CN102585700B - Method for preparing UV (ultraviolet)-curable high-temperature-resistant and corrosion-resistant organic silicon/silica hybrid coating - Google Patents
Method for preparing UV (ultraviolet)-curable high-temperature-resistant and corrosion-resistant organic silicon/silica hybrid coating Download PDFInfo
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- CN102585700B CN102585700B CN201210010995.0A CN201210010995A CN102585700B CN 102585700 B CN102585700 B CN 102585700B CN 201210010995 A CN201210010995 A CN 201210010995A CN 102585700 B CN102585700 B CN 102585700B
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Abstract
The invention discloses a method for preparing an UV (ultraviolet)-curable high-temperature-resistant and corrosion-resistant organic silicon/silica hybrid coating. In the method, tetraethoxysilane is taken as an inorganic phase precursor, methyltriethoxysilane and diphenyldimethoxysilane are taken as organic phase precursors, then the mixed liquor of gamma-methacryloxy silane and a free-radical photo-initiator is added, and an UV-curable organic silicon/silica hybrid sol can be prepared by using a sol-gel method; and after a base material is coated, the base material is cured by ultraviolet light for 30-300s so as to obtain an organic silicon/silica hybrid coating, thereby forming hybrid gel space network structure taking Si-O-Si bonds as a skeleton. The method disclosed by the invention has the following technical effects: the hybrid coating subjected to ultraviolet-light curing forms a denser network structure, thereby facilitating the improvement of comprehensive properties, and especially facilitating the improvement of corrosion resistance; and the denser network structure can form a physical 'barrier' better so as to prevent corrosive substances such as water and chemical reagents and the like from contacting a substrate.
Description
Technical field
The present invention relates to a kind of preparation method of organosilicon/silica hybrid coatings, relate in particular to a kind of preparation method of high temperature resistant, corrosion resistant organosilicon/silica hybrid coatings of uV curable.
Background technology
The develop rapidly of modern science and technology is had higher requirement to the performance of material, and the material of single character can not meet the needs of development well, and Composite has become the main flow trend of modern material development.
Hybrid inorganic-organic materials is a kind of matrix material of excellent performance, and it is by certain physics or chemical process, organic phase to be attached in inorganic network, and forms the organic-inorganic network mutually running through; Organic phase wherein and inorganic phase are by chemical bond (covalent linkage or coordinate bond), hydrogen bond or Van der Waals force combination on nanometer level, and the size that is separated is not more than nano level.
The structure of hybrid inorganic-organic materials and performance and traditional matrix material are essentially different.In traditional matrix material, be dispersed in inorganic component size in polymer-based carbon conventionally all more than micron order, only as filler or weighting agent, to the performance of material, can only play limited strengthening action.Hybrid inorganic-organic materials is as a kind of finely dispersed heterogeneous material, interfacial area between organic phase and inorganic phase is very large, interfacial interaction is strong, make common sharply clearly interface thicken, site size is conventionally at nano level, even reach in some cases " molecular level ", these constructional features make hybrid inorganic-organic materials have obvious advantage than traditional matrix material.It combines the good characteristic of organic polymer and inorganic materials, has good mechanical property, resistance to elevated temperatures and good snappiness; In addition, hybrid inorganic-organic materials can be in very little scope (molecular level) control the structure of material, make the performance of material produce abundant variation, at machinery, optics, electronics, separation, catalysis, chemistry and many fields such as biological, have broad application prospects.
As far back as 20 century 70s, in fact oneself is through having occurred the hybrid material of polymkeric substance/silicon-dioxide, and just people are not also recognizing performance that it is special and the meaning of practical application at that time; C.Gleitrer in 1980 propose the concept of hybrid material; Within 1984, Schmidt prepares organic-inorganic materials with sol-gel method; Since the nineties, both at home and abroad the preparation method of hybrid material, performance, kind and application have been conducted extensive research
Prepare at present hybrid inorganic-organic materials and mainly contain graft process, blending method, sol-gel method and self-assembling technique.Wherein, sol-gel method (Sol-Gel method) is the earliest for the preparation of the method for hybrid material, also be to use so far the most extensive, the most perfect preparation method of development, it has the excellent characteristics such as prepared by room temperature (or a little more than room temperature), component is controlled, product structure is meticulous, purity is high.Therefore the present invention selects sol-sol legal system for organosilicon/SiO 2 hybrid colloidal sol of uV curable.Sol-Gel legal system is that to take metal alkoxide or metal alkoxide be presoma for the principle of hybrid material, after hydrolysis, polycondensation, form colloidal sol under certain condition, then through processing modes such as solvent evaporates or heating, colloidal sol (Sol) is converted into and there is the cancellated gel in space.
Organosilicon/silicon dioxide nano composite material is the class high-performance organic/inorganic hybridization material that recent development is got up, it take silicon-dioxide as inorganic component, by strong chemical bond and organic phase combination, thereby the performances such as the thermotolerance of raising polymkeric substance, oxidation-resistance, hardness, the coating compactness prepared by this hybrid material is good, resistance of aging is strong, has improved the resistance to corrosion of coating.On Si, introduce active group or functional R group, the organosilicon of take is prepared hybrid material as core, will form the molecular level hybrid inorganic-organic materials of a class brand new and property.
UV-curing technology is that a kind of environment-friendly type is solidified technology, and ultraviolet curable coating, after being subject to UV-irradiation, photochemical reaction occurs, thereby cause polymerization, crosslinked, make liquid coating moment become solid film, because it has solvent-free discharge, not only safety but also free from environmental pollution; Curing speed fast (tens seconds or several minutes), production efficiency is high, is applicable to streamline and produces; Save the energy, power consumption is about 1/5 ~ 1/10 of heat curing coating; Coating performance is excellent, has the plurality of advantages such as good rub resistance, solvent resistance and polluting proofing property, therefore obtains and develops rapidly.
Photocurable Silicone Material is efficient, energy-conservation owing to having excellent properties and the photocuring technology of organosilicon material concurrently, is subject to people and more and more pays close attention to; Meanwhile, the organic phase in organosilicon/SiO 2 hybrid system, inorganic phase and two alternate coupling agents all adopt material, and this hybrid systems consistency is good, and material high comprehensive performance makes it have wide application prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high temperature resistant, corrosion resistant organosilicon/silica hybrid coatings of uV curable, the method curing and dying order simply, rapidly and efficiently, energy-conserving and environment-protective, with low cost, coating machine performance, high temperature resistant and corrosion resistance nature is good, is applicable to industrialization pipelining.
The object of the present invention is achieved like this, its method steps is as follows: at room temperature by stoichiometric number, dehydrated alcohol, hydrochloric acid and distilled water are dropped in quantitative tetraethoxy successively to reaction
5min ~ 85minafter add successively again the mixed solution of quantitative Union carbide A-162, dimethoxydiphenylsilane and γ-methacryloxypropyl silane and radical photoinitiator, reaction 25min ~ 3h post-heating is extremely
50 ~ 80℃, condensing reflux 1h ~ 6h obtains organosilicon/SiO 2 hybrid colloidal sol of water white uV curable, after being chilled to room temperature, sealing and standing is standby, the hybrid collosol of sealing and standing is filmed on matrix by spread coating, after solvent evaporates, carry out ultraviolet light polymerization and obtain organosilicon/silica hybrid coatings.Each component add-on ratio is respectively n (tetraethoxy): n (Union carbide A-162): n (dimethoxydiphenylsilane): n (γ-methacryloxypropyl silane)=0.001 ~ 500:0.001 ~ 500:0.001 ~ 200:0.001 ~ 200; N (dehydrated alcohol): n (distilled water): n (hydrochloric acid): n (Si)=0.001 ~ 500:0 ~ 100:0.0001 ~ 50:0.01 ~ 1000, n wherein (Si) represents the total mole number of tetraethoxy, Union carbide A-162, dimethoxydiphenylsilane, γ-methacryloxypropyl silane add-on; The add-on of light trigger is 0.1% ~ 10% of solid content (weight); The ultraviolet light polymerization time is: 30s ~ 300s; The thickness of organosilicon/silica hybrid coatings is
2 ~ 2000micron.
The present invention is usingd tetraethoxy as inorganic phase presoma, Union carbide A-162 and dimethoxydiphenylsilane are as organic phase presoma, ethanol is as cosolvent, and hydrochloric acid is as catalyzer, and adds the mixed solution of γ-methacryloxypropyl silane and radical photoinitiator.Employing sol-gel method at room temperature stirring reaction prepares organosilicon/SiO 2 hybrid colloidal sol that can carry out ultraviolet light polymerization after hydrolysis, polycondensation.Hybrid collosol sealing and standing one-tenthization adopts brushing method to film after for some time, carry out ultraviolet light polymerization after solvent evaporates is complete, obtains organosilicon/silica hybrid coatings.
Preparation feedback of the present invention and principle are as follows:
In the present invention organic phase, inorganic phase presoma under alcohol solvent and hydrochloric acid catalysis effect, be hydrolyzed, polycondensation, prepare organosilicon/SiO 2 hybrid colloidal sol.
Hydrolysis reaction is as follows.
1. the hydrolysis reaction of tetraethoxy
2. the hydrolysis reaction of Union carbide A-162
3. the hydrolysis reaction of dimethoxydiphenylsilane
in hydrolysis reaction product with hydroxyl can carry out polycondensation with hydroxyl, there is dehydrating condensation; Also can and alkoxyl group (methoxyl group, oxyethyl group) carry out polycondensation, produce alcohol roh (R is methyl and ethyl), there is dealcoholysis condensation.But no matter carry out which kind of polycondensation, finally all formation be take to Si-O-Si key as the interconnective spacial framework of skeleton.Body series polycondensation process is as follows.
5. dehydrating condensation
6. dealcoholysis condensation
Through hydrolysis, after polycondensation, form and take the hybrid collosol that Si-O-Si key is skeleton, transparent and homogeneous, and in γ-methacryloxypropyl silane with C=C double bond structure can be the basis that provides of ultraviolet light polymerization reaction.
Hybrid collosol after sealing ageing for some time is coated on base material, after solvent evaporates, carries out ultraviolet light polymerization.
Technique effect of the present invention is, hybrid coating after ultraviolet light polymerization, formed more fine and close network structure, be conducive to the raising of over-all properties, be particularly advantageous in corrosion proof raising, finer and close network structure can form better physics " barrier " and stop contacting of the corrosivess such as water, chemical reagent and matrix.
Embodiment
embodiment 1
At room temperature press stoichiometric number by dehydrated alcohol, hydrochloric acid and distilled water drop in quantitative tetraethoxy successively, after reaction 5min ~ 85min, add successively more quantitative Union carbide A-162, the mixed solution of dimethoxydiphenylsilane and γ-methacryloxypropyl silane and radical photoinitiator, reaction 25min ~ 3h post-heating to 50 ~ 80 ℃, condensing reflux 1h ~ 6h obtains organosilicon/SiO 2 hybrid colloidal sol of water white uV curable, after being chilled to room temperature, sealing and standing is standby, the hybrid collosol of sealing and standing is filmed on matrix by spread coating, after solvent evaporates, carry out ultraviolet light polymerization and obtain organosilicon/silica hybrid coatings, and obtain organosilicon/silica hybrid coatings after ultraviolet light polymerization 60s.
Coating performance is as follows: hardness is 0.8513, and snappiness is 1mm, and sticking power is 1 grade, and impact strength is 50kgcm; At 400 ℃, calcination 1h coating is intact; Water resistance test, resistance to salt water test 1440h matrix surface is corrosion-free, and neutral salt spray test, wet-heat resisting experiment are intact through 1440h testing coating.
Embodiment 2
At room temperature press stoichiometric number by dehydrated alcohol, hydrochloric acid and distilled water drop in quantitative tetraethoxy successively, after reaction 5min ~ 85min, add successively more quantitative Union carbide A-162, the mixed solution of dimethoxydiphenylsilane and γ-methacryloxypropyl silane and radical photoinitiator, reaction 25min ~ 3h post-heating to 50 ~ 80 ℃, condensing reflux 1h ~ 6h obtains organosilicon/SiO 2 hybrid colloidal sol of water white uV curable, after being chilled to room temperature, sealing and standing is standby, the hybrid collosol of sealing and standing is filmed on matrix by spread coating, after solvent evaporates, carry out ultraviolet light polymerization and obtain organosilicon/silica hybrid coatings, and obtain organosilicon/silica hybrid coatings after ultraviolet light polymerization 60s.
Coating performance is as follows: hardness is 0.8961, and snappiness is 1mm, and sticking power is 1 grade, and impact strength is 50kgcm; At 450 ℃, calcination 1h coating is intact; Water resistance test, resistance to salt water test 1440h matrix surface is corrosion-free, and neutral salt spray test, wet-heat resisting experiment are intact through 1440h testing coating.
Claims (3)
1. a uV curable is high temperature resistant, the preparation method of corrosion resistant organosilicon/silica hybrid coatings, it prepares desired raw material: tetraethoxy, Union carbide A-162, dimethoxydiphenylsilane, dehydrated alcohol, hydrochloric acid, distilled water, γ-methacryloxypropyl silane, radical photoinitiator, it is characterized in that preparation method is: at room temperature by stoichiometric number by dehydrated alcohol, hydrochloric acid and distilled water drop in quantitative tetraethoxy successively, after reaction 5min ~ 85min, add successively more quantitative Union carbide A-162, the mixed solution of dimethoxydiphenylsilane and γ-methacryloxypropyl silane and radical photoinitiator, reaction 25min ~ 3h post-heating to 50 ~ 80 ℃, condensing reflux 1h ~ 6h obtains organosilicon/SiO 2 hybrid colloidal sol of water white uV curable, after being chilled to room temperature, sealing and standing is standby, the hybrid collosol of sealing and standing is filmed on matrix by spread coating, after solvent evaporates, carry out ultraviolet light polymerization and obtain organosilicon/silica hybrid coatings, described each raw material add-on mol ratio is: tetraethoxy: Union carbide A-162: dimethoxydiphenylsilane: γ-methacryloxypropyl silane=0.001 ~ 500:0.001 ~ 500:0.001 ~ 200:0.001 ~ 200, dehydrated alcohol: distilled water: hydrochloric acid: Si=0.001 ~ 500:0 ~ 100:0.0001 ~ 50:0.01 ~ 1000, Si wherein represents the total mole number of tetraethoxy, Union carbide A-162, dimethoxydiphenylsilane, γ-methacryloxypropyl silane add-on, the add-on of light trigger is 0.1% ~ 10% of solid content.
2. the preparation method of high temperature resistant, the corrosion resistant organosilicon/silica hybrid coatings of a kind of uV curable according to claim 1, is characterized in that the ultraviolet light polymerization time is: 30s ~ 300s.
3. the preparation method of high temperature resistant, the corrosion resistant organosilicon/silica hybrid coatings of a kind of uV curable according to claim 1, is characterized in that: the thickness of organosilicon/silica hybrid coatings is 2 ~ 2000 microns.
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