CN103436125B - A kind of vinylformic acid organosilicon water milk type coating and its preparation method and application - Google Patents
A kind of vinylformic acid organosilicon water milk type coating and its preparation method and application Download PDFInfo
- Publication number
- CN103436125B CN103436125B CN201310385442.8A CN201310385442A CN103436125B CN 103436125 B CN103436125 B CN 103436125B CN 201310385442 A CN201310385442 A CN 201310385442A CN 103436125 B CN103436125 B CN 103436125B
- Authority
- CN
- China
- Prior art keywords
- vinylformic acid
- water
- type coating
- milk type
- acrylate copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention belongs to acrylic coating technical field, disclose a kind of vinylformic acid organosilicon water milk type coating and its preparation method and application.This vinylformic acid organosilicon water milk type coating comprises the component of following parts by weight: 100 parts, water; Emulsifying agent 0.1 ~ 4 part; Liquid hydrogen containing polysiloxane 5 ~ 20 parts; Acrylate copolymer 5 ~ 50 parts.Vinylformic acid organosilicon water milk type coating of the present invention, silicone content in the polymer up to more than 10%, organosilicon and acrylate copolymer compound in relative broad range, cured at room temperature film forming.Preparation technology of the present invention is simple, gained good emulsion stability; There is after this vinylformic acid organosilicon water milk type coating film-forming good mechanical mechanics property (hardness can up to 3H) and excellent waterproof hydrophobicity performance, resistance to acids and bases, weathering resistance, adhesive power (can reach 2.5MPa) and suitable stripping strength (up to 23g/cm).
Description
Technical field
The invention belongs to technical field of aqueous paint, particularly a kind of vinylformic acid organosilicon water milk type coating and its preparation method and application.
Background technology
Coating Water-borne modification is important measures of current environment-friendly and energy-saving emission-reduction.Liquid polydimethylsiloxane water miscible liquid technology of preparing comparatively perfect, but do not have crosslinked group because of it, can not at room temperature drying and forming-film; With the organosilicon coating that silicone resin is the preparation of main film forming matter, then there is excellent resistant of high or low temperature, water resisting property, chemical proofing and the special surface property of film-forming properties and organosilicon polymer itself, have outstanding performance and tempting application prospect preparing in solvent based coating.But due to the highly cross-linked structure of silicone resin, be difficult to directly under mechanical high-speed dispersion, realize the dispersion in water and prepare stable silicone resin water miscible liquid.The obtained resin emulsion of the emulsion polymerization method of carrying out for raw material with the low viscosity precursor silane of silicone resin is usually very unstable, and practical application is very limited.
Polysiloxane has low surface tension and excellent waterproof contaminated resistance, there are extraordinary water-fast, humidity and anti-adhesion effects, it is one of the ideal material of water-proof material, separant, but need heat (150 ~ 200 DEG C) to solidify, wetting property is bad, bad to body material attachment, and when temperature is higher, the physical strength of paint film is bad, particularly polysiloxane water miscible liquid, dispersion film-forming properties is not good, uneven in substrate surface dispersion, very easily produces local and gather formation piebald in drying process.
For improving sticking power and the film-forming properties of water-emulsion organic silicon, people introduce the acrylic polymer with excellent film-forming properties and good adhesion.Current organosilicon-modified acrylate base polymer emulsion is due to the restriction of molecular designing and manufacturing process, silicone content is very low, normal lower than 10% in the polymer, just there is a large amount of gels even crosslinking curing when preparing emulsion in the emulsion extremely unstable when silicone content improves.Due to the compatibility problem of acrylic polymer and organosilicon polymer, film often can produce macroface and be separated, and has a strong impact on the performance of film.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of vinylformic acid organosilicon water milk type coating.In this coating, silicone content can up to more than 10% in polymkeric substance (liquid hydrogen containing polysiloxane and acrylate copolymer), liquid hydrogen containing polysiloxane and acrylate copolymer also can be compounded to form the coating of different purposes in relative broad range, different ratios obtains organosilicon-modified acrylic polymer coating based on acrylate copolymer and respectively based on the acryl-modified silicone resin coating of liquid hydrogen containing polysiloxane, all at room temperature can solidify, and there is excellent infiltration film-forming properties and waterproof resistance to acids and bases and weather resistance.
Another object of the present invention is the preparation method providing a kind of aforesaid propylene acid organosilicon water milk type coating.
Still a further object of the present invention is the surfacecti proteon providing aforesaid propylene acid organosilicon water milk type coating in construction substrate, the application in the release film of ceramic condenser, wrapping material, release coating, releasing agent.
Object of the present invention is realized by following proposal:
A kind of vinylformic acid organosilicon water milk type coating, comprises the component of following parts by weight: 100 parts, water; Emulsifying agent 0.1 ~ 4 part; Liquid hydrogen containing polysiloxane 5 ~ 20 parts; Acrylate copolymer 5 ~ 50 parts.
Described liquid hydrogen containing polysiloxane refers at least one in hydrogeneous methyl-silicone oil and the hydrogeneous methyl-silicone oil of glycidyl allyl ether Si―H addition reaction modification.
Preferably, in described liquid hydrogen containing polysiloxane, the hydrogen richness of activated silica hydrogen bond is 0.15 ~ 1.5wt% of polymethyl siloxane total amount.
When in liquid hydrogen containing polysiloxane, hydrogen richness is lower than 0.15wt%, because of excessively slow with acrylate copolymer speed of response, and the not enough and not easily film forming of crosslinking degree.When hydrogen content is higher than 1.5wt%, the vinylformic acid organosilicon water milk type coating of gained easily produces more hydrogen when room temperature is placed, and easily forms flatulence, and affects the film forming of coating, cause the appearance of pore during storage.
Described emulsifying agent refers to the emulsifying agent containing unsaturated double-bond.Emulsifying agent is for the preparation of hydrogen containing polysiloxane water miscible liquid.
Preferably, described emulsifying agent refers at least one in sorbitan monooleate and polyoxyethylene sorbitan oleic acid ester.
Described sorbitan monooleate comprises monoesters, dibasic acid esters and three esters, like that Pan-80(S-80), Si Pan-83(S-83) and Si Pan-85(S-85) at least one.
Described polyoxyethylene sorbitan oleic acid ester comprises monoesters, dibasic acid esters and three esters, as tween-80 (T-80), tween-83(T-83) and tween 85 (T-85) at least one.
More preferably, described emulsifying agent refers to S-80 and T-80.
The present invention's liquid hydrogen containing polysiloxane used, containing activated silica hydrogen bond in molecule, also slowly can form chemical bond with the oleate units carbon carbon unsaturated double-bond generation microfacies mutual effect in this Pan of emulsifier molecules, tween and become organosilicon polymer, easily be dispersed under external force in micella, si-h bond and unsaturated carbon-carbon double bond are discharged to micella inside, polarity polyoxyethylene chain link in emulsifier molecules is outside and interact with water molecules discharged to micella, forms stable emulsion.
Described acrylate copolymer refers at least one in emulsified acrylic acid multipolymer and water-dispersible acrylic polysiloxane.
Preferably, the vinylformic acid in described acrylate copolymer and methacrylic acid unit total content are 10 ~ 30wt% of polymer solids content.
Described emulsified acrylic acid multipolymer is prepared by following methods: (methyl) vinylformic acid and (methyl) acrylate monomer are passed through free radical water emulsion polymerization at 70 ~ 90 DEG C, obtains emulsified acrylic acid multipolymer.
Described water-dispersible acrylic polysiloxane is prepared by following methods: by vinylformic acid and hydrogeneous methyl-silicone oil and allyl polyether by catalytic addition reaction, obtain water-dispersible acrylic polysiloxane;
Or prepared by following methods: vinylformic acid and hydrogeneous methyl-silicone oil also pass through machinery emulsification method by catalytic addition reaction at 50 ~ 70 DEG C, obtain water-dispersible acrylic polysiloxane.
Described acrylate copolymer, containing polarity carboxyl, in coating system, carboxyl is outside discharged to micella, makes emulsion-stabilizing.
The present invention utilizes the si-h bond in hydrogen containing siloxane and the carboxyl in acrylate copolymer dehydrogenation reaction at room temperature slowly to occur and crosslinking curing film forming.
Preferably, vinylformic acid organosilicon water milk type coating of the present invention, also can add suitable filler, pigment.
The preparation method of aforesaid propylene acid organosilicon water milk type coating, comprises following concrete steps:
By the mechanical high-speed emulsification at room temperature to 50 DEG C of liquid hydrogen containing polysiloxane, emulsifying agent and water, obtain water-latex type hydrogen containing polysiloxane, mix with under acrylate copolymer room temperature, obtain vinylformic acid organosilicon water milk type coating.
Preferably, the amount of emulsifying agent used is 0.1 ~ 4wt% of total Water in vinylformic acid organosilicon water milk type coating.
The present invention first forms water-latex type hydrogen containing polysiloxane liquid hydrogen containing polysiloxane, emulsifying agent mixing and emulsifying, because emulsifying agent enters into silicone molecules chain, and the active hydrogen in liquid hydrogen containing polysiloxane and the carboxyl reaction in acrylate copolymer, significantly improve water-repellancy water tolerance and the intensity of gained vinylformic acid organosilicon water milk type coating.
Preferably, in preparation method's preparation process of described vinylformic acid organosilicon water milk type coating, neutralizing agent, defoamer, flow agent, thickening material or suitable water can also be added.
Hydrogen containing polysiloxane emulsion of the present invention can mix according to arbitrary proportion with the dispersible acrylate copolymer of water or polymer emulsion, preferably the part by weight of liquid hydrogen containing polysiloxane and acrylate copolymer is 5 ~ 20:5 ~ 50, and the per-cent of liquid hydrogen containing polysiloxane in organosilicon and acrylate copolymer gross weight is more than 10%.The composite coating of preparation has excellent infiltration film-forming properties.
Water-borne coatings of the present invention has the good feature of environmental protection and energy saving and ambient temperature curable, acid and alkali-resistance, weathering resistance, the protective coating of durable water resistant can be formed, can be applicable to the surfacecti proteon of construction substrate, be preferably pottery, stone material, cement products, gypsum, inner-outer wall etc. inorganic porous, also can be used as the release film of ceramic condenser, wrapping material etc., release coating, releasing agent.
Different ratios liquid hydrogen containing polysiloxane is applicable to different purposes from the coating that acrylate copolymer compound obtains, and because silicone molecules itself is submissiveer when liquid hydrogen containing polysiloxane content is higher, film snappiness is good, and integral waterproofing is good; During acrylate copolymer content height, film-forming properties is better, and intensity hardness is higher.Acrylate copolymer is that the coating film-forming properties of master is better, hardness is high, the main release film being used as the surfacecti proteon, ceramic condenser, wrapping material etc. of construction substrate, organosilicon is that the coating integral hydrophobic of master is stronger, is mainly used as the release coating such as ceramic condenser, wrapping material, releasing agent etc.
Mechanism of the present invention is:
Vinylformic acid organosilicon water milk type coating of the present invention, silicone content is in the polymer up to more than 10%, and compound tense still can the uniform curing film forming of room temperature in relative broad range for organosilicon and acrylate copolymer.In drying process, along with the volatilization of moisture, micella is close to each other, time to a certain extent, micella interpenetrates, and hydrogen containing polysiloxane molecule and acrylate copolymer molecule contact with each other, and the si-h bond of polarity, epoxy group(ing) and carboxyl attract each other and form stronger hydrogen bond or even chemical bond, contribute to both macroscopical homogeneous systems of dispersed formation on the one hand, contribute to film-forming on the other hand.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) silicone content is high, paintable, and room temperature can be uniform curing: silicone content of the present invention in the polymer can up to more than 10%, and compound tense still can the uniform curing film forming of room temperature in relative broad range for organosilicon and acrylate copolymer.The Electronic interactions of carboxyl in acrylate copolymer easily and in inorganic substrate and can be uniformly dispersed on substrate surface, also can interact with the si-h bond in hydrogen containing polysiloxane molecule or epoxide group and form hydrogen bond or chemical bond, acrylate copolymer molecule is combined with polysiloxane molecule high dispersing, forms homogeneous cured film under room temperature.
Though widely used simethicone emulsion is on the market stablized, without crosslinked group, long-term in oily after coated substrate.Occur to be separated significantly in drying process after dimethyl-silicon oil hydrosol and acrylic emulsion compound, silicone oil is separated out on surface.
(2) technique is simple, good emulsion stability: containing activated silica hydrogen bond in hydrogen containing polysiloxane molecule, absorption emulsifier molecules and with the oleate units carbon carbon unsaturated double-bond generation microfacies mutual effect in this Pan of emulsifying agent, tween molecule, easily be dispersed in micella under mechanical external force effect, si-h bond and unsaturated carbon-carbon double bond are discharged to micella inside, the semipolar polyoxyethylene chain of tween molecule is outside and interact with water molecules discharged to micella, forms stable emulsion.Contain polarity carboxyl in acryl copolymer latex or vinylformic acid organosilicon polymer, the free-radical polymerized or mechanical high-speed emulsion process preparation by water miscible liquid, carboxyl is outside discharged to micella, emulsion-stabilizing.Water miscible liquid can deposit more than 1 year by ambient-temp-stable.
Brush after mixing under hydrogen containing polysiloxane water miscible liquid and water-latex type or water-dispersible acrylate copolymer in proportion room temperature during use.
Silicone resin or silicone resin organic solvent dissolution liquid are difficult to the manufacture of direct mechanical emulsify at a high speed method; Namely breakdown of emulsion caking or solidification is there is in the water miscible liquid manufactured by letex polymerization with the presoma silane of silicone resin in 7 days.
(3) good mechanical mechanics property and excellent waterproof hydrophobicity performance, resistance to acids and bases, resistance to weathering resistance: in acrylate copolymer molecule carboxyl and high-content low surface energy hydrogen containing polysiloxane in the interaction such as silicon hydrogen base, epoxy group(ing), high dispersing crosslinking curing becomes homogeneous cured film.Cured film has certain hardness (can up to 3H), adhesive power (can reach 2.5MPa) and suitable stripping strength (up to 23g/cm).Water molecules or other acidic molecular, alkali molecules, contaminant molecule not easily wetting near and destroy the network of crosslinking curing, there is significant surface hydrophobic lotus leaf effect, resistance to acids and bases and weathering resistance.
The same with dimethyl silicone oil when hydrogen containing polysiloxane is used alone can not crosslinking curing film forming, very little to adhesion, stripping strength is little.Water droplet molecule is close to each other with silicone molecule under self-gravity action on not dry silicone oil surface, along with time lapse molecular interaction is strengthened, and the spherical serious fasciation of the globule and and at silicon oil membrane surface display bunching, surface hydrophobic lotus leaf effect is not obvious.There is fracture decomposition destruction in Si-O key under strongly-acid molecule or alkali molecules effect, loses protective effect.Therefore, its cement-based material in alkalescence or to lose efficacy when using for a long time in acid rain climatope.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Example 1: the preparation of hydrogen containing polysiloxane emulsion
(1) directly prepare
By emulsifying agent 6g sorbitan monooleate S-80(and Si Pan-80), 14g polyoxyethylene sorbitan oleic acid ester T-80(and tween-80) and after 200g water mixes, at room temperature under high-speed stirring, (1500 revs/min) slowly drip 202 high hydrogeneous methyl-silicone oil (containing active hydrogen 1.5wt%) 100g respectively, be added dropwise to complete rear continuation stirring 10 minutes, then stirring at low speed is changed into 10 minutes, stop stirring, prepare hydrogen containing polysiloxane emulsion S1(active hydrogen 1.5wt%) 320g.
After 2gS-80,3gT-80,1gT-85 and 200g water is mixed, be warming up to 40 DEG C, under high-speed stirring, (1500 revs/min) slowly drip hydrogeneous methyl-silicone oil (containing active hydrogen 0.75wt%) 100g respectively, be added dropwise to complete rear continuation stirring 10 minutes, then stirring at low speed is changed into 10 minutes, stop stirring, prepare hydrogen containing polysiloxane emulsion S2(active hydrogen 0.75wt%) 306g.
After 0.5gS-83,0.5gS-85,1gT-83 and 200g water is mixed, be warming up to 50 DEG C, under high-speed stirring, (1500 revs/min) slowly drip hydrogeneous methyl-silicone oil (containing active hydrogen 0.15wt%) 100g respectively, be added dropwise to complete rear continuation stirring 10 minutes, then stirring at low speed is changed into 10 minutes, stop stirring, prepare hydrogen containing polysiloxane emulsion S3(active hydrogen 0.15wt%) 302g.
(2) preparation of glycidyl allyl ether modification hydrogen containing polysiloxane emulsion
After hydrogeneous methyl-silicone oil (active hydrogen 0.75wt%) 100g and 11.4g glycidyl allyl ether is mixed, 0.3g platinum catalyst (the divinyl tetramethyl disiloxane solution of platinum is added under stirring, platinum 1800ppm), be warming up to 50 DEG C, react 3 hours.Cooling, obtain the hydrogeneous poly-tetramethyldisiloxane of 111.4g liquid olefinic propyl glycidyl ether modification, active hydrogen content is measured as 0.6wt%.Get its 100g, then prepare 306g glycidyl allyl ether modification polymethyl siloxane emulsion ES1 according to the method for the above-mentioned S2 of preparation emulsion.
After low hydrogeneous methyl-silicone oil (active hydrogen 0.36wt%) 100g and 20g glycidyl allyl ether is mixed, 0.3g platinum catalyst (the divinyl tetramethyl disiloxane solution of platinum is added under stirring, platinum 1800ppm), be warming up to 60 DEG C, react 3 hours.Cooling, obtain the hydrogeneous poly-tetramethyldisiloxane of 120g liquid olefinic propyl glycidyl ether modification, active hydrogen content is measured as 0.15wt%.Get its 100g, then prepare 306g glycidyl allyl ether modification polymethyl siloxane emulsion ES2 according to the method for the above-mentioned S2 of preparation emulsion.
Example 2: the preparation of acrylate copolymer
(1) preparation of AA emulsion
After methacrylic acid 30g and ethyl propenoate 70g is mixed, slowly be added drop-wise in the 190g aqueous solution containing 2g polyoxyethylene nonylphenol ether (NP-10) and 1g Sodium dodecylbenzene sulfonate under fast stirring, half an hour dropwises, then add the ammonium persulphate of 0.3g, prepare pre-emulsion.Then its 50g is got, joining 10g contains in the aqueous solution of 0.2g ammonium persulphate, stir, warming-in-water to 70 DEG C reaction, starts during blue light to appear to drip remaining pre-emulsion, dropwise in 1 hour, continue to be incubated half an hour, be then warming up to 85 DEG C and be incubated half an hour, cooling, supplement moisture content to 303g, an obtained milk sap P1.
After vinylformic acid 10g, ethyl propenoate 70g, methyl acrylate 10g, butyl methacrylate 10g are mixed, slowly be added drop-wise in the 190g aqueous solution containing 2gNP-10 and 1g Sodium dodecylbenzene sulfonate under fast stirring, half an hour dropwises, then add the Potassium Persulphate of 0.3g, prepare pre-emulsion.Then its 50g is got, joining 10g contains in the aqueous solution of 0.2g Potassium Persulphate, stir, warming-in-water to 70 DEG C reaction, starts during blue light to appear to drip remaining pre-emulsion, dropwise in 1 hour, continue to be incubated half an hour, be then warming up to 85 DEG C and be incubated half an hour, cooling, supplement moisture content to 303g, an obtained milk sap P2.
After vinylformic acid 5g, methacrylic acid 10g, methyl methacrylate 15g, ethyl propenoate 60g, Octyl methacrylate 10g are mixed, slowly be added drop-wise in the 190g aqueous solution containing 2gNP-10 and 1g Sodium dodecylbenzene sulfonate under fast stirring, half an hour dropwises, then add the ammonium persulphate of 0.3g, prepare pre-emulsion.Then its 50g is got, joining 10g contains in the aqueous solution of 0.2g ammonium persulphate, stir, warming-in-water to 70 DEG C reaction, starts during blue light to appear to drip remaining pre-emulsion, dropwise in 1 hour, continue to be incubated half an hour, be then warming up to 85 DEG C and be incubated half an hour, cooling, supplement moisture content to 303g, an obtained milk sap P3.
(2) preparation of acrylic polysiloxane and emulsion thereof
After low hydrogeneous methyl-silicone oil (active hydrogen 0.75wt%) 43g, low hydrogeneous methyl-silicone oil (active hydrogen 0.36wt%) 27g, toluene 100g are mixed with vinylformic acid 30g, 0.3g platinum catalyst (the divinyl tetramethyl disiloxane solution of platinum is added under stirring, platinum 1800ppm), be warming up to 50 DEG C, react 2 hours, be then warming up to 70 DEG C of reactions 1 hour.Underpressure distillation, removing solvent toluene, cooling, obtains 100g not containing the vinylformic acid polymethyl siloxane of activated silica hydrogen bond.Get its 100g, in the water medium of 100g, prepare 202g vinylformic acid polymethyl siloxane latex A S1 according to the method for the above-mentioned S3 of preparation emulsion.
After low hydrogeneous methyl-silicone oil (active hydrogen 0.15wt%) 90g is mixed with vinylformic acid 10g, add 0.3g platinum catalyst (the divinyl tetramethyl disiloxane solution of platinum, platinum 1800ppm) under stirring, be warming up to 60 DEG C, react 2 hours, be then warming up to 70 DEG C of reactions 1 hour.Cooling, obtains 100g not containing the vinylformic acid polymethyl siloxane of activated silica hydrogen bond.Get its 100g, in the water medium of 100g, prepare 202g vinylformic acid polymethyl siloxane latex A S2 according to the method for the above-mentioned S3 of preparation emulsion.
After low hydrogeneous methyl-silicone oil (active hydrogen 0.36wt%) 62g, toluene 100g are mixed with vinylformic acid 10g, allyl polyether (contents of ethylene 7.0wt%) 28g, 0.3g platinum catalyst (the divinyl tetramethyl disiloxane solution of platinum is added under stirring, platinum 1800ppm), be warming up to 50 DEG C, react 2 hours, be then warming up to 70 DEG C of reactions 1 hour.Underpressure distillation, removing solvent toluene, cooling, obtain can the 100g of self-emulsifying containing the vinylformic acid polymethyl siloxane AS3 of activated silica hydrogen bond.
Embodiment 3 ~ 17: the preparation of vinylformic acid organosilicon water milk type coating
The hydrogen containing polysiloxane emulsion obtained according to above-mentioned example 1 ~ 2 and acrylate copolymer prepare vinylformic acid organosilicon water milk type coating by the formula of table 1 respectively, concrete operations are as follows: carry out compound by under hydrogen containing polysiloxane emulsion and acrylate copolymer or its emulsion normal temperature, and supplement corresponding water, obtain corresponding vinylformic acid organosilicon water milk type coating after stirring respectively, wherein each component concentration is in table 2.
Experiment proves, at ambient temperature, hydrogen containing polysiloxane emulsion S1, S2, S3, ES1, ES2 and acrylic polysiloxane latex A S1, AS2, AS3 still stablize after storing 1 year, without floating oil, layering, precipitation, caking, gelatin phenomenon.
The formula table of table 1 vinylformic acid organosilicon water milk type coating
(note: in table in S1, S2, S3, ES1, ES2, AS1, AS2, AS3 before numeral be the weight of this numbered samples)
The component concentration of table 2 vinylformic acid organosilicon water milk type coating
| Embodiment | Water (g) | Emulsifying agent (g) | Hydrogen containing polysiloxane (g) | Acrylate copolymer (g) |
| Example 3 | 100 | 1 | 5 | 5 |
| Example 4 | 100 | 1 | 5 | 50 |
| Example 5 | 100 | 4 | 20 | 50 |
| Example 6 | 100 | 1.2 | 20 | 5 |
| Example 7 | 100 | 0.1 | 5 | 5 |
| Example 8 | 100 | 0.1 | 5 | 50 |
| Example 9 | 100 | 1.1 | 10 | 30 |
| Example 10 | 100 | 0.3 | 5 | 5 |
| Example 11 | 100 | 1.2 | 20 | 5 |
| Example 12 | 100 | 1.2 | 20 | 40 |
| Example 13 | 100 | 0.6 | 10 | 30 |
| Example 14 | 100 | 0.7 | 5 | 50 |
| Example 15 | 100 | 1.2 | 20 | 5 |
| Example 16 | 100 | 0.8 | 20 | 50 |
| Example 17 | 100 | 0.9 | 15 | 30 |
Embodiment 18: the performance index of vinylformic acid organosilicon water milk type coating
Performance measurement is carried out to the vinylformic acid organosilicon water milk type coating that embodiment 1,3 ~ 17 prepares, the results are shown in Table 3.Testing method is as follows:
(1) film-forming properties: the water miscible liquid that embodiment 1,3 ~ 17 prepares is diluted with water to respectively 10% concentration (hydrogen containing polysiloxane and acrylic copolymer total amount), then be coated on the neutral base material sheet glass of dried and clean equably, natural drying at room temperature observes film forming solidification situation for 3 days afterwards.
(2) apparent hydrophobic nature: after the water miscible liquid that embodiment 1,3 ~ 17 prepares being diluted with water to respectively 5% concentration (hydrogen containing polysiloxane and acrylic copolymer total amount), by 150g/m
2consumption be coated in the neutral sandstone surface of porous, drying at room temperature 3 days, then drips the globule with plastic dropper in block faces, keeps 3 minutes and observes the globule in the change in shape of each block faces and inclination landing effect simultaneously.
After separately the water miscible liquid that embodiment 1,3 ~ 17 prepares being diluted with water to 5% concentration (hydrogen containing polysiloxane and acrylic copolymer total amount) respectively, by 70g/m
2consumption be coated in untreated weakly acidic pH base material polished tile surface, drying at room temperature 3 days, then drip the globule with plastic dropper on polished tile surface, keep 5 minutes and the change in shape of the observation globule on each brick surface and inclination landing effect simultaneously.If globule gross distortion or completely dissolve are laid in substrate surface, the globule does not tumble or viscous from the teeth outwards, illustrates that its apparent hydrophobic nature is poor in a large number.If the globule easily tumbles when globule slight deformation or contact surface tilt, illustrate that its apparent hydrophobic nature is good.
(3) alkali resistance: after the water miscible liquid that embodiment 1,3 ~ 17 prepares being diluted with water to respectively 10% concentration (hydrogen containing polysiloxane and acrylic copolymer total amount), by 300g/m
2consumption be coated in alkalescence cement mortar block (cement 100: river sand 2: water 50, room temperature maintenance 28 days) all surfaces, test block submerged after 3 days by drying at room temperature, place and naturally dry afterwards for 7 days, drip 5 seconds in the watering of test block surface continuous spraying, observe the Infiltrating of water droplet at each test block surface.If water droplet enters base material at substrate surface complete wetting, surfacecti proteon is described by dissolved destruction, alkali resistance is poor.
(4) acid rain resistance, weathering resistance: after the water miscible liquid that embodiment 1,3 ~ 17 prepares being diluted with water to respectively 5% concentration (hydrogen containing polysiloxane and acrylic copolymer total amount), by 50g/m
2consumption be coated in granite face, drying at room temperature, after 3 days, is placed on outdoor with inclined-plane miter angle, take out after 6 months, rinse rear natural drying at room temperature well 1 day with water, drip 5 seconds in the watering of block faces continuous spraying, observe the Infiltrating of water droplet in each block faces.If water droplet enters base material at substrate surface complete wetting, surfacecti proteon destroyed is described, acid rain resistance, weathering resistance are poor.
(5) peel test force (with reference to peel test force standard GB/T7122-1996): by standard method coating acrylic-silicone on TESA moral Sha adhesive tape, it be 20mm length is the rectangular of 200mm that adhesive tape shape was cut into width after 3 days by drying at room temperature, with standard pressure roller, adhesive tape is pressed 20 hours (pressure 20g/cm at normal temperatures along length direction on standard stainless steel strip
2), with off-type force test machine test draw speed be 30cm/min, draw angle be 180 ° time drawing force be off-type force.
The performance index of table 3 vinylformic acid organosilicon water milk type coating
From table 3, hydrogen containing polysiloxane emulsion S1 in example 1 and ES1 is when neutral or weakly acidic pH substrate glass, sandstone and untreated polished tile are used alone on the surface, the same with dimethyl polysiloxane emulsion, still in oily after moisture evaporation, can not film-forming.Water droplet molecule accelerates contact close to each other with silicone molecule under gravity, and the globule is disappeared on the sandstone of porous, and gross distortion in polished tile also occurs serious bunching, and apparent hydrophobic effect is poor.In alkaline cement-based material, the Si-O key in pure polysiloxane molecule is subject to OH
-the etch of ion and rupture to decompose and destroy, lose protective effect, it is inner that water molecules immerses the base material losing surfacecti proteon, and strong basicity resisting is not good.
Although organosilicon polymer has excellent ultraviolet-resistant capacity, but in acid rain climatope, fracture is there is and decomposes destruction in the Si-O key in polysiloxane molecule under strongly-acid proton-effect, lose protective effect, water droplet molecule is very fast to spread on the base material losing protective effect, to complete wetting base material, acid rain resistant climatope performance is not good.
The vinylformic acid organosilicon water-latex type composite coating cured at room temperature that example 3 ~ 17 is prepared reticulates structure, and water droplet molecule is not easily at its surface infiltration, and globule distortion is little, and surface hydrophobic lotus leaf effect is obvious.Under strong basicity or acid outdoor environment, reticulated structure is not easily destroyed, and still remains good protective effect, has significant resistance to acids and bases and weathering resistance.
The vinylformic acid organosilicon water-latex type composite coating drying and forming-film performance that embodiment 3 ~ 17 is prepared is good, there is certain surface strength and suitable peeling force, and along with the increase of acrylate copolymer content, surface strength and peeling force increase gradually, be applicable to different stripping demands.And the peeling force of pure organosilicon S1, ES1 is very little, at below 1g/cm.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a vinylformic acid organosilicon water milk type coating, is characterized in that the component comprising following parts by weight: 100 parts, water; Emulsifying agent 0.1 ~ 4 part; Liquid hydrogen containing polysiloxane 5 ~ 20 parts; Acrylate copolymer 5 ~ 50 parts;
Described liquid hydrogen containing polysiloxane refers at least one in hydrogeneous methyl-silicone oil and the hydrogeneous methyl-silicone oil of glycidyl allyl ether Si―H addition reaction modification;
Described acrylate copolymer refers to water-dispersible acrylic polysiloxane;
In described liquid hydrogen containing polysiloxane, the hydrogen richness of activated silica hydrogen bond is 0.15 ~ 1.5wt% of polymethyl siloxane total amount.
2. vinylformic acid organosilicon water milk type coating according to claim 1, is characterized in that: described emulsifying agent refers to the emulsifying agent containing unsaturated double-bond.
3. vinylformic acid organosilicon water milk type coating according to claim 1, is characterized in that: described emulsifying agent refers at least one in sorbitan monooleate and polyoxyethylene sorbitan oleic acid ester; Vinylformic acid in described acrylate copolymer and methacrylic acid unit total content are 10 ~ 30wt% of polymer solids content.
4. vinylformic acid organosilicon water milk type coating according to claim 1, it is characterized in that: described water-dispersible acrylic polysiloxane is prepared by following methods: by vinylformic acid and hydrogeneous methyl-silicone oil and allyl polyether by catalytic addition reaction, obtain water-dispersible acrylic polysiloxane;
Or prepared by following methods: vinylformic acid and hydrogeneous methyl-silicone oil also pass through machinery emulsification method by catalytic addition reaction at 50 ~ 70 DEG C, obtain water-dispersible acrylic polysiloxane.
5. vinylformic acid organosilicon water milk type coating according to claim 3, is characterized in that: described sorbitan monooleate refers at least one in Si Pan-80, Si Pan-83 and Si Pan-85; Described polyoxyethylene sorbitan oleic acid ester refers at least one in tween-80, tween-83 and tween 85.
6. a preparation method for the vinylformic acid organosilicon water milk type coating according to any one of Claims 1 to 5, is characterized in that comprising following concrete steps:
By the mechanical high-speed emulsification at room temperature to 50 DEG C of liquid hydrogen containing polysiloxane, emulsifying agent and water, obtain water-latex type hydrogen containing polysiloxane, mix with under acrylate copolymer room temperature, obtain vinylformic acid organosilicon water milk type coating.
7. the vinylformic acid organosilicon water milk type coating according to any one of Claims 1 to 5 in the surfacecti proteon of construction substrate, the application in the release film of ceramic condenser, wrapping material, release coating, releasing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310385442.8A CN103436125B (en) | 2013-08-29 | 2013-08-29 | A kind of vinylformic acid organosilicon water milk type coating and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310385442.8A CN103436125B (en) | 2013-08-29 | 2013-08-29 | A kind of vinylformic acid organosilicon water milk type coating and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103436125A CN103436125A (en) | 2013-12-11 |
| CN103436125B true CN103436125B (en) | 2015-11-18 |
Family
ID=49689848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310385442.8A Active CN103436125B (en) | 2013-08-29 | 2013-08-29 | A kind of vinylformic acid organosilicon water milk type coating and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103436125B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231918B (en) * | 2014-09-19 | 2016-06-29 | 中科院广州化学有限公司 | The quick-dry type oiliness infiltration nano combined protective agent of film-forming type and preparation method and application |
| CN105732909B (en) * | 2016-04-15 | 2018-02-23 | 武汉赫斯特涂层材料股份有限公司 | A kind of preparation method of acrylic polysiloxane water-based emulsion |
| CN107034675B (en) * | 2017-04-21 | 2019-04-19 | 潍坊佳诚数码材料有限公司 | A kind of preparation method of modified organic silicon textile coating agent |
| CN109293945A (en) * | 2017-07-24 | 2019-02-01 | 疏科纳米疏水科技有限公司 | Environment-friendly type nano hydrophobic lotions and its preparation method and application method |
| CN107686691B (en) * | 2017-09-07 | 2021-01-26 | 福建格林春天新材料股份有限公司 | Water-based acrylic release silicone oil and preparation method and application thereof |
| CN109810252B (en) * | 2018-12-26 | 2021-05-04 | 福建拓烯新材料科技有限公司 | Preparation method of organic silicon resin microemulsion |
| CN112063331A (en) * | 2020-09-24 | 2020-12-11 | 芜湖韩保光学新材料有限公司 | Environment-friendly silica gel protective film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1634934A1 (en) * | 2003-06-13 | 2006-03-15 | Ge Toshiba Silicones Co., Ltd. | Coating composition |
| CN101898902A (en) * | 2009-05-31 | 2010-12-01 | 上海市涂料研究所 | Concrete penetrant capable of being directly applied to wet surface |
| CN102051120A (en) * | 2009-11-03 | 2011-05-11 | 汉高股份有限及两合公司 | Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating |
| CN103242693A (en) * | 2012-02-06 | 2013-08-14 | 纳米及先进材料研发院有限公司 | Multi-functional environmental coating composition with mesoporous silica nanomaterials |
-
2013
- 2013-08-29 CN CN201310385442.8A patent/CN103436125B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1634934A1 (en) * | 2003-06-13 | 2006-03-15 | Ge Toshiba Silicones Co., Ltd. | Coating composition |
| CN101898902A (en) * | 2009-05-31 | 2010-12-01 | 上海市涂料研究所 | Concrete penetrant capable of being directly applied to wet surface |
| CN102051120A (en) * | 2009-11-03 | 2011-05-11 | 汉高股份有限及两合公司 | Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating |
| CN103242693A (en) * | 2012-02-06 | 2013-08-14 | 纳米及先进材料研发院有限公司 | Multi-functional environmental coating composition with mesoporous silica nanomaterials |
Non-Patent Citations (1)
| Title |
|---|
| "低表面能有机硅树脂的改性及研究进展(一)";李学玲等;《中国涂料》;20130131;第28卷(第1期);32-35 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103436125A (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103436125B (en) | A kind of vinylformic acid organosilicon water milk type coating and its preparation method and application | |
| CN104193289B (en) | A kind of hydrophobicity protective coating and preparation method thereof | |
| CN105542644A (en) | Nanometer silica-modified aqueous polyurethane waterproof paint and preparation method thereof | |
| CN101818024B (en) | Aqueous emulsion type organic silicon antifouling paint and preparation method and application thereof | |
| US20080107864A1 (en) | Method of Making a Surface Hydrophobic | |
| CN106675395B (en) | A kind of building surface permeable organic silicon protective agent and preparation method thereof | |
| CN105837112A (en) | Two-component polymer cement waterproof coating | |
| CN111518456B (en) | Permeable waterproof alkali-resistant coating and preparation method thereof | |
| CN110183963A (en) | A kind of graphene oxide-TEOS/ silane composite gel material and its preparation method and application | |
| CN101555385B (en) | Water-reducible silicone coating and preparation method thereof | |
| CN101115696A (en) | Aqueous emulsions of functional alkoxysilanes and condensed oligomers thereof, their preparation and use for surface treatment | |
| CN104231918B (en) | The quick-dry type oiliness infiltration nano combined protective agent of film-forming type and preparation method and application | |
| CN103725141A (en) | Water-based emulsion for protecting external wall of building and preparation method for water-based emulsion | |
| CN103408707A (en) | Amphiphilic crosslinkable fluorosilicon resin, water-borne coating and super-amphiphobic coating prepared through water-borne coating | |
| CN102838319A (en) | Environment-friendly concrete waterproof oil-repellent organic silicon material and preparation method thereof | |
| CN1919889A (en) | Organosilicon epoxide acrylate water dispersion, preparation method and application thereof | |
| CN111100555A (en) | Water-based penetration self-healing high polymer modified asphalt waterproof coating with hydrophobic surface and preparation method and application thereof | |
| CN104559366A (en) | Waterproof architectural paint | |
| CN108300047A (en) | A kind of indoor anti-pollution water-water coating and preparation method thereof | |
| CN109439110A (en) | A kind of high-performance water-based glass wine bottle coating and preparation method thereof | |
| CN105001728A (en) | Organic and inorganic complex finishing varnish | |
| CN106752593A (en) | A kind of safe environment protection type finishing varnish and preparation method thereof | |
| JP2915803B2 (en) | Water-based water-repellent and waterproof coating agent | |
| CN106518160B (en) | A kind of weather-proof semi-permeable type clear-water concrete protective agent and preparation method thereof of breathing freely | |
| CN112029408A (en) | Environment-friendly waterproof coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |