrylate; Described fluorinated acrylate monomer is vinylformic acid trifluoro methyl esters, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate or dodecafluoroheptyl methacrylate, it is characterized in that step is as follows:
1) contains the preparation of the monomer of isocyanate groups: under nitrogen protection, vulcabond is mixed with Benzoyl chloride, carry out the oil bath heating under stirring, when temperature reaches 65 ℃, add dibasic alcohol, and at 65 ℃ of lower reaction 2h that continue, make ending isocyanate prepolymer, prepared ending isocyanate prepolymer is dissolved with tetrahydrofuran (THF), then add the function monomer contain two keys, stir under the nitrogen protection and at 40 ℃ of reaction 4h, make and contain isocyanate-monomer;
2) copolymer coated preparation; After will containing the monomer of isocyanic ester, fluorine-containing (methyl) acrylate monomer, linking agent and photosensitizers mixing, film at sheet metal, then utilize UV-light to cause by the copolyreaction film forming;
3) anneal; Dry film is taken out, put into baking oven, at 120 ℃ of lower anneal 10min, then cooling gets final product at normal temperatures;
The mol ratio of described vulcabond, Benzoyl chloride and dibasic alcohol is 4:0.01:1; The described function monomer that contains two keys is hydroxyethyl methylacrylate or N hydroxymethyl acrylamide; The volume ratio of described ending isocyanate prepolymer and tetrahydrofuran (THF) is that 1:2, ending isocyanate prepolymer and the amount ratio that contains the function monomer of two keys are that the mol ratio of isocyano and hydroxyl is 2:1; Described linking agent is ethylene glycol dimethacrylate or trimethylol propane trimethyl methyl acrylate; Described photosensitizers is 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone and 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-mixture of one or both arbitrary proportions in the 1-acetone; Describedly contain the monomer of isocyanic ester and the mass ratio of acrylate containing fluorine monomer is 7:3 to 5:5; The consumption of linking agent is the 5-10% of copolyreaction monomer total mass; The consumption of photosensitizers is the 2-4% of copolyreaction monomer total mass.
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| CN105669932B (en) * | 2016-01-13 | 2018-05-11 | 中山大学 | A kind of smooth self-repairing cross-linked polymer and its preparation method and application |
| CN106394572A (en) * | 2016-10-21 | 2017-02-15 | 苏州大成电子科技有限公司 | Wear-resisting panoramic train carriage |
| KR101947594B1 (en) * | 2017-04-13 | 2019-02-14 | 주식회사 쎄코 | Self-healing polyvinyl and method for preparing the same |
| CN109735194A (en) * | 2019-01-16 | 2019-05-10 | 常熟理工学院 | Ultraviolet light solidifies scratch resistance selfreparing TPU stealth film and preparation method thereof |
| CN115746602B (en) * | 2022-11-12 | 2023-12-01 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
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| CN102040900A (en) * | 2010-11-11 | 2011-05-04 | 常州大学 | Fluorocoating resin and preparation method thereof |
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| CN102040900A (en) * | 2010-11-11 | 2011-05-04 | 常州大学 | Fluorocoating resin and preparation method thereof |
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| Baghdachi, J., et al..Design and Development of Self - Healing polymers and coatings.《ACS Symposium Series》.2010,第3-20页. |
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